BACKBONE CLEAVABLE POLYMETHACRYLATES VIA THIONOLACTONE COMONOEMERS

Abstract

The present disclosure provides thionolactones (e.g., compounds of Formula II, and tautomers and salts thereof). The thionolactones may be useful as comonomers to copolymerize with other comonomers, e.g., methacrylates (e.g., MMA) to generate copolymers, e.g., random copolymers. The copolymers may be degradable (e.g., backbone degradable). The copolymers may be useful for waste management or biodegradability.

Claims

1. A compound of the Formula II: ##STR00060## or a tautomer or salt thereof, wherein: each instance of R.sup.10 is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, CN, OR.sup.b, SCN, SR.sup.b, SSR.sup.b, N.sub.3, NO, N(R.sup.b).sub.2, NO.sub.2, C(O)R.sup.b, C(O)OR.sup.b, C(O)SR.sup.b, C(O)N(R.sup.b).sub.2, C(NR.sup.b)R.sup.b, C(NR.sup.b)OR.sup.b, C(NR.sup.b)SR.sup.b, C(NR.sup.b)N(R.sup.b).sub.2, S(O)R.sup.b, S(O)OR.sup.b, S(O)SR.sup.b, S(O)N(R.sup.b).sub.2, S(O).sub.2R.sup.b, S(O).sub.2OR.sup.b, S(O).sub.2SR.sup.b, S(O).sub.2N(R.sup.b).sub.2, OC(O)R.sup.b, OC(O)OR.sup.b, OC(O)SR.sup.b, OC(O)N(R.sup.b).sub.2, OC(NR.sup.b)R.sup.b, OC(NR.sup.b)OR.sup.b, OC(NR.sup.b)SR.sup.b, OC(NR.sup.b)N(R.sup.b).sub.2, OS(O)R.sup.b, OS(O)OR.sup.b, OS(O)SR.sup.b, OS(O)N(R.sup.b).sub.2, OS(O).sub.2R.sup.b, OS(O).sub.2OR.sup.b, OS(O).sub.2SR.sup.b, OS(O).sub.2N(R.sup.b).sub.2, ON(R.sup.b).sub.2, SC(O)R.sup.b, SC(O)OR.sup.b, SC(O)SR.sup.b, SC(O)N(R.sup.b).sub.2, SC(NR.sup.b)R.sup.b, SC(NR.sup.b)OR.sup.b, SC(NR.sup.b)SR.sup.b, SC(NR.sup.b)N(R.sup.b).sub.2, NR.sup.bC(O)R.sup.b, NR.sup.bC(O)OR.sup.b, NR.sup.bC(O)SR.sup.b, NR.sup.bC(O)N(R.sup.b).sub.2, NR.sup.bC(NR.sup.b)R.sup.b, NR.sup.bC(NR.sup.b)OR.sup.b, NR.sup.bC(NR.sup.b)SR.sup.b, NR.sup.bC(NR.sup.b)N(R.sup.b).sub.2, NR.sup.bS(O)R.sup.b, NR.sup.bS(O)OR.sup.b, NR.sup.bS(O)SR.sup.b, NR.sup.bS(O)N(R.sup.b).sub.2, NR.sup.bS(O).sub.2R.sup.b, NR.sup.bS(O).sub.2OR.sup.b, NR.sup.bS(O).sub.2SR.sup.b, NR.sup.bS(O).sub.2N(R.sup.b).sub.2, Si(R.sup.b).sub.3, Si(R.sup.b).sub.2OR.sup.b, Si(R.sup.b)(OR.sup.b).sub.2, Si(OR.sup.b).sub.3, OSi(R.sup.b).sub.3, OSi(R.sup.b).sub.2OR.sup.b, OSi(R.sup.b)(OR.sup.b).sub.2, or OSi(OR.sup.b).sub.3; each instance of R.sup.11 is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, CN, OR.sup.b, SCN, SR.sup.b, SSR.sup.b, N.sub.3, NO, N(R.sup.b).sub.2, NO.sub.2, C(O)R.sup.b, C(O)OR.sup.b, C(O)SR.sup.b, C(O)N(R.sup.b).sub.2, C(NR.sup.b)R.sup.b, C(NR.sup.b)OR.sup.b, C(NR.sup.b)SR.sup.b, C(NR.sup.b)N(R.sup.b).sub.2, S(O)R.sup.b, S(O)OR.sup.b, S(O)SR.sup.b, S(O)N(R.sup.b).sub.2, S(O).sub.2R.sup.b, S(O).sub.2OR.sup.b, S(O).sub.2SR.sup.b, S(O).sub.2N(R.sup.b).sub.2, OC(O)R.sup.b, OC(O)OR.sup.b, OC(O)SR.sup.b, OC(O)N(R.sup.b).sub.2, OC(NR.sup.b)R.sup.b, OC(NR.sup.b)OR.sup.b, OC(NR.sup.b)SR.sup.b, OC(NR.sup.b)N(R.sup.b).sub.2, OS(O)R.sup.b, OS(O)OR.sup.b, OS(O)SR.sup.b, OS(O)N(R.sup.b).sub.2, OS(O).sub.2R.sup.b, OS(O).sub.2OR.sup.b, OS(O).sub.2SR.sup.b, OS(O).sub.2N(R.sup.b).sub.2, ON(R.sup.b).sub.2, SC(O)R.sup.b, SC(O)OR.sup.b, SC(O)SR.sup.b, SC(O)N(R.sup.b).sub.2, SC(NR.sup.b)R.sup.b, SC(NR.sup.b)OR.sup.b, SC(NR.sup.b)SR.sup.b, SC(NR.sup.b)N(R.sup.b).sub.2, NR.sup.bC(O)R.sup.b, NR.sup.bC(O)OR.sup.b, NR.sup.bC(O)SR.sup.b, NR.sup.bC(O)N(R.sup.b).sub.2, NR.sup.bC(NR.sup.b)R.sup.b, NR.sup.bC(NR.sup.b)OR.sup.b, NR.sup.bC(NR.sup.b)SR.sup.b, NR.sup.bC(NR.sup.b)N(R.sup.b).sub.2, NR.sup.bS(O)R.sup.b, NR.sup.bS(O)OR.sup.b, NR.sup.bS(O)SR.sup.b, NR.sup.bS(O)N(R.sup.b).sub.2, NR.sup.bS(O).sub.2R.sup.b, NR.sup.bS(O).sub.2OR.sup.b, NR.sup.bS(O).sub.2SR.sup.b, NR.sup.bS(O).sub.2N(R.sup.b).sub.2, Si(R.sup.b).sub.3, Si(R.sup.b).sub.2OR.sup.b, Si(R.sup.b)(OR.sup.b).sub.2, Si(OR.sup.b).sub.3, OSi(R.sup.b).sub.3, OSi(R.sup.b).sub.2OR.sup.b, OSi(R.sup.b)(OR.sup.b).sub.2, or OSi(OR.sup.b).sub.3; each instance of R.sup.b is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; each of n3 and n4 is independently 0, 1, 2, 3, or 4; R.sup.18 is substituted or unsubstituted aryl, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, or substituted or unsubstituted heteroaryl; and R.sup.19 is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; provided that no instance of R.sup.10, R.sup.11, R.sup.18, and R.sup.19 comprises one or more non-aromatic unsaturated CC bonds.

2. The compound of claim 1, or a tautomer or salt thereof, wherein the compound is of the formula: ##STR00061##

3. The compound of claim 1, or a tautomer or salt thereof, wherein the compound is of the formula: ##STR00062##

4. The compound of claim 1, or a tautomer or salt thereof, wherein n3 is 1.

5. The compound of claim 1, or a tautomer or salt thereof, wherein n3 is 0.

6-19. (canceled)

20. The compound of claim 1, wherein the compound is of the formula: ##STR00063## or a tautomer or salt thereof.

21. The compound of claim 1, wherein the compound is of the formula: ##STR00064## or a tautomer or salt thereof.

22. The compound of claim 1, wherein the compound is of the formula: ##STR00065## or a tautomer or salt thereof.

23-93. (canceled)

94. The compound of claim 2, or a tautomer or salt thereof, wherein n3 is 1.

95. The compound of claim 2, or a tautomer or salt thereof, wherein n3 is 0.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0109] The figures are exemplary and do not limit the scope of the present disclosure.

[0110] FIG. 1 shows DFT calculations for MMA radical addition to thionolactone (DOT) derivative showing that TS2 is rate-limiting step.

[0111] FIG. 2 shows stabilizing TS2 with benzylic functional groups should lower the barrier to copolymerization. The effect of benzylic substituent(s) on the energy profile was evaluated using DFT calculations. The calculations employed the wB97X-D3/def2-DZVP level of theory, and the electronic energies of all optimized structures were reevaluated using wB97X-D3/def2-TZVP.

[0112] FIG. 3 shows synthesis of F-p-CF.sub.3PhDOT: a thionolactone with benzylic substitution.

[0113] FIG. 4 shows synthesis of PFPhDOT: another thionolactone with benzylic substitution.

[0114] FIG. 5 shows kinetic experiments for various benzylic PhDOT derivatives showing consumption of both DOT and MMA. Derivatives depicted are 10% PhDOT, 10% p-MePhDOT, 10% p-FPhDOT, 10% Me-p-CF.sub.3PhDOT, 10% p-CF.sub.3PhDOT.

[0115] FIG. 6 shows kinetic experiments for various benzylic PhDOT derivatives showing consumption of both DOT and MMA. Derivatives depicted are 10% F-p-CF.sub.3PhDOT and 10% PFPhDOT.

[0116] FIG. 7 shows that Meyer-Lowry fitting of the low-conversion kinetic data gives reactivity ratios.

[0117] FIG. 8 shows that F-p-CF.sub.3PhDOT copolymerizes with MMA under bulk free radical conditions (SEC data).

[0118] FIG. 9 shows that copolymers of F-p-CF.sub.3PhDOT with MMA are degradable as shown by SEC.

[0119] FIG. 10 shows that fragment size of F-p-CF.sub.3PhDOT with MMA copolymer degradation depends on DOT loading.

[0120] FIG. 11 shows that F-p-CF.sub.3PhDOT with MMA copolymers degrades in the presence of propylamine; PMMA does not.

[0121] FIG. 12 shows similar findings for PFPhDOT with MMA.

[0122] FIG. 13 shows further similar findings for PFPhDOT with MMA.

[0123] FIG. 14 shows similar findings for PFPhDOT with MMA.

[0124] FIG. 15 shows similar findings for PFPhDOT with MMA.

[0125] FIG. 16 shows that PMMA crosslinked networks with thionolactone are dissolvable with propylamine.

[0126] FIGS. 17A and 17B. FIG. 17A shows Monte Carlo simulation evaluating the dependence of the efficiency of CCs on reactivity ratios. The simulations were done assuming 2.5% CC loading and a degree of polymerization (DP) of 1,000. The colors reflect the size of the degraded fragments relative to the size of the original polymer. Regions I-V represent different reactivity ratio scenarios. FIG. 17B shows examples of simulated polymer sequences for Regions I-V: the horizontal black lines represent the polymers, grown from left to right; the vertical lines indicate the positions of CCs on the polymer chain.

[0127] FIG. 18 shows that a relative Gibbs free energy profile for an MMA radical reacting with either MMA or DOT was calculated in order to model the homopropagation and crosspropagation of a chain ending with MMA.

[0128] FIGS. 19A to 19D show synthetic routes which have been developed to synthesize bDOTs with either (FIG. 19A) one or (FIG. 19B) two functional groups at the benzylic position (indicated by a circle marked with an asterisk). Simultaneous functionalization of the aryl ring (circles with no asterisk) can be achieved using appropriate starting materials. FIG. 19C shows overall yields of bDOT synthesis. FIG. 19D shows the copolymerization reactivity of the bDOTs with MMA was measured under RAFT conditions. F.sub.bDOT values were determined by comparing the integrations of the aromatic CH peaks with the MMA OCH.sub.3 peaks in .sup.1H NMR spectra. Molar masses were determined by analytical SEC and referenced against PMMA standards.

[0129] FIGS. 20A to 20C. FIG. 20A shows a series of bDOTs which were synthesized for the optimization of copolymerization reactivity. FIG. 20B shows that the conversion of the monomers was measured over time using quantitative .sup.1H NMR. FIG. 20C shows reactivity ratios which were determined by fitting the conversion data to the Meyer-Lowry equation.

[0130] FIG. 21 shows that Monte Carlo simulation evaluates the effectiveness of aryl bDOTs as CCs. The heat map generated from the simulation visualizes the ratio of degraded fragment size to copolymer size as a function of reactivity ratios, at a 2.5 mol % CC loading for DP 1000 copolymers.

[0131] FIGS. 22A to 22C. FIG. 22A shows that bulk free-radical copolymerization of MMA and F-p-CF.sub.3PhDOT yields copolymers with variable composition, termed dPMMA(f.sub.bDOT). These copolymers were evaluated for their degradation into OMMA(f.sub.bDOT) under an aminolysis condition. FIG. 22B shows NMR spectra of the copolymers. F.sub.bDOT values were determined by comparing the integrations of the aromatic CH peaks (indicated by dashed rectangle) and MMA OCH.sub.3 peaks (indicated by dotted circle). The integrations are shown below each spectrum. FIG. 22C shows SEC traces and M.sub.n,SEC for vPMMA, dPMMA(f.sub.bDOT), and OMMA(f.sub.bDOT). Molar masses from SEC were referenced to PMMA standards.

[0132] FIGS. 23A to 23C. FIG. 23A shows DSC traces from the second heating ramp at 10 C./minute. FIG. 23B shows TGA traces acquired at 10 C./minute. FIG. 23C shows DMA temperature sweeps at constant amplitude and frequency.

[0133] FIGS. 24A to 24B show Mulliken spin population analysis of TS-D2 for DOT. FIG. 24A shows CYLview visualization displaying spin populations of heavy atoms. Spin populations on hydrogen atoms are omitted for clarity. FIG. 24B shows a cartoon representation; the areas of the circles are proportional to the spin population on each atom. The circles outlined with a dotted line are positive; the circles with no outline are negative.

[0134] FIG. 25 shows a summary of the synthesis of MeDOT and PhDOT.

[0135] FIG. 26 shows a summary of the synthesis of Me.sub.2DOT.

[0136] FIG. 27 shows a summary of the synthesis of p-MePhDOT.

[0137] FIG. 28 shows a summary of the synthesis of p-CF.sub.3PhDOT.

[0138] FIG. 29 shows a summary of the synthesis of F-p-CF.sub.3PhDOT.

[0139] FIG. 30 shows a summary of the synthesis of PFPhDOT.

[0140] FIGS. 31A to 31B show conversion measured versus reaction time for the copolymerization of (FIG. 31A) MeDOT or (FIG. 31B) Me.sub.2DOT with MMA.

[0141] FIG. 32 shows conversion measured over reaction time for the copolymerization of PhDOT and MMA.

[0142] FIG. 33 shows .sup.1H NMR (400 MHz, CDCl.sub.3) of P(MMA-co-PhDOT).

[0143] FIG. 34 shows .sup.13C{.sup.1H} NMR (101 MHz, CDCl.sub.3) of P(MMA-co-PhDOT).

[0144] FIG. 35 shows a contour plot of a .sup.1H-.sup.13C HSQC NMR spectrum of P(MMA-co-PhDOT).

[0145] FIG. 36 shows SEC analysis of the purified polymers (A) and the fragments post-degradation (B). The molecular weights and dispersities of the polymers are summarized in Table 2. The traces have been normalized based on their respective areas.

[0146] FIG. 37 shows a control deconstruction experiment using vPMMA.

[0147] FIG. 38 shows screening for deconstruction conditions using dPMMA(2.5): All aminolysis conditions resulted in deconstructed fragments with the same molecular weight distribution.

[0148] FIGS. 39A to 39B show .sup.1H NMR analysis for the evaluation of deconstructed fragments.

[0149] FIG. 40 shows monomer conversions measured at different timepoints for bulk free-radical copolymerization of F-p-CF.sub.3PhDOT and MMA.

[0150] FIG. 41 shows a comparison of the performance of bDOTs (PhDOT and F-p-CF.sub.3PhDOT) as CCs in bulk free-radical copolymerizations.

[0151] FIG. 42 shows synthesis and deconstruction of dPMMA using AIBN as an initiator.

[0152] FIG. 43 shows a graphical overview depicting copolymerization and deconstruction.

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS OF THE PRESENT DISCLOSURE

[0153] In one aspect, the present disclosure provides a compound of the Formula II:

##STR00005##

or a tautomer or salt thereof, wherein: [0154] each instance of R.sup.10 is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, CN, OR.sup.b, SCN, SR.sup.b, SSR.sup.b, N.sub.3, NO, N(R.sup.b).sub.2, NO.sub.2, C(O)R.sup.b, C(O)OR.sup.b, C(O)SR.sup.b, C(O)N(R.sup.b).sub.2, C(NR.sup.b)R.sup.b, C(NR.sup.b)OR.sup.b, C(NR.sup.b)SR.sup.b, C(NR.sup.b)N(R.sup.b).sub.2, S(O)R.sup.b, S(O)OR.sup.b, S(O)SR.sup.b, S(O)N(R.sup.b).sub.2, S(O).sub.2R.sup.b, S(O).sub.2OR.sup.b, S(O).sub.2SR.sup.b, S(O).sub.2N(R.sup.b).sub.2, OC(O)R.sup.b, OC(O)OR.sup.b, OC(O)SR.sup.b, OC(O)N(R.sup.b).sub.2, OC(NR.sup.b)R.sup.b, OC(NR.sup.b)OR.sup.b, OC(NR.sup.b)SR.sup.b, OC(NR.sup.b)N(R.sup.b).sub.2, OS(O)R.sup.b, OS(O)OR.sup.b, OS(O)SR.sup.b, OS(O)N(R.sup.b).sub.2, OS(O).sub.2R.sup.b, OS(O).sub.2OR.sup.b, OS(O).sub.2SR.sup.b, OS(O).sub.2N(R.sup.b).sub.2, ON(R.sup.b).sub.2, SC(O)R.sup.b, SC(O)OR.sup.b, SC(O)SR.sup.b, SC(O)N(R.sup.b).sub.2, SC(NR.sup.b)R.sup.b, SC(NR.sup.b)OR.sup.b, SC(NR.sup.b)SR.sup.b, SC(NR.sup.b)N(R.sup.b).sub.2, NR.sup.bC(O)R.sup.b, NR.sup.bC(O)OR.sup.b, NR.sup.bC(O)SR.sup.b, NR.sup.bC(O)N(R.sup.b).sub.2, NR.sup.bC(NR.sup.b)R.sup.b, NR.sup.bC(NR.sup.b)OR.sup.b, NR.sup.bC(NR.sup.b)SR.sup.b, NR.sup.bC(NR.sup.b)N(R.sup.b).sub.2, NR.sup.bS(O)R.sup.b, NR.sup.bS(O)OR.sup.b, NR.sup.bS(O)SR.sup.b, NR.sup.bS(O)N(R.sup.b).sub.2, NR.sup.bS(O).sub.2R.sup.b, NR.sup.bS(O).sub.2OR.sup.b, NR.sup.bS(O).sub.2SR.sup.b, NR.sup.bS(O).sub.2N(R.sup.b).sub.2, Si(R.sup.b).sub.3, Si(R.sup.b).sub.2OR.sup.b, Si(R.sup.b)(OR.sup.b).sub.2, Si(OR.sup.b).sub.3, OSi(R.sup.b).sub.3, OSi(R.sup.b).sub.2OR.sup.b, OSi(R.sup.b)(OR.sup.b).sub.2, or OSi(OR.sup.b).sub.3; [0155] each instance of R.sup.11 is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, CN, OR.sup.b, SCN, SR.sup.b, SSR.sup.b, N.sub.3, NO, N(R.sup.b).sub.2, NO.sub.2, C(O)R.sup.b, C(O)OR.sup.b, C(O)SR.sup.b, C(O)N(R.sup.b).sub.2, C(NR.sup.b)R.sup.b, C(NR.sup.b)OR.sup.b, C(NR.sup.b)SR.sup.b, C(NR.sup.b)N(R.sup.b).sub.2, S(O)R.sup.b, S(O)OR.sup.b, S(O)SR.sup.b, S(O)N(R.sup.b).sub.2, S(O).sub.2R.sup.b, S(O).sub.2OR.sup.b, S(O).sub.2SR.sup.b, S(O).sub.2N(R.sup.b).sub.2, OC(O)R.sup.b, OC(O)OR.sup.b, OC(O)SR.sup.b, OC(O)N(R.sup.b).sub.2, OC(NR.sup.b)R.sup.b, OC(NR.sup.b)OR.sup.b, OC(NR.sup.b)SR.sup.b, OC(NR.sup.b)N(R.sup.b).sub.2, OS(O)R.sup.b, OS(O)OR.sup.b, OS(O)SR.sup.b, OS(O)N(R.sup.b).sub.2, OS(O).sub.2R.sup.b, OS(O).sub.2OR.sup.b, OS(O).sub.2SR.sup.b, OS(O).sub.2N(R.sup.b).sub.2, ON(R.sup.b).sub.2, SC(O)R.sup.b, SC(O)OR.sup.b, SC(O)SR.sup.b, SC(O)N(R.sup.b).sub.2, SC(NR.sup.b)R.sup.b, SC(NR.sup.b)OR.sup.b, SC(NR.sup.b)SR.sup.b, SC(NR.sup.b)N(R.sup.b).sub.2, NR.sup.bC(O)R.sup.b, NR.sup.bC(O)OR.sup.b, NR.sup.bC(O)SR.sup.b, NR.sup.bC(O)N(R.sup.b).sub.2, NR.sup.bC(NR.sup.b)R.sup.b, NR.sup.bC(NR.sup.b)OR.sup.b, NR.sup.bC(NR.sup.b)SR.sup.b, NR.sup.bC(NR.sup.b)N(R.sup.b).sub.2, NR.sup.bS(O)R.sup.b, NR.sup.bS(O)OR.sup.b, NR.sup.bS(O)SR.sup.b, NR.sup.bS(O)N(R.sup.b).sub.2, NR.sup.bS(O).sub.2R.sup.b, NR.sup.bS(O).sub.2OR.sup.b, NR.sup.bS(O).sub.2SR.sup.b, NR.sup.bS(O).sub.2N(R.sup.b).sub.2, Si(R.sup.b).sub.3, Si(R.sup.b).sub.2OR.sup.b, Si(R.sup.b)(OR.sup.b).sub.2, Si(OR.sup.b).sub.3, OSi(R.sup.b).sub.3, OSi(R.sup.b).sub.2OR.sup.b, OSi(R.sup.b)(OR.sup.b).sub.2, or OSi(OR.sup.b).sub.3; [0156] each instance of R.sup.b is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; [0157] each of n3 and n4 is independently 0, 1, 2, 3, or 4; [0158] R.sup.18 is substituted or unsubstituted aryl, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, or substituted or unsubstituted heteroaryl; and [0159] R.sup.19 is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; [0160] provided that no instance of R.sup.10, R.sup.11, R.sup.18, and R.sup.19 comprises one or more non-aromatic unsaturated CC bonds.

[0161] In certain embodiments, the compound is of the formula:

##STR00006##

[0162] In certain embodiments, the compound is of the formula:

##STR00007##

[0163] In certain embodiments, the compound is of the formula:

##STR00008##

[0164] In certain embodiments, the compound is of the formula:

##STR00009##

[0165] In certain embodiments, the compound is of the formula:

##STR00010##

[0166] In certain embodiments, the compound is of the formula:

##STR00011##

[0167] In certain embodiments, the compound is of the formula:

##STR00012##

[0168] In certain embodiments, n3 is 1. In certain embodiments, n3 is 0.

[0169] In certain embodiments, n4 is 0. In certain embodiments, n4 is 1.

[0170] In certain embodiments, at least one of n3 and n4 is 1, 2, 3, or 4. In certain embodiments, at least one of n3 and n4 is 1. In certain embodiments, each of n3 and n4 is 1, 2, 3, or 4. In certain embodiments, each of n3 and n4 is 1.

[0171] In certain embodiments, at least one is two. In certain embodiments, at least one instance is two instances. In certain embodiments, at least one is each. In certain embodiments, at least one instance is each instance. In certain embodiments, two or more instances of the same moiety (e.g., R.sup.10, R.sup.11, R.sup.a, R.sup.b, or R.sup.c) are the same as each other. In certain embodiments, two or more instances of the same moiety are different from each other.

[0172] In certain embodiments, at least one instance of R.sup.10 or R.sup.11 is an electron-withdrawing group. In certain embodiments, at least one instance of R.sup.10 or R.sup.11 is more electron-withdrawing than H. In certain embodiments, at least one instance of R.sup.10 or R.sup.11 is not more electron-withdrawing than CF.sub.3.

[0173] In certain embodiments, at least one instance of R.sup.10 or R.sup.11 is halogen, preferably, fluoro. In certain embodiments, at least one instance of R.sup.10 or R.sup.11 is Cl. In certain embodiments, at least one instance of R.sup.10 or R.sup.11 is halogen, substituted or unsubstituted, C.sub.1-6 alkyl, OR.sup.aa, SR.sup.aa, N(R.sup.cc).sub.2, CN, SCN, NO.sub.2, C(O)R.sup.aa, C(O)OR.sup.aa, C(O)N(R.sup.c).sub.2, OC(O)R.sup.aa, OC(O)OR.sup.c, OC(O)N(R.sup.c).sub.2, NR.sup.cC(O)R.sup.aa, NR.sup.cC(O)OR.sup.aa, or NR.sup.cC(O)N(R.sup.c).sub.2, wherein each instance of R.sup.c is independently hydrogen or substituted or unsubstituted C.sub.1-6 alkyl. In certain embodiments, at least one instance of R.sup.10 or R.sup.11 is halogen, CN, SCN, NO.sub.2, C(O)R.sup.c, C(O)OR.sup.aa, C(O)N(R.sup.c).sub.2, OC(O)R.sup.aa, OC(O)OR.sup.aa, OC(O)N(R.sup.c), NR.sup.cC(O)R.sup.c, NR.sup.cC(O)OR.sup.c, NR.sup.cC(O)N(R.sup.c).sub.2, or C.sub.1-6 alkyl substituted with one or more halogen, wherein each instance of R.sup.c is independently hydrogen or substituted or unsubstituted C.sub.1-6 alkyl. In certain embodiments, at least one instance of R.sup.10 or R.sup.11 is substituted or unsubstituted alkyl, O(substituted or unsubstituted alkyl), or S(substituted or unsubstituted alkyl). In certain embodiments, at least one instance of R.sup.10 or R.sup.11 is unsubstituted C.sub.1-6 alkyl, C.sub.1-6 alkyl substituted with one or more fluoro, O(unsubstituted C.sub.1-6 alkyl), O(C.sub.1-6 alkyl substituted with one or more fluoro), S(unsubstituted C.sub.1-6 alkyl), or S(C.sub.1-6 alkyl substituted with one or more fluoro). In certain embodiments, at least one instance of R.sup.10 or R.sup.11 is CH.sub.3. In certain embodiments, at least one instance of R.sup.10 or R.sup.11 is CH.sub.2F, CHF.sub.2, or CF.sub.3. In certain embodiments, at least one instance of R.sup.10 or R.sup.11 is CN.

[0174] In certain embodiments, R.sup.18 is substituted or unsubstituted aryl. In certain embodiments, R.sup.18 is substituted or unsubstituted phenyl. In certain embodiments, R.sup.18 is unsubstituted phenyl. In certain embodiments, R.sup.18 is para-monosubstituted phenyl. In certain embodiments, R.sup.18 is ortho-monosubstituted phenyl. In certain embodiments, R.sup.18 is meta-monosubstituted phenyl. In certain embodiments, R.sup.18 is polysubstituted phenyl. In certain embodiments, R.sup.18 is disubstituted phenyl. In certain embodiments, R.sup.18 is persubstituted phenyl. In certain embodiments, R.sup.18 is unsubstituted phenyl or phenyl substituted with one or more: halogen, substituted or unsubstituted, C.sub.1-6 alkyl, OR.sup.c, SR.sup.c, N(R.sup.c).sub.2, CN, SCN, NO.sub.2, C(O)R.sup.c, C(O)OR.sup.c, C(O)N(R.sup.c).sub.2, OC(O)R.sup.c, OC(O)OR.sup.c, OC(O)N(R.sup.c).sub.2, NR.sup.cC(O)R.sup.c, NR.sup.cC(O)OR.sup.c, and/or NR.sup.cC(O)N(R.sup.c).sub.2, wherein each instance of R.sup.c is independently hydrogen or substituted or unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.18 is unsubstituted phenyl or phenyl substituted with one or more: halogen, CN, SCN, NO.sub.2, C(O)R.sup.c, C(O)OR.sup.c, C(O)N(R.sup.c).sub.2, OC(O)R.sup.c, OC(O)OR.sup.c, OC(O)N(R.sup.c).sub.2, NR.sup.cC(O)R.sup.c, NR.sup.cC(O)OR.sup.c, NR.sup.cC(O)N(R.sup.c).sub.2, and/or C.sub.1-6 alkyl substituted with one or more halogen, wherein each instance of R.sup.c is independently hydrogen or substituted or unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.18 is unsubstituted phenyl or phenyl substituted with one or more: halogen, unsubstituted C.sub.1-6 alkyl, and/or C.sub.1-6 alkyl substituted with one or more fluoro. In certain embodiments, R.sup.18 is fluoro phenyl, difluoro phenyl, or trifluoro phenyl. In certain embodiments, R.sup.18 is (trifluoromethyl) phenyl. In certain embodiments, R.sup.18 is para-(trifluoromethyl) phenyl. In certain embodiments, R.sup.18 is (fluoromethyl) phenyl or (difluoromethyl) phenyl. In certain embodiments, R.sup.18 is substituted phenyl and is more electron-withdrawing than unsubstituted phenyl. In certain embodiments, R.sup.18 is substituted phenyl and is not more electron-withdrawing than perfluorophenyl.

[0175] In certain embodiments, R.sup.18 is substituted or unsubstituted alkyl. In certain embodiments, R.sup.18 is unsubstituted C.sub.1-6 alkyl or C.sub.1-6 alkyl substituted with one or more fluoro. In certain embodiments, R.sup.18 is CH.sub.3. In certain embodiments, R.sup.18 is CH.sub.2F, CHF.sub.2, or CF.sub.3.

[0176] In certain embodiments, R.sup.19 is hydrogen. In certain embodiments, R.sup.19 is substituted or unsubstituted alkyl. In certain embodiments, R.sup.19 is unsubstituted C.sub.1-6 alkyl or C.sub.1-6 alkyl substituted with one or more fluoro. In certain embodiments, R.sup.19 is unsubstituted C.sub.1-6 alkyl or C.sub.1-6 alkyl substituted with one or more fluoro. In certain embodiments, R.sup.19 is CH.sub.3. In certain embodiments, R.sup.18 is CH.sub.2F, CHF.sub.2, or CF.sub.3.

[0177] In certain embodiments, the carbon atom to which R.sup.18 is attached is in the R configuration. In certain embodiments, the carbon atom to which R.sup.18 is attached is in the S configuration.

[0178] In certain embodiments, the compound is of the formula:

##STR00013##

or a tautomer or salt thereof.

[0179] In certain embodiments, the compound is of the formula:

##STR00014##

or a tautomer or salt thereof.

[0180] In certain embodiments, the compound is of the formula:

##STR00015##

or a tautomer or salt thereof.

[0181] In another aspect, the present disclosure provides a copolymer comprising: [0182] m1 instances of a first type of repeating units of Formula i:

##STR00016## [0183] m2 instances of a second type of repeating units of Formula ii:

##STR00017##

or a tautomer thereof; [0184] optionally one or more types of crosslinking units; and [0185] optionally one or more types of additional repeating units; [0186] wherein: [0187] m1 is an integer between 10 and 1,000,000, inclusive; [0188] m2 is an integer between 2 and 1,000,000, inclusive; [0189] R.sup.1, R.sup.2, and R.sup.3 are each independently hydrogen, halogen, or substituted or unsubstituted alkyl; [0190] R.sup.4 is C(O)OR.sup.a, C(O)N(R.sup.a).sub.2, substituted or unsubstituted alkyl, halogen, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, CN, OR.sup.a, SCN, SR.sup.a, SSR.sup.a, N.sub.3, NO, N(R.sup.a).sub.2, NO.sub.2, C(O)R.sup.a, C(O)SR.sup.a, C(NR.sup.a)R.sup.a, C(NR.sup.a)OR.sup.a, C(NR.sup.a)SR.sup.a, C(NR.sup.a)N(R.sup.a).sub.2, S(O)R.sup.a, S(O)OR.sup.a, S(O)SR.sup.a, S(O)N(R.sup.a).sub.2, S(O).sub.2R.sup.a, S(O).sub.2OR.sup.a, S(O).sub.2SR.sup.a, S(O).sub.2N(R.sup.a).sub.2, OC(O)R.sup.a, OC(O)OR.sup.a, OC(O)SR.sup.a, OC(O)N(R.sup.a).sub.2, OC(NR.sup.a)R.sup.a, OC(NR.sup.a)OR.sup.a, OC(NR.sup.a)SR.sup.a, OC(NR.sup.a)N(R.sup.a).sub.2, OS(O)R.sup.a, OS(O)OR.sup.a, OS(O)SR.sup.a, OS(O)N(R.sup.a).sub.2, OS(O).sub.2R.sup.a, OS(O).sub.2OR.sup.a, OS(O).sub.2SR.sup.a, OS(O).sub.2N(R.sup.a).sub.2, ON(R.sup.a).sub.2, SC(O)R.sup.a, SC(O)OR.sup.a, SC(O)SR.sup.a, SC(O)N(R.sup.a).sub.2, SC(NR.sup.a)R.sup.a, SC(NR.sup.a)OR.sup.a, SC(NR.sup.a)SR.sup.a, SC(NR.sup.a)N(R.sup.a).sub.2, NR.sup.aC(O)R.sup.a, NR.sup.aC(O)OR.sup.a, NR.sup.aC(O)SR.sup.a, NR.sup.aC(O)N(R.sup.a).sub.2, NR.sup.aC(NR.sup.a)R.sup.a, NR.sup.aC(NR.sup.a)OR.sup.a, NR.sup.aC(NR.sup.a)SR.sup.a, NR.sup.aC(NR.sup.a)N(R.sup.a).sub.2, NR.sup.aS(O)R.sup.a, NR.sup.aS(O)OR.sup.a, NR.sup.aS(O)SR.sup.a, NR.sup.aS(O)N(R.sup.a).sub.2, NR.sup.aS(O).sub.2R.sup.a, NR.sup.aS(O).sub.2OR.sup.a, NR.sup.aS(O).sub.2SR.sup.a, NR.sup.aS(O).sub.2N(R.sup.a).sub.2, Si(R.sup.a).sub.3, Si(R.sup.a).sub.2OR.sup.a, Si(R.sup.a)(OR.sup.a).sub.2, Si(OR.sup.a).sub.3, OSi(R.sup.a).sub.3, OSi(R.sup.a).sub.2OR.sup.a, OSi(R.sup.a)(OR.sup.a).sub.2, or OSi(OR.sup.a).sub.3; [0191] each instance of R.sup.a is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; [0192] each instance of R.sup.10 is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, CN, OR.sup.b, SCN, SR.sup.b, SSR.sup.b, N.sub.3, NO, N(R.sup.b).sub.2, NO.sub.2, C(O)R.sup.b, C(O)OR.sup.b, C(O)SR.sup.b, C(O)N(R.sup.b).sub.2, C(NR.sup.b)R.sup.b, C(NR.sup.b)OR.sup.b, C(NR.sup.b)SR.sup.b, C(NR.sup.b)N(R.sup.b).sub.2, S(O)R.sup.b, S(O)OR.sup.b, S(O)SR.sup.b, S(O)N(R.sup.b).sub.2, S(O).sub.2R.sup.b, S(O).sub.2OR.sup.b, S(O).sub.2SR.sup.b, S(O).sub.2N(R.sup.b).sub.2, OC(O)R.sup.b, OC(O)OR.sup.b, OC(O)SR.sup.b, OC(O)N(R.sup.b).sub.2, OC(NR.sup.b)R.sup.b, OC(NR.sup.b)OR.sup.b, OC(NR.sup.b)SR.sup.b, OC(NR.sup.b)N(R.sup.b).sub.2, OS(O)R.sup.b, OS(O)OR.sup.b, OS(O)SR.sup.b, OS(O)N(R.sup.b).sub.2, OS(O).sub.2R.sup.b, OS(O).sub.2OR.sup.b, OS(O).sub.2SR.sup.b, OS(O).sub.2N(R.sup.b).sub.2, ON(R.sup.b).sub.2, SC(O)R.sup.b, SC(O)OR.sup.b, SC(O)SR.sup.b, SC(O)N(R.sup.b).sub.2, SC(NR.sup.b)R.sup.b, SC(NR.sup.b)OR.sup.b, SC(NR.sup.b)SR.sup.b, SC(NR.sup.b)N(R.sup.b).sub.2, NR.sup.bC(O)R.sup.b, NR.sup.bC(O)OR.sup.b, NR.sup.bC(O)SR.sup.b, NR.sup.bC(O)N(R.sup.b).sub.2, NR.sup.bC(NR.sup.b)R.sup.b, NR.sup.bC(NR.sup.b)OR.sup.b, NR.sup.bC(NR.sup.b)SR.sup.b, NR.sup.bC(NR.sup.b)N(R.sup.b).sub.2, NR.sup.bS(O)R.sup.b, NR.sup.bS(O)OR.sup.b, NR.sup.bS(O)SR.sup.b, NR.sup.bS(O)N(R.sup.b).sub.2, NR.sup.bS(O).sub.2R.sup.b, NR.sup.bS(O).sub.2OR.sup.b, NR.sup.bS(O).sub.2SR.sup.b, NR.sup.bS(O).sub.2N(R.sup.b).sub.2, Si(R.sup.b).sub.3, Si(R.sup.b).sub.2OR.sup.b, Si(R.sup.b)(OR.sup.b).sub.2, Si(OR.sup.b).sub.3, OSi(R.sup.b).sub.3, OSi(R.sup.b).sub.2OR.sup.b, OSi(R.sup.b)(OR.sup.b).sub.2, or OSi(OR.sup.b).sub.3; [0193] each instance of R.sup.11 is independently halogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, CN, OR.sup.b, SCN, SR.sup.b, SSR.sup.b, N.sub.3, NO, N(R.sup.b).sub.2, NO.sub.2, C(O)R.sup.b, C(O)OR.sup.b, C(O)SR.sup.b, C(O)N(R.sup.b).sub.2, C(NR.sup.b)R.sup.b, C(NR.sup.b)OR.sup.b, C(NR.sup.b)SR.sup.b, C(NR.sup.b)N(R.sup.b).sub.2, S(O)R.sup.b, S(O)OR.sup.b, S(O)SR.sup.b, S(O)N(R.sup.b).sub.2, S(O).sub.2R.sup.b, S(O).sub.2OR.sup.b, S(O).sub.2SR.sup.b, S(O).sub.2N(R.sup.b).sub.2, OC(O)R.sup.b, OC(O)OR.sup.b, OC(O)SR.sup.b, OC(O)N(R.sup.b).sub.2, OC(NR.sup.b)R.sup.b, OC(NR.sup.b)OR.sup.b, OC(NR.sup.b)SR.sup.b, OC(NR.sup.b)N(R.sup.b).sub.2, OS(O)R.sup.b, OS(O)OR.sup.b, OS(O)SR.sup.b, OS(O)N(R.sup.b).sub.2, OS(O).sub.2R.sup.b, OS(O).sub.2OR.sup.b, OS(O).sub.2SR.sup.b, OS(O).sub.2N(R.sup.b).sub.2, ON(R.sup.b).sub.2, SC(O)R.sup.b, SC(O)OR.sup.b, SC(O)SR.sup.b, SC(O)N(R.sup.b).sub.2, SC(NR.sup.b)R.sup.b, SC(NR.sup.b)OR.sup.b, SC(NR.sup.b)SR.sup.b, SC(NR.sup.b)N(R.sup.b).sub.2, NR.sup.bC(O)R.sup.b, NR.sup.bC(O)OR.sup.b, NR.sup.bC(O)SR.sup.b, NR.sup.bC(O)N(R.sup.b).sub.2, NR.sup.bC(NR.sup.b)R.sup.b, NR.sup.bC(NR.sup.b)OR.sup.b, NR.sup.bC(NR.sup.b)SR.sup.b, NR.sup.bC(NR.sup.b)N(R.sup.b).sub.2, NR.sup.bS(O)R.sup.b, NR.sup.bS(O)OR.sup.b, NR.sup.bS(O)SR.sup.b, NR.sup.bS(O)N(R.sup.b).sub.2, NR.sup.bS(O).sub.2R.sup.b, NR.sup.bS(O).sub.2OR.sup.b, NR.sup.bS(O).sub.2SR.sup.b, NR.sup.bS(O).sub.2N(R.sup.b).sub.2, Si(R.sup.b).sub.3, Si(R.sup.b).sub.2OR.sup.b, Si(R.sup.b)(OR.sup.b).sub.2, Si(OR.sup.b).sub.3, OSi(R.sup.b).sub.3, OSi(R.sup.b).sub.2OR.sup.b, OSi(R.sup.b)(OR.sup.b).sub.2, or OSi(OR.sup.b).sub.3; [0194] each instance of R.sup.b is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a nitrogen protecting group when attached to a nitrogen atom, an oxygen protecting group when attached to an oxygen atom, or a sulfur protecting group when attached to a sulfur atom; [0195] each of n3 and n4 is independently 0, 1, 2, 3, or 4; [0196] R.sup.18 is substituted or unsubstituted aryl, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, or substituted or unsubstituted heteroaryl; and [0197] R.sup.19 is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; [0198] provided that no instance of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.10, R, R.sup.18, and R.sup.19 comprises one or more non-aromatic unsaturated CC bonds.

[0199] In another aspect, the present disclosure provides a copolymer prepared by a method comprising (e.g., consisting essentially of) polymerizing a first type of monomers, a second type of monomers, optionally one or more types of crosslinkers, and optionally one or more additional types of monomers, wherein: [0200] the first type of monomers is of Formula I:

##STR00018## [0201] or a tautomer or salt thereof; [0202] the second type of monomers is a compound provided herein, or a tautomer or salt thereof; and [0203] each type of the crosslinkers, if present, is independently a small molecule comprising two or more non-aromatic unsaturated CC bonds.

[0204] In certain embodiments, m1 is an integer between 30 and 100, between 100 and 300, between 300 and 1000, between 1000 and 3000, between 3000 and 10000, inclusive. In certain embodiments, m1 is an integer between 300 and 3000, inclusive.

[0205] In certain embodiments, m2 is an integer between 3 and 10, between 10 and 30, between 30 and 100, between 100 and 300, between 300 and 1000, or between 1000 and 3000, inclusive. In certain embodiments, m2 is an integer between 30 and 300, inclusive.

[0206] In certain embodiments, m1:m2 is between 1:1 and 3:1, between 3:1 and 10:1, between 10:1 and 30:1, between 30:1 and 100:1, between 100:1 and 300:1, or between 300:1 and 1000:1, inclusive. In certain embodiments, m1:m2 is between 3:1 and 100:1, inclusive.

[0207] In certain embodiments, R.sup.1 is hydrogen. In certain embodiments, R.sup.1 is substituted or unsubstituted alkyl. In certain embodiments, R.sup.1 is substituted or unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.1 is CH.sub.3.

[0208] In certain embodiments, R.sup.2 is hydrogen. In certain embodiments, R.sup.2 is substituted or unsubstituted alkyl. In certain embodiments, R.sup.2 is substituted or unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.2 is CH.sub.3.

[0209] In certain embodiments, R.sup.3 is hydrogen. In certain embodiments, R.sup.3 is substituted or unsubstituted alkyl. In certain embodiments, R.sup.3 is substituted C.sub.1-C.sub.6 alkyl. In certain embodiments, R.sup.3 is unsubstituted C.sub.1-C.sub.6 alkyl. In certain embodiments, R.sup.3 is CH.sub.3.

[0210] In certain embodiments, each of R.sup.1, R.sup.2, and R.sup.3 is hydrogen.

[0211] In certain embodiments, R.sup.4 is C(O)OR.sup.a; wherein R.sup.a is substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. In certain embodiments, R.sup.4 is C(O)N(R.sup.a).sub.2; wherein each R.sup.a is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted carbocyclyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl; provided that at least one R.sup.a is not hydrogen. In certain embodiments, R.sup.4 is C(O)OMe. In certain embodiments, R.sup.4 is C(O)NMe.sub.2. In certain embodiments, R.sup.4 is C(O)O.sup.tBu, C(O)OBn, or C(O)OCH.sub.2CH.sub.2OMe.

[0212] In certain embodiments, the first type of repeating units is of the formula:

##STR00019##

[0213] In certain embodiments, the first type of monomers is of the formula:

##STR00020##

[0214] In certain embodiments, the first type of repeating units is of the formula:

##STR00021##

[0215] In certain embodiments, the first type of monomers is of the formula:

##STR00022##

[0216] In certain embodiments, the second type of repeating units is of the formula:

##STR00023##

[0217] In certain embodiments, the second type of repeating units is of the formula:

##STR00024##

[0218] In certain embodiments, the second type of repeating units is of the formula:

##STR00025##

[0219] In certain embodiments, the second type of repeating units is of the formula:

##STR00026##

[0220] In certain embodiments, the second type of repeating units is of the formula:

##STR00027##

[0221] In certain embodiments, the second type of repeating units is of the formula:

##STR00028##

[0222] In certain embodiments, the second type of repeating units is of the formula:

##STR00029## [0223] R.sup.10, n3, R.sup.11, n4, R.sup.18, and R.sup.19 are as described herein.

[0224] In certain embodiments, n3 is 1. In certain embodiments, n3 is 0.

[0225] In certain embodiments, n4 is 0. In certain embodiments, n4 is 1.

[0226] In certain embodiments, at least one instance of R.sup.10 or R.sup.11 is halogen, preferably, fluoro. In certain embodiments, at least one instance of R.sup.10 or R.sup.11 is substituted or unsubstituted alkyl, O(substituted or unsubstituted alkyl), or S(substituted or unsubstituted alkyl). In certain embodiments, at least one instance of R.sup.10 or R.sup.11 is unsubstituted C.sub.1-6 alkyl, C.sub.1-6 alkyl substituted with one or more fluoro, O(unsubstituted C.sub.1-6 alkyl), O(C.sub.1-6 alkyl substituted with one or more fluoro), S(unsubstituted C.sub.1-6 alkyl), or S(C.sub.1-6 alkyl substituted with one or more fluoro).

[0227] In certain embodiments, R.sup.18 is substituted or unsubstituted aryl. In certain embodiments, R.sup.18 is substituted or unsubstituted phenyl. In certain embodiments, R.sup.18 is unsubstituted phenyl or phenyl substituted with one or more: halogen, substituted or unsubstituted, C.sub.1-6 alkyl, OR.sup.c, SR.sup.c, N(R.sup.c).sub.2, CN, SCN, NO.sub.2, C(O)R.sup.c, C(O)OR.sup.c, C(O)N(R.sup.c).sub.2, OC(O)R.sup.c, OC(O)OR.sup.c, OC(O)N(R.sup.c).sub.2, NR.sup.cC(O)R.sup.c, NR.sup.cC(O)OR.sup.c, and/or NR.sup.cC(O)N(R.sup.c).sub.2, wherein each instance of R.sup.c is independently hydrogen or substituted or unsubstituted C.sub.1-6 alkyl. In certain embodiments, R.sup.18 is unsubstituted phenyl or phenyl substituted with one or more: halogen, unsubstituted C.sub.1-6 alkyl, and/or C.sub.1-6 alkyl substituted with one or more fluoro. In certain embodiments, R.sup.18 is substituted or unsubstituted alkyl. In certain embodiments, R.sup.18 is unsubstituted C.sub.1-6 alkyl or C.sub.1-6 alkyl substituted with one or more fluoro.

[0228] In certain embodiments, R.sup.19 is hydrogen. In certain embodiments, R.sup.19 is substituted or unsubstituted alkyl. In certain embodiments, R.sup.19 is unsubstituted C.sub.1-6 alkyl or C.sub.1-6 alkyl substituted with one or more fluoro.

[0229] In certain embodiments, the second type of repeating units is of the formula:

##STR00030## [0230] or a tautomer thereof.

[0231] In certain embodiments, the second type of repeating units is of the formula:

##STR00031## [0232] or a tautomer thereof.

[0233] In certain embodiments, the second type of repeating units is of the formula:

##STR00032## [0234] or a tautomer thereof.

[0235] In certain embodiments, the method of polymerizing comprises substantially no crosslinkers.

[0236] In certain embodiments, the method of polymerizing comprises substantially no additional types of monomers.

[0237] In certain embodiments, at least one additional type of monomers is an end-group-forming monomer. In certain embodiments, at least one additional type of monomers is a chain transfer agent. In certain embodiments, at least one additional type of monomers is a dithioate (e.g., (substituted or unsubstituted, C.sub.1-6 alkyl)-SC(S)-(substituted or unsubstituted phenyl)).

[0238] In certain embodiments, the molar ratio of the first type of repeating units to all additional type of repeating units or the molar ratio of the first type of monomers to all additional types of monomers is between 3:1 and 10:1, between 10:1 and 30:1, between 30:1 and 100:1, between 100:1 and 300:1, between 300:1 and 1000:1, inclusive.

[0239] In certain embodiments, at least one type of the crosslinking units is of the formula:

##STR00033## [0240] wherein: [0241] each instance of L.sup.1 is independently substituted or unsubstituted, C.sub.1-100 alkylene or substituted or unsubstituted, C.sub.2-100 heteroalkylene, optionally wherein one or more backbone carbon atoms of the C.sub.1-100 alkylene and/or C.sub.2-100 heteroalkylene are independently replaced with substituted or unsubstituted carbocyclylene, substituted or unsubstituted heterocyclylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene; and [0242] each instance of R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, and R.sup.17 is independently hydrogen, halogen, or substituted or unsubstituted alkyl; [0243] provided that no instance of L.sup.1, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, and R.sup.17 comprises one or more non-aromatic unsaturated CC bonds.

[0244] In certain embodiments, at least one type of the crosslinkers is of the formula:

##STR00034## [0245] or a tautomer or salt thereof, wherein: [0246] each instance of L.sup.1 is independently substituted or unsubstituted, C.sub.1-100 alkylene or substituted or unsubstituted, C.sub.2-100 heteroalkylene, optionally wherein one or more backbone carbon atoms of the C.sub.1-100 alkylene and/or C.sub.2-100 heteroalkylene are independently replaced with substituted or unsubstituted carbocyclylene, substituted or unsubstituted heterocyclylene, substituted or unsubstituted arylene, or substituted or unsubstituted heteroarylene; and [0247] each instance of R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, and R.sup.17 is independently hydrogen, halogen, or substituted or unsubstituted alkyl; [0248] provided that no instance of L.sup.1, R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, and R.sup.17 comprises one or more non-aromatic unsaturated CC bonds.

[0249] In certain embodiments, at least one instance of L.sup.1 is independently substituted or unsubstituted, C.sub.1-100 alkylene or substituted or unsubstituted, C.sub.2-100 heteroalkylene. In certain embodiments, at least one instance of L.sup.1 is substituted or unsubstituted, C.sub.2-12 heteroalkylene. In certain embodiments, at least one instance of L.sup.1 is unsubstituted C.sub.2-12 heteroalkylene or C.sub.2-12 heteroalkylene substituted with one or more: oxo, unsubstituted C.sub.1-6 alkyl, and/or C.sub.1-6 alkyl substituted with one or more fluoro. In certain embodiments, at least one instance of L.sup.1 is C(O)O(CH.sub.2).sub.p1OC(O), wherein each instance of p1 is independently 2, 3, 4, 5, or 6.

[0250] In certain embodiments, each instance of R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, and R.sup.17 is independently hydrogen or substituted or unsubstituted, C.sub.1-6 alkyl. In certain embodiments, each instance of R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, and R.sup.17 is independently hydrogen or unsubstituted C.sub.1-3 alkyl. In certain embodiments, each instance of R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, and R.sup.17 is independently hydrogen or CH.sub.3. In certain embodiments, each instance of R.sup.12, R.sup.13, R.sup.14, R.sup.15, R.sup.16, and R.sup.17 is hydrogen.

[0251] In certain embodiments, no instance of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.10, R.sup.11, R.sup.18, and R.sup.19 comprises one or more non-aromatic CC double bonds. In certain embodiments, no instance of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.10, R.sup.11, R.sup.18, and R.sup.19 comprises one or more non-aromatic CC triple bonds.

[0252] In certain embodiments, the copolymer is substantially uncrosslinked.

[0253] In certain embodiments, the molar ratio of the first type of repeating units to all types of crosslinking units or the molar ratio of the first type of monomers to all types of crosslinkers is between 2:1 and 10:1, between 10:1 and 30:1, or between 30:1 and 100:1, inclusive.

[0254] In certain embodiments, the crosslinking degree of the copolymer is between 0.1% and 0.3%, between 0.3% and 1%, between 1% and 3%, between 3% and 10%, between 10% and 20%, or between 20% and 50%, inclusive, mole:mole. In certain embodiments, the crosslinking degree of the copolymer is not more than 0.1%, not more than 1%, or not more than 10%, inclusive, mole:mole. In certain embodiments, the crosslinking degree is determined by the consumption of the monomers that are polymerized to form the copolymer. In certain embodiments, the crosslinking degree is determined by the consumption of the comonomers and crosslinkers that are polymerized to form the copolymer.

[0255] In certain embodiments, the number-average molecular weight of the copolymer as determined by gel permeation chromatography is between 1 kDa and 3 kDa, between 3 kDa and 10 kDa, between 10 kDa and 30 kDa, between 30 kDa and 100 kDa, between 100 kDa and 300 kDa, between 300 kDa and 1,000 kDa, between 1,000 kDa and 3,000 kDa, or between 3,000 kDa and 10,000 kDa.

[0256] In certain embodiments, the number-average molecular weight of the copolymer as determined by gel permeation chromatography is between 2 kDa and 3 kDa, between 3 kDa and 4 kDa, between 4 kDa and 6 kDa, between 6 kDa and 8 kDa, or between 8 kDa and 10 kDa.

[0257] In certain embodiments, the number-average molecular weight of the copolymer as determined by gel permeation chromatography is between 100 kDa and 300 kDa, between 300 kDa and 1,000 kDa, between 1,000 kDa and 3,000 kDa, or between 3,000 kDa and 10,000 kDa.

[0258] In certain embodiments, the number-average molecular weight of the copolymer as determined by size exclusion chromatography is between 1 kDa and 3 kDa, between 3 kDa and 10 kDa, between 10 kDa and 30 kDa, between 30 kDa and 100 kDa, between 100 kDa and 300 kDa, between 300 kDa and 1,000 kDa, between 1,000 kDa and 3,000 kDa, or between 3,000 kDa and 10,000 kDa. In certain embodiments, the number-average molecular weight of the copolymer as determined by gel size exclusion chromatography is between 2 kDa and 3 kDa, between 3 kDa and 4 kDa, between 4 kDa and 6 kDa, between 6 kDa and 8 kDa, or between 8 kDa and 10 kDa.

[0259] In certain embodiments, the number-average molecular weight of the copolymer as determined by size exclusion chromatography is between 100 kDa and 300 kDa, between 300 kDa and 1,000 kDa, between 1,000 kDa and 3,000 kDa, or between 3,000 kDa and 10,000 kDa.

[0260] In certain embodiments, the copolymer is a random copolymer. In certain embodiments, the copolymer is a statistical copolymer. In certain embodiments, the copolymer is a block copolymer.

[0261] In certain embodiments, the copolymer is degradable after reacting with a nucleophile.

[0262] In another aspect, the present disclosure provides a composition comprising: [0263] a compound provided herein, or a tautomer or salt thereof; and [0264] optionally an excipient.

[0265] In certain embodiments, the excipient is one single excipient. In certain embodiments, the excipient is a mixture of two or more (e.g., three) excipients. In certain embodiments, the excipient is a solvent described herein.

[0266] In another aspect, the present disclosure provides a composition comprising: [0267] a copolymer provided herein; and [0268] optionally an excipient.

[0269] In another aspect, the present disclosure provides a kit comprising: [0270] the compound, or a tautomer or salt thereof, or the composition; and [0271] instructions for using the compound, tautomer, salt, or composition.

[0272] In another aspect, the present disclosure provides a kit comprising: [0273] the copolymer or the composition; and [0274] instructions for using the copolymer or composition.

[0275] In another aspect, the present disclosure provides a method of preparing the copolymer comprising (e.g., consisting essentially of) polymerizing the first type of monomers, the second type of monomers, optionally the crosslinkers, and optionally the additional types of monomers.

[0276] In certain embodiments, the step of polymerizing is polymerizing by a radical polymerization reaction.

[0277] In certain embodiments, the molar ratio of the first type of repeating units to the second type of repeating units, or the molar ratio of the first type of monomers to the second type of monomers is between 1:0.01 and 1:0.03, between 1:0.03 and 1:0.1, between 1:0.1 and 1:0.3, between 1:0.3 and 1:0.5, between 1:0.5 and 1:0.6, or between 1:0.6 and 1:0.7, inclusive. In certain embodiments, the molar ratio of the first type of monomers to the second type of monomers is between 1:0.05 and 1:0.12, inclusive. In certain embodiments, the molar ratio of the first type of repeating units to the second type of repeating units, or the molar ratio of the first type of monomers to the second type of monomers is between 1:0.025 and 1:0.25, inclusive.

[0278] In certain embodiments, the step of polymerizing further comprises a radical initiator. In certain embodiments, the radical initiator is substantially one single radical initiator. In certain embodiments, the radical initiator is a mixture of two or more (e.g., three) radical initiators. In certain embodiments, the radical initiator is an azo compound, organic peroxide, or inorganic peroxide. In certain embodiments, the radical initiator is 2,2-azobis(2-methylpropionitrile) (AIBN), 1,1-diazene-1,2-diyldicyclohexanecarbonitrile (ACHN), di-tert-butyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, acetone peroxide, or peroxydisulfate salt. In certain embodiments, the radical initiator is dichlorine.

[0279] In certain embodiments, the molar ratio of the radical initiator to the first type of monomers is between 0.0001:1 and 0.0003:1, between 0.0003:1 and 0.001:1, between 0.001:1 and 0.003:1, or between 0.003:1 and 0.01:1, inclusive.

[0280] In certain embodiments, the step of polymerizing further comprises a solvent. In certain embodiments, the solvent is substantially one single solvent. In certain embodiments, the solvent is a mixture of two or more (e.g., three) solvents (e.g., solvents described in this paragraph). In certain embodiments, the solvent is an organic solvent. In certain embodiments, the solvent is an aprotic solvent. In certain embodiments, the solvent is an ether solvent. In certain embodiments, the solvent is a ketone solvent. In certain embodiments, the solvent is an alkane solvent. In certain embodiments, the solvent is an aromatic organic solvent. In certain embodiments, the solvent is benzene, toluene, o-xylene, m-xylene, or p-xylene, or a mixture thereof. In certain embodiments, the solvent is toluene. In certain embodiments, the solvent is a non-aromatic organic solvent. In certain embodiments, the solvent is acetonitrile, dioxane, or tetrahydrofuran, or a mixture thereof. In certain embodiments, the solvent is acetonitrile. In certain embodiments, the solvent is acetone, chloroform, dichloromethane, diethyl ether, ethyl acetate, methyl tert-butyl ether, or 2-methyltetrahydrofuran, or a mixture thereof. In certain embodiments, the solvent is dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or a mixture thereof. In certain embodiments, the boiling point of the solvent at about 1 atm is between 30 and 50, between 50 and 70, between 70 and 100, between 100 and 130, between 130 and 160, or between 16 and 200 C., inclusive.

[0281] In certain embodiments, the step of polymerizing is substantially free of a solvent.

[0282] In certain embodiments, the temperature of the step of polymerizing is between 20 and 40, between 40 and 60, between 60 and 90, between 90 and 120, or between 12 and 150 C., inclusive. In certain embodiments, the temperature of the step of polymerizing is between 8 and 120 C., inclusive. In certain embodiments, the temperature of the step of polymerizing is substantially constant over the time duration of the step of polymerizing. In certain embodiments, the temperature of the step of polymerizing is a variable temperature (e.g., 5, 10, 15, or 20 C.) over the time duration of the step of polymerizing.

[0283] In certain embodiments, the time duration of the step of polymerizing is between 1 and 3 hours, between 3 and 8 hours, between 8 and 24 hours, between 1 and 3 days, or between 3 and 7 days, inclusive. In certain embodiments, the time duration of the step of polymerizing is between 2 and 24 hours, inclusive.

[0284] In another aspect, the present disclosure provides a method of degrading the copolymer comprising reacting the copolymer with a nucleophile.

[0285] In certain embodiments, immediately after the step of degrading, between 10% and 20%, between 20% and 30%, between 30% and 50%, between 50% and 70%, or between 70% and 90% of the CS bonds in the backbone of the copolymer is cleaved.

[0286] In certain embodiments, the step of reacting the copolymer with the nucleophile comprises a second time duration. In certain embodiments, the second time duration is between 10 minute and 1 hour, between 1 and 8 hours, between 8 and 24 hours, between 1 and 3 days, or between 3 and 7 days, inclusive. In certain embodiments, the second time duration is between 8 hours and 3 days.

[0287] In certain embodiments, the nucleophile degrades the copolymer under ambient conditions. In certain embodiments, the step of reacting the copolymer with the nucleophile comprises a second temperature. In certain embodiments, the second temperature is ambient temperature. In certain embodiments, the second temperature is between 20 and 40, between 40 and 60, between 60 and 80, between 80 and 100, or between 10 and 120 C., inclusive. In certain embodiments, the second temperature is between 4 and 60 C., inclusive. In certain embodiments, the second temperature is substantially constant over the second time duration. In certain embodiments, the second temperature is a variable temperature (e.g., 5, 10, 15, or 20 C.) over the second time duration.

[0288] In certain embodiments, the nucleophile is an amine. In certain embodiments, the nucleophile is an aliphatic amine. In certain embodiments, the nucleophile is aromatic amine. In certain embodiments, the nucleophile is (substituted or unsubstituted alkyl)-NH.sub.2, preferably (unsubstituted C.sub.2-6 alkyl)-NH.sub.2. In certain embodiments, the nucleophile is n-propylamine. In certain embodiments, the nucleophile is (substituted or unsubstituted alkyl).sub.2NH or (substituted or unsubstituted alkyl).sub.3N. In certain embodiments, the nucleophile is (substituted or unsubstituted, C.sub.1-6 alkyl).sub.2NH or (substituted or unsubstituted, C.sub.1-6 alkyl).sub.3N. In certain embodiments, the nucleophile is (alkyl substituted at least with SH)NH.sub.2, preferably HS(CH.sub.2).sub.2-6NH.sub.2. In certain embodiments, the nucleophile is an amidine (e.g., 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), diminazene, benzamidine, pentamidine, or paranyline). In certain embodiments, the nucleophile is a primary amine. In certain embodiments, the nucleophile is methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, n-pentylamine, n-hexylamine, cyclohexylamine, ethanolamine (i.e., 2-aminoethanol), tris (i.e., 2-amino-2-hydroxymethyl-propane-1,3-diol), ethylenediamine, triethylenediamine, or aniline. In certain embodiments, the nucleophile is a secondary amine. In certain embodiments, the nucleophile is dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, ethylisopropylamine, dicyclohexylamine, methylethanolamine, pyrrolidine, piperidine, morpholine, piperazine, or 1,4-bis-(3-aminopropyl)piperazine. In certain embodiments, the nucleophile is a tertiary amine. In certain embodiments, the nucleophile is trimethylamine, triethylamine, diisopropylethylamine (DIPEA), tri-n-butylamine, 4-dimethylaminopyridine (DMAP), or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). In certain embodiments, the nucleophile is a thiol. In certain embodiments, the nucleophile is (substituted or unsubstituted alkyl)-SH, preferably (unsubstituted C.sub.2-6 alkyl)-SH.

[0289] In certain embodiments, the nucleophile is substantially one compound. In certain embodiments, the nucleophile is a mixture of two or more (e.g., three) compounds. In certain embodiments, the nucleophile is a mixture of two or more amines. In certain embodiments, the nucleophile is a mixture of (1) (substituted or unsubstituted, C.sub.1-6 alkyl)-NH.sub.2, (substituted or unsubstituted, C.sub.1-6 alkyl).sub.2NH, or (substituted or unsubstituted, C.sub.1-6 alkyl).sub.3N (e.g., at between 80% and 99%, v/v, inclusive); and an amidine (e.g., DBU) (e.g., at between 1% and 20%, v/v, inclusive).

[0290] In certain embodiments, the step of reacting the copolymer with the nucleophile comprises no solvent.

[0291] In certain embodiments, the step of reacting the copolymer with the nucleophile comprises a second solvent. In certain embodiments, the second solvent is substantially one single solvent. In certain embodiments, the second solvent is a mixture of two or more (e.g., three) solvents (e.g., solvents described in this paragraph). In certain embodiments, the second solvent is an organic solvent. In certain embodiments, the second solvent is an aprotic solvent. In certain embodiments, the second solvent is an ether solvent. In certain embodiments, the second solvent is a ketone solvent. In certain embodiments, the second solvent is an alkane solvent. In certain embodiments, the second solvent is an alcohol solvent. In certain embodiments, the second solvent is an aromatic organic solvent. In certain embodiments, the second solvent is benzene, toluene, o-xylene, m-xylene, or p-xylene, or a mixture thereof. In certain embodiments, the second solvent is a non-aromatic organic solvent. In certain embodiments, the second solvent is acetonitrile, dioxane, or tetrahydrofuran, or a mixture thereof. In certain embodiments, the second solvent is acetonitrile. In certain embodiments, the second solvent is acetone, chloroform, dichloromethane, diethyl ether, ethyl acetate, methyl tert-butyl ether, or 2-methyltetrahydrofuran, or a mixture thereof. In certain embodiments, the second solvent is dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, or a mixture thereof. In certain embodiments, the second solvent is an inorganic solvent (e.g., water). In certain embodiments, the boiling point of the second solvent at about 1 atm is between 30 and 50, between 50 and 70, between 70 and 100, between 100 and 130, between 130 and 160, or between 16 and 200 C., inclusive.

[0292] In certain embodiments, a step of a method described herein is under a pressure between 0.5 and 1.1 atm (e.g., between 0.8 and 1.1 atm), inclusive.

EXAMPLES

[0293] In order that the present disclosure may be more fully understood, the following examples are set forth. The synthetic and biological examples described in this application are offered to illustrate the compounds, pharmaceutical compositions, and methods provided herein and are not to be construed in any way as limiting their scope.

Example 1. Mechanism-Guided Discovery of Cleavable Comonomers for Backbone Deconstructable Polymethylmethacrylate (PMMA)

[0294] This example describes the design of a class of benzyl-functionalized thionolactones (bDOTs). Guided by detailed mechanistic analyses, the introduction of radical-stabilizing substituents to bDOTs was shown to enable markedly increased and tunable copolymerization reactivity with methyl methacrylate (MMA). Through iterative optimizations of molecular structure, a specific bDOT, F-p-CF.sub.3PhDOT, was discovered to copolymerize with MMA to achieve a nearly even distribution within the resulting copolymers. High molecular weight deconstructable PMMA (dPMMA, M.sub.n>120 kDa) with low percentages of F-p-CF.sub.3PhDOT (1.8 and 3.8%) were prepared using industrially relevant bulk free radical copolymerization. The thermomechanical properties dPMMA are similar to PMMA; however, the former were shown to degrade into low-molecular-weight fragments (<6.5 kDa) under mild aminolysis conditions. This example presents a radical ring-opening CC capable of nearly random copolymerization with MMA without crosslinking.

[0295] High-performance polymers often pose end-of-life management challenges. Integrating chemical deconstructability into these polymers is advantageous, as it not only facilitates their degradation but also provides opportunities for recycling and upcycling through further chemical processing of deconstructed fragments. This integration can be achieved through the cleavable comonomer (CC) approach, in which small molecules known as CCs are incorporated into the polymer backbone via copolymerization, introducing functionalities that are cleavable by external triggers..sup.1-7 For an effective implementation, the CC needs to be compatible with existing industrial polymerization methods, allowing for its rapid incorporation into current manufacturing processes. In addition, the CC loading needs to be minimal to avoid compromising the desirable properties of the original material and to minimize the impact on cost while still enabling maximal deconstruction. Therefore, an optimal CC should exhibit favorable copolymerization reactivity with the monomer and polymerization reaction of interest, ensuring the formation of the smallest possible degraded fragments at low loadings.

[0296] In chain-growth polymers, the copolymerization behavior of a CC with a target monomer (M) is governed by two reactivity ratios based on terminal models:

[00001]$r_M=\frac{k_{M\mathrm{to}M}}{k_{M\mathrm{to}\mathrm{CC}}},r_{\mathrm{CC}}=\frac{k_{\mathrm{CC}\mathrm{to}\mathrm{CC}}}{k_{\mathrm{CC}\mathrm{to}M}}$ [0297] where k.sub.A to B represents the rate constant for propagation from a chain ending in monomer A to monomer B (A and B each being either M or CC)..sup.8 When both reactivity ratios are >1 or <1, blocky or alternating copolymers result, respectively. A random comonomer distribution occurs when both r.sub.M and r.sub.CC are exactly equal to one. Gradient structures (in controlled radical polymerizations) or compositional drift (in free-radical polymerizations) emerge when one reactivity ratio is >1 and the other <1, with the monomer having the larger reactivity ratio being consumed first. Previous studies have used Monte Carlo simulations to examine copolymer sequences based on reactivity ratios..sup.9-15 This methodology can be extended to model fragment sizes post degradation in the context of the CC approach..sup.16-18 For example, simulations were conducted involving 2.5% CC loading with a degree of polymerization (DP) of 1,000 and plotted the weight-average molecular weight (M.sub.w) of the oligomeric fragments obtained after CC cleavage relative to the M.sub.w of the starting copolymer under various reactivity ratio scenarios (FIG. 17A; see Simulation Details section for further information). The use of M.sub.w for the plotting conveys information about the largest fragments, which is important for assessing the performance of a CC. As shown in FIG. 17A, the fragment size remains largely unaffected by r.sub.CC across a 0.01-100 range due to the low CC loading of 2.5%. Fluctuations in r.sub.M, e.g., ranging from 0.1 to 10, may have a substantial impact. The size reaches its minimum when r.sub.M is equal to one, indicating that an optimal CC requires an r.sub.M value close to one for the most efficient deconstruction. Examples of simulated polymer sequences corresponding to different regions of FIG. 17A are illustrated in FIG. 17B. A deviation from the ideal (Region I) may produce a notable composition gradient in the copolymer structure (Region II-V), which results in inefficient deconstruction. These findings suggest the importance of reactivity ratios in the development of CCs and provide guidance for the preferred values: r.sub.M being as close as possible to 1, while r.sub.CC being less significance if it falls within the range of 0.01-100.

[0298] Vinyl polymers, which account for half of all polymers produced, are limited in their deconstructability because of their carbon-carbon backbones, which has driven the development of CCs.sup.19-21 or post-polymerization methods.sup.22-25 to install cleavable bonds. Because a large fraction of vinyl polymers are synthesized industrially through radical polymerization, various classes of CCs that are compatible with this process have been developed via three main approaches: 1) copolymerizing dioxygen to introduce cleavable peroxy bonds.sup.26-38; 2) using comonomers with functional groups that can generate radicals in the polymer backbone to trigger deconstruction.sup.39-45; and 3) employing comonomers capable of radical ring-opening polymerization (rROP) to introduce cleavable functionality..sup.46,47 Among these approaches, rROP CCs have been extensively studied as they offer molecular tunability and enable a variety of deconstruction mechanisms.

[0299] Despite recent advances in rROP chemistry, formulating efficient rROP CCs for methacrylates remains challenging. Cyclic ketene acetals (CKAs).sup.48-50 and sulfide-based cyclic methacrylates (SCMs).sup.51-60 are examples of rROP CCs, and they have been explored for their ability to copolymerize with methacrylic monomers.sup.61-76 (FIG. 17B, I and II). Copolymerizations of methacrylates with CKAs exhibit pronounced compositional gradients (r.sub.M significantly exceeds one), while copolymerizations with SCMs display improved reactivity but can lead to the formation of unwanted crosslinks. Moreover, these CCs introduce ester functionalities into the polymer backbone, the cleavage of which can compromise the ester functional groups in the methacrylate monomers unless a weaker bond is deliberately incorporated into the CC..sup.51,56 Recently, thionolactones (TLs) have emerged as a type of rROP CC for enabling the installation of thioester linkages into polymer backbones, the latter of which may be efficiently and selectively cleaved under comparatively mild conditions (FIG. 17B, III)..sup.77 TLs have proven successful as CCs for various vinyl polymers. An example is the TL molecule dibenzo[c,e]oxepine-5(7H)-thione, commonly referred to as DOT, which has demonstrated copolymerization reactivity with various acrylate,.sup.5, 78-86 acrylamide,.sup.78,80,81 and styrenic.sup.4, 82-85, 87 monomers; however, there have been no successful instances of TLs copolymerizing with methacrylates without exhibiting negligible reactivity or pronounced compositional gradients,.sup.88 which can be attributed to their reactivity ratios being far from optimal.

[0300] To develop a TL optimized for methacrylates, the potential energy landscape of propagation was investigated, as reactivity ratios are intrinsically associated with the kinetics of propagation. In particular, development of a CC for methyl methacrylate (MMA) was pursued, as this is a widely used type of methacrylate, and it has broad applications ranging from transparent glass substitutes to automotive components and surface coatings..sup.89,90 This example details the mechanism-driven development of a new class of CCs, termed benzylic-functionalized DOTs, or bDOTs (FIG. 17B, IV), which led to the discovery of an efficient CC, F-p-CF.sub.3PhDOT, designed for use with the commodity polymer polymethylmethacrylate (PMMA). This example demonstrates the excellent compatibility of F-p-CF.sub.3PhDOT with bulk free-radical polymerization (FRP) methods, which are standard in the production of high molecular weight industrial PMMA. Moreover, the favorable reactivity ratios of F-p-CF.sub.3PhDOT enable efficient deconstruction of PMMA without compromising material properties, thereby confirming its effectiveness as a CC. F-p-CF.sub.3PhDOT is capable of introducing well-distributed thioester functionalities into polymethacrylates, thus facilitating efficient degradation at low CC loadings.

[0301] DFT calculations enable the mechanism-guided design of bDOTs.

[0302] A mechanistic investigation was performed to on the inability of DOT to copolymerize with MMA under radical polymerization conditions. As discussed, the copolymerization behavior of DOT and MMA may be governed by two reactivity ratios:

[00002]$r_{\mathrm{MMA}}=\frac{k_{\mathrm{MMA}\mathrm{to}\mathrm{MMA}}}{k_{\mathrm{MMA}\mathrm{to}\mathrm{DOT}}},r_{\mathrm{DOT}}=\frac{k_{\mathrm{DOT}\mathrm{to}\mathrm{DOT}}}{k_{\mathrm{DOT}\mathrm{to}\mathrm{MMA}}}$ [0303] where k.sub.A to B represents the rate constant for propagation from a chain ending in monomer A to monomer B (A and B being MMA or DOT). A previous report indicated that DOT acts as a spectator during copolymerization with MMA, with MMA undergoing homopolymerization..sup.78 Thus, a propagating chain ending in MMA homopropagates considerably faster than it cross-propagates, which would correspond to a large r.sub.MMA. Further, as the simulations show (FIG. 17A), r.sub.MMA would have a more dominant influence on the copolymerization behavior than r.sub.DOT in circumstances where a minimal amount of DOT is added to the reaction mixture as a CC. Accordingly, density functional theory (DFT) calculations were employed to model the competition between homopropagation and cross-propagation of a propagating chain ending in MMA (FIG. 18). To reduce the computational cost, the homopropagation was simplified as radical 1 adding to MMA, and the cross-propagation was modeled as 1 adding to DOT, followed by -scission and ring-opening, ultimately leading to the incorporation of DOT. This is an example where a computational tool was employed to analyze the copolymerization between TLs and methacrylates. Guillaneuf and co-workers.sup.85 recently reported on the use of DFT calculations to aid in the development of a TL with improved reactivity for styrene and acrylate monomers. Their approach involved defining a composite rate constant that combines the multi-step process of radical addition to TLs, which may be beneficial for evaluating and predicting the reactivity of CCs when there are known molecules that copolymerize with the monomer of interest as reference points, as is the case with styrene and acrylates. By contrast, the present example involves analyzing the entire radical addition potential energy landscape and identifying key transition states that determine the reactivity ratios, which enables the discovery of a CC tailored for a challenging target monomer where no current solutions exist (e.g., MMA) and provides detailed mechanistic understanding of the impacts of CC molecular modification on the energy profile of rROP.

[0304] The DFT calculations described herein suggested that the rate-determining step for the cross-propagation of a chain ending with MMA may be the ring-opening of DOT, as evidenced by its calculated transition state (TS-D1) energy being 8.1 kcal/mol higher than that for the addition step (TS-D2). Although the kinetic barrier for cross-propagation is thermally accessible (G.sup..sub.C=14.4 kcal/mol), it is 7.4 kcal/mol higher than that for homopropagation (G.sup..sub.H=7.0 kcal/mol). This finding aligns with experimental observations where DOT acts as a spectator during MMA homopolymerization. The propagations leading to the formation of M1 and D2 are deemed irreversible at an appreciable concentration of MMA, as the subsequent monomer addition to form MM1 and DM1, respectively, is kinetically more favorable by >12 kcal/mol than the reverse reaction regenerating 1 and D1. Consequently, monomer addition to propagating chains ending in MMA is likely to be under Curtin-Hammett control, with the energy difference between TS-M1 and TS-D2 (G.sup..sub.C-H) dictating the reactivity ratio r.sub.MMA. Thus, lowering the energy of TS-D2 to match that of TS-M1, such that r.sub.MMA nears the optimal value of one as shown in FIG. 17A, may be important for achieving the copolymerization of DOT and MMA. Mulliken spin population analysis of the rate-determining transition state, TS-D2, showed that the benzylic carbon of DOT carries the highest spin population of 0.489 (FIGS. 24A-24B), which suggests that introducing radical-stabilizing substituent(s) onto the benzylic carbon of DOT might enable the copolymerization of DOT and MMA by lowering the energy of TS-D2.

[0305] To test this hypothesis, the calculated relative Gibbs free energy profiles for 1 propagating with DOT were compared to bDOTs 7-methylDOT (MeDOT), 7,7-dimethylDOT (Me.sub.2DOT), and 7-phenylDOT (PhDOT) (FIG. 2). All three derivatives were calculated to have a lower TS-D2 than the parent DOT. PhDOT was predicted to exhibit TS-D2 energy of 5.9 kcal/mol, which is 1.1 kcal/mol below that of TS-M1. Bolstered by these computational results, the synthesis of bDOTs was performed to experimentally assess their copolymerization reactivity with MMA.

Synthesis of bDOTs and Evaluation of Copolymerization Reactivity.

[0306] Synthetic routes were developed to facilitate the syntheses of bDOTs (FIGS. 19A-19B). A palladium-catalyzed Suzuki coupling involving 2-bromostyrene and the derivatives of either 2-formyl or 2-methoxycarbonyl phenylboronic acid was utilized, followed by a Grignard reaction that installed the benzylic substituents (circles marked by asterisks, FIGS. 19A-19C). The use of 2-formyl phenylboronic acid as a starting material allows for the introduction of one benzylic substituent, whereas 2-methoxycarbonyl phenylboronic acid enables two. Employing 4-substituted 2-formyl phenylboronic acid derivatives enables aryl ring functionalization (circles not marked by asterisks, FIGS. 19A-19C), potentially altering solubility and reactivity..sup.87 Subsequent to the introduction of benzylic substituent(s), oxidative lactonization followed by thionation furnishes the desired bDOT. The advantages of these pathways include: 1) the introduction of benzylic substitution(s) via a Grignard reaction, which allows for the incorporation of diverse functional groups depending on the chosen Grignard reagent, and 2) the capability to introduce either one or two benzylic substituents using an analogous route, an option not achieved with previous synthetic methods that relied on transesterification to form the lactone..sup.78,79,87

[0307] MeDOT and PhDOT were successfully synthesized from 2-bromostyrene and 2-formyl phenylboronic acid (FIG. 25). A Suzuki coupling employing the 3rd-generation Buchwald precatalyst Sphos Pd G3 yielded the coupled product 2-vinyl-[1,1-biphenyl]-2-carbaldehyde with a 98.6% yield. This step was followed by a Grignard reaction using MeMgBr and PhMgBr for MeDOT and PhDOT, respectively. Subsequent OsO.sub.4-catalyzed oxidative cyclization formed lactones 7-methyldibenzo[c,e]oxepin-5(7H)-one (MeDOO) and 7-phenyldibenzo[c,e]oxepin-5(7H)-one (PhDOO), with two-step yields of 45.3% and 51.5%, respectively. The final step involved thionation using Lawesson's reagent to produce MeDOT and PhDOT. The overall yield for MeDOT synthesis (24.5%) was on par with that reported for DOT (26.6%), 79 with a thionation yield of 54.9%. By contrast, PhDOT was synthesized at a lower overall yield of 9.7% due to its reduced thionation yield of 19.1%. The major side products of the thionation were identified as the isomerized thiolactone 7-phenyldibenzo[c,e]thiepin-5(7H)-one (PhDTO) and the overthionated 7-phenyldibenzo[c,e]thiepine-5(7H)-thione (PhDTT). Me.sub.2DOT was synthesized beginning with an Sphos Pd G3-catalyzed Suzuki coupling between 2-formyl phenylboronic acid and 2-methoxycarbonyl phenylboronic acid, achieving a coupling yield of 85.2%. Subsequently, a Grignard reaction introduced two methyl groups with a 78.8% yield, and OsO.sub.4-mediated lactonization yielded 7,7-dimethyldibenzo[c,e]oxepin-5(7H)-one (Me.sub.2DOO) with a 47.8% yield. For the thionation step, a reduced temperature (65 C.) and an alternative solvent (THF) were employed to mitigate excessive isomerization. The thionation yield was 5.8% (FIG. 26).

[0308] Each bDOT (initial feed f.sub.bDOT=10 mol %) was tested for its potential to undergo copolymerization with MMA under reversible addition-fragmentation chain transfer (RAFT) polymerization conditions, with 1,1-azobis(cyanocyclohexane) (ACHN) as the initiator, 1 mol % 2-cyano-2-propyl benzodithioate as the chain transfer agent (CTA), and a reaction temperature of 100 C. (FIG. 19D). RAFT conditions facilitated the measurement of copolymerization kinetics and the determination of reactivity ratios by suppressing competing termination pathways in free radical copolymerization. bDOT conversions were measured as a function of time through quantitative .sup.1H NMR. As with DOT, no conversion was observed for MeDOT (FIG. 31A). While Me.sub.2DOT displayed a gradual transformation into an unidentified species, it also did not participate in copolymerization with MMA (FIG. 31B). PhDOT was consumed throughout its copolymerization with MMA to produce copolymer P(MMA-co-PhDOT) (FIG. 32). No isomerization from TL to the corresponding thiolactone was observed for any of the bDOTs under these copolymerization conditions.

[0309] .sup.13C NMR analysis of the purified P(MMA-co-PhDOT) showed signals at =191 ppm, characteristic of thioester carbons, which is consistent with the successful incorporation of PhDOT into the polymer (FIG. 34). Moreover, the complete disappearance of the singlet benzylic CH peak at =6.34 ppm and its shift to =5.5-5.9 ppm suggested that every introduced comonomer underwent ring-opening to contribute a thioester to the polymer (FIG. 33). The overall incorporation (F.sub.bDOT) of PhDOT, however, was modest as determined by quantitative .sup.1H NMR analysis, where F.sub.bDOT was only 3.4% for an f.sub.bDOT of 10%.

[0310] Enhanced bDOT reactivity was pursued by further modulating the electronic properties of the benzylic substituent for impacting the stability of the transition state radical (vide supra). Para Me and CF.sub.3 substituents were introduced onto the phenyl ring of PhDOT using the appropriate phenyl Grignard reagent, generating bDOTs p-MePhDOT (FIG. 27) and p-CF.sub.3PhDOT (FIG. 28), respectively. Aryl bDOTs with stronger electron-withdrawing character, 10-fluoro-7-(4-(trifluoromethyl)phenyl)DOT (F-p-CF.sub.3PhDOT) and 7-(pentafluorophenyl)DOT (PFPhDOT), were also prepared (FIG. 20A). F-p-CF.sub.3PhDOT was synthesized starting from 5-fluoro-2-formylphenylboronic acid following an otherwise identical synthetic route to p-CF.sub.3PhDOT (FIG. 29). PFPhDOT was produced using the pentafluorophenyl Grignard reagent (FIG. 30). A correlation between the electron withdrawing ability of the benzylic substituent and the stability of the resulting bDOT toward isomerization to the corresponding thiolactone (and thus the synthesis yield) under thionation conditions was observed. For example, the thionation yields of p-CF.sub.3PhDOT, F-p-CF.sub.3PhDOT, and PFPhDOT were 48.5%, 45.2%, and 49.7%, respectively, which were much higher than that for PhDOT (19.1%). By contrast, the synthesis of p-MePhDOT involved a combination of reduced temperature (65 C.) and THF as a solvent to avoid excessive isomerization, leading to a thionation yield of 8.1% (FIG. 27). Overall, these findings are consistent with the build-up of a partial positive charge on the benzylic carbon during the transition state of the isomerization reaction.

[0311] Conversions of MMA and each aryl bDOT (p-MePhDOT, PhDOT, p-CF.sub.3PhDOT, F-p-CF.sub.3PhDOT, and PFPhDOT; f.sub.bDOT=10 mol %) were measured versus time via .sup.1H NMR using the RAFT copolymerization conditions outlined above (FIG. 20B). The conversion data were fitted to the integrated terminal copolymerization model reported by Meyer-Lowry,.sup.91,92 providing r.sub.MMA values of 8.6 for p-MePhDOT, 3.8 for PhDOT, 2.2 for p-CF.sub.3PhDOT, 1.4 for F-p-CF.sub.3PhDOT, and 0.65 for PFPhDOT (FIG. 20C). These findings suggest that electron withdrawing groups may increase the reactivity of these bDOTs, shifting the r.sub.MMA to smaller values; r.sub.MMA approaches the ideal value of 1 as it transitions from p-MePhDOT to F-p-CF.sub.3PhDOT and falls below 1 for PFPhDOT. The r.sub.DOT values for p-MePhDOT, PhDOT, p-CF.sub.3PhDOT, and F-p-CF.sub.3PhDOT were measured to be within the range of 0.1 to 13; the variation of r.sub.DOT in this range may not significantly affect the deconstruction efficiency, assuming an f.sub.bDOT of 2.5% (FIG. 17A); however, for PFPhDOT, r.sub.DOT was measured to be larger than 100.

[0312] The efficiency of the aryl bDOTs as CCs can be predicted by comparing them on the heat map from Monte-Carlo simulations based on their experimentally measured reactivity ratios (FIG. 21). p-MePhDOT, with a large r.sub.MMA of 8.6 and an r.sub.DOT>1, may form a blocky copolymer with MMA, with the MMA blocks predominantly appearing earlier than the p-MePhDOT blocks, rendering it less efficient as a CC. PhDOT and p-CF.sub.3PhDOT, with their r.sub.MMA>1 and r.sub.DOT<1, may form gradient copolymers with MMA, with earlier segments of these copolymers comprising mostly MMA and the CCs distributed in the latter segments. Among these two, p-CF.sub.3PhDOT may produce relatively less gradient in the polymer and accordingly, smaller deconstruction fragment sizes due to its smaller r.sub.MMA. F-p-CF.sub.3PhDOT, with an r.sub.MMA of 1.4 and an r.sub.DOT of 2.9, may produce copolymers with slight blockiness; however, its r.sub.MMA close to 1 may result in a well-distributed CC composition in the copolymer chains, making it highly efficient as a CC.F-p-CF.sub.3PhDOT is positioned on the heatmap (FIG. 21) in a region suggesting nearly ideal deconstruction into small molar mass fragments. PFPhDOT, despite its r.sub.MMA being close to 1, has an exceedingly large r.sub.DOT, indicating a strong propensity for homopropagation. Therefore, its copolymer with MMA may have PFPhDOT blocks at the earlier parts of the chains with negligible distribution in the latter parts, making it less efficient as a CC. Overall, these results demonstrate a significant improvement in understanding and tuning bDOT CC performance, facilitated by mechanism-guided molecular design.

[0313] Application to F-p-CF.sub.3PhDOT PMMA synthesis via free radical copolymerization.

[0314] Having identified F-p-CF.sub.3PhDOT as a promising candidate for copolymerization with MMA, its performance was subsequently evaluated under solvent-free FRP conditions used for high molecular weight PMMA synthesis in industry.sup.89 (Note: F-p-CF.sub.3PhDOT displayed good solubility in MMA: >233 mg/mL). F-p-CF.sub.3PhDOT was combined with MMA in varied feed ratios (f.sub.bDOT=0% (control), 2.5%, 5%, and 10%) and heated to 100 C. in the presence of ACHN for 8 hours (FIG. 22A). The resulting virgin PMMA (f.sub.bDOT=0%, vPMMA) and the copolymers, dPMMA(f.sub.bDOT), were isolated by repeated precipitation in methanol. Quantitative .sup.1H NMR analysis of the isolated copolymers showed F.sub.bDOT values of 1.8%, 3.8%, and 8.7% for the f.sub.bDOT=2.5%, 5.0%, and 10%, respectively (FIG. 22B). The number-average molar masses (M.sub.n,SEC) of vPMMA, dPMMA(2.5), dPMMA(5.0), and dPMMA(10) were all above 120 kDa as determined by size exclusion chromatography (SEC, FIG. 22C).

[0315] Deconstruction of copolymers dPMMA(2.5), dPMMA(5.0), and dPMMA(10) was achieved by treating each sample with 5 v/v % DBU in neat propylamine at 50 C. for 24 hours (FIG. 22A). Exposing vPMMA to these conditions did not lead to any observable decrease in molar mass (FIG. 37). By contrast, the bDOT-containing copolymers underwent deconstruction into low molar mass oligomethylmethacrylate (OMMA) fragments designated as OMMA(f.sub.bDOT). M.sub.n,SEC decreased by more than 20-fold with bDOT loading, with OMMA(2.5), OMMA(5.0), and OMMA(10) having an M.sub.n,SEC of 6.5 kDa, 5.3 kDa, and 3.6 kDa, respectively (FIG. 22C). Similarly, M.sub.w,SEC, for OMMA(2.5), OMMA(5.0), and OMMA(10) decreased by more than 20-fold to 25.2 kDa, 16.6 kDa, and 10.4 kDa, respectively. Complete deconstruction was also achievable under milder conditions, as demonstrated for dPMMA(2.5), using neat propylamine at room temperature (FIG. 38). Altogether, these results demonstrate that F-p-CF.sub.3PhDOT efficiently copolymerizes with MMA under free radical polymerization conditions to generate high molecular weight, deconstructable copolymers that can be cleaved into oligomers with >20-fold reduction in molar mass. These results represent an example of a thionolactone comonomer that undergoes efficient copolymerization with MMA.

[0316] Properties of deconstructable PMMA.

[0317] As noted above, an ideal CC should not negatively impact the desirable properties of the polymer in which it is used. One of the properties of PMMA is its colorlessness and transparency after processing, which allows for its application as glass substitutes. Although F-p-CF.sub.3PhDOT is yellow, it loses its color once polymerized, resulting in vPMMA, dPMMA(2.5), and dPMMA(5.0) being colorless and visually indistinguishable. Purified vPMMA, dPMMA(2.5), and dPMMA(5.0) showed no difference in color. The transparency of vPMMA and dPMMA(5.0) after compression molding also showed no notable difference. The thermal properties of dPMMA(2.5) and dPMMA(5.0) were investigated and compared to that of vPMMA using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The glass transition temperatures (T.sub.g) of dPMMA(2.5) and dPMMA(5.0) were 133.0 C. and 134.0 C., respectively, which are slightly higher yet nearly indistinguishable from the 131.9 C. measured for vPMMA (FIG. 23A). The thermal decomposition temperatures at 5% mass loss (Td, 5%) exhibited moderate increase, shifting from 239 C. to 275 C. for dPMMA(2.5) and to 274 C. for dPMMA(5.0) (FIG. 23B). The thermomechanical properties of dPMMA(2.5) and dPMMA(5.0) were further studied using dynamic mechanical analysis (DMA). Compression-molded rectangular bars displayed temperature sweep curves nearly identical to those of vPMMA, except for a slight increase in T.sub.g that was observed with increased f.sub.bDOT. The elastic moduli (E) were consistent across vPMMA, dPMMA(2.5), and dPMMA(5.0), with values of 2.610.15 GPa, 2.790.33 GPa, and 2.870.21 GPa (averaged from 25-30 C. for triplicate runs), respectively, aligning well with the reported values for commercial PMMA (2.76-3.30 GPa.sup.93) (FIG. 23C). These findings showed that while F-p-CF.sub.3PhDOT provided thioester-based deconstructable PMMA, it did not negatively impact the properties of PMMA, and instead led to a slight increase in T.sub.g.

[0318] In summary, this example describes an efficient TL CC for methacrylates and demonstrates its excellent compatibility with solvent-free FRP. This cleavable-comonomer may be useful for polymethacrylate end-of-life management, along with various orthogonal depolymerization strategies..sup.94-107 Central to this advancement was the realization from mechanistic analysis that: 1) lowering the transition state energy of the DOT ring-opening step may be important to modulating r.sub.MMA to approach the ideal value of 1; and 2) such lowering may be achieved through benzylic functionalization.

General Experimental Details

General Considerations

[0319] All reactions were performed using standard Schlenk techniques unless stated otherwise. All glassware was dried in a 120 C. oven overnight or flame-dried prior to use. Molecular sieves (4 ) were activated by heating at 220 C. for three days under a nitrogen atmosphere and for three more days under vacuum, before storage in a glovebox. Analytical thin layer chromatography (TLC) was performed on Baker-Flex Precoated Flexible TLC Sheets, impregnated with a fluorescent indicator (254 nm). Visualization of compounds on TLC plates was achieved by exposure to ultraviolet light. Column chromatography was executed using Fischer Chemical 40-63 m, 230-400 mesh silica gel. Preparative gel-permeation chromatography (prep-GPC) was performed on a JAI Preparative Recycling HPLC (LaboACE-LC-5060) system equipped with 2.5HR and 2HR columns in series (20 mm ID600 mm length) using chloroform as the eluent.

General Materials Information

[0320] Unless otherwise noted, all reagents and starting materials were purchased from commercial vendors (Millipore-Sigma, Alfa Aesar, Strem, Ambeed, Beantown Chemical, Apollo Scientific, or Matrix Scientific) and used as received. Anhydrous THF, DMF, and toluene were purchased from Millipore-Sigma, packaged in Sure/Seal bottles, and used as received. Deuterated chloroform (CDCl.sub.3) and deuterated dichloromethane (CD.sub.2Cl.sub.2) were purchased from Cambridge Isotope Laboratories (CIL). Deuterated toluene (Tol-d8) was purchased from either CIL or Millipore-Sigma. It was dried over and distilled from CaH.sub.2, degassed by four freeze-pump-thaw cycles, then stored in a glovebox over activated 4 molecular sieves. Methyl methacrylate (MMA) was purchased from Millipore-Sigma. It was dried and had its stabilizer removed by passing it through a column of activated alumina, then degassed by four freeze-pump-thaw cycles, and stored in the dark in a freezer inside a glovebox; it was used within 1 month. .sup.1H NMR after 1 month of storage indicated no observable loss of quality. 1,1-Azobis(cyclohexanecarbonitrile) (ACHN) was recrystallized from absolute ethanol as colorless crystals and were stored either in a fridge (2 C.) or a freezer inside a glovebox.

General Analytical Information

[0321] NMR spectra were recorded on either Bruker AVANCE III DRX 400 or Neo 500 spectrometers at room temperature. Proton (.sup.1H) chemical shifts are indicated in ppm and were calibrated to residual solvent peaks (CDCl.sub.3: 7.26 ppm, CD.sub.2Cl.sub.2: 5.32 ppm, Tol-d8: 2.08 ppm). All carbon (.sup.13C) NMR recordings were proton-decoupled and their chemical shifts are also shown in ppm, referenced to the solvent's carbon resonance (CDCl.sub.3: 77.16 ppm). Fluorine (.sup.19F) chemical shifts are also shown in ppm but are not referenced to a particular resonance. All NMR data were analyzed and processed using MestReNOVA. Quantitative .sup.1H NMR spectroscopy was performed using 1,4-bis(trimethylsilyl)benzene, 1,1,2,2-tetrachloroethane, or dibromomethane as an internal standard. High-resolution mass spectra were recorded on JEOL AccuTOF 4G equipped with an ionSense DART. Analytical size exclusion chromatography (SEC) was performed on a Tosoh EcoSEC HLC-8320 with dual TSKgel SuperH3000 columns and an ethanol-stabilized chloroform mobile phase. Samples were filtered through 0.2 m PTFE syringe filters before injection into the instrument. Molar mass values were calculated according to linear polymethylmethacrylate calibration standards. Thermal Gravimetric Analysis (TGA) studies were performed on samples of approximately 2-5 mg. The analyses were conducted using a TGA/DSC 2 STAR System (Mettler-Toledo) equipped with a Gas Controller GC 200 Star System. The studies were carried out with a temperature ramp of 10 C./minute. Differential Scanning Calorimetry (DSC) analyses were conducted using a TGA/DSC 2 STAR System (Mettler-Toledo), equipped with an RCS1-3277 DSC cell and a DSC1-0107 cooling system. Each sample, weighing about 3-6 mg, was sealed in an aluminum pan and subjected to three heating/cooling cycles ranging from 40 C. to 140 C. at a rate of 10 C./minute. The glass transition temperatures (T.sub.g) were recorded from the second heating ramp. DSC traces from the second and third heating cycles were identical for all samples reported in this example. Rectangular bars of vPMMA, dPMMA(2.5), and dPMMA(5.0) for DMA were prepared through compression molding. Circular samples were created by iteratively filling a disk with a diameter of 30 mm and a thickness of 0.51 mm with pulverized polymer and pressing it at 5 tons of pressure and 135 C. for 30 minutes. This process was repeated three times to produce a transparent circular polymer disk. Rectangular bars were then cut from this disk and sanded to achieve uniformity. DMA was performed on a Discovery DMA 850 System (TA). Samples were tested in tensile mode. Measurements were recorded at a frequency of 1.0 Hz and an amplitude of 1.0 m from 40-150 C. at a ramp rate of 2 C./minute with a data sampling interval of 3 s/pt, using a 125% force tracking and 0.01 N preload force. Data were collected using Trios software and exported to Microsoft Excel for analysis.

Simulation Details

Generation of Contour Plots (FIG. 17A and FIG. 21)

[0322] Monte Carlo copolymerization simulations were conducted, targeting an average chain length of 1000 monomers and simulating a total of 4000 chains. To generate the contour plots, 625 pairs of reactivity ratios were simulated. This covered all combinations of 25 different r.sub.M values, chosen at equal intervals in logspace(1, 1), and r.sub.CC values, chosen at equal intervals in logspace(2, 2) for FIG. 17A or logspace (3, 3) for FIG. 21. The data were interpolated to create a gradient illustration.

[0323] For each combination of reactivity ratios, a Monte Carlo simulation of the copolymerization process was conducted based on the Mayo-Lewis model. This involved generating a polymer array to represent the composition of each polymer chain. The chains were initialized with a monomer chosen based on the initial monomer amounts. The type of addition to occur was randomly selected based on the cumulative sum of propagation probabilities, which was calculated by considering the current amounts of monomers and the reactivity ratios. Depending on the reaction type, a polymer chain was randomly chosen for propagation. The selected chain was extended by adding either M or CC. After each addition, the length, molecular weight, and terminal monomer identity of the chain, and the remaining amount of each monomer were updated. The propagation probabilities were recalculated to reflect the new composition of the monomer pool and the current terminal monomer of each chain. The simulation continued until the predetermined number of monomers had reacted. For each polymer chain in the array, the runs of monomers (repeated elements), their lengths, and their values were analyzed using a predefined function. The weight-average molecular weight of the nondegradable segments was calculated based on the lengths of consecutive Ms.

[0324] Using the surfc function, a surface plot was generated to represent the decrease in polymer molecular weight after degradation across different combinations of reactivity ratios. For enhanced visualization, the axes were set to a logarithmic scale.

Generation of Linear Sequences (FIG. 17B)

[0325] For each pair of reactivity ratios, a Monte Carlo simulation of the copolymerization process was conducted based on the Mayo-Lewis model. A polymer array was generated to represent a polymer chain. The chain was initialized with a monomer chosen based on the initial monomer amounts. The type of reaction to occur was randomly selected based on the cumulative sum of propagation probabilities, which was calculated by considering the current amounts of monomers and the reactivity ratios. Depending on the reaction type, the chain was extended by adding either M or CC. After each addition, the remaining amount of each monomer was updated. The propagation probabilities were recalculated to reflect the new composition of the monomer pool and the current terminal monomer of the chain. The simulation continued until the predetermined number of monomers had reacted.

Computational Details

General Computational Information

[0326] All Density Functional Theory (DFT) calculations were carried out using ORCA 5.0.4..sup.108 Geometry optimizations were performed using Head-Gordon's wB97X hybrid functional,.sup.109 supplemented with Grimme's D3 dispersion correction (wB97X-D3)..sup.110 All intermediate and transition state geometries were optimized using the def2-SVP basis set..sup.111,112 The Resolution of Identity and Chain-of-Spheres (RIJCOSX) approximation was applied,.sup.113,114 as implemented in ORCA 5.0.4, in conjunction with an auxiliary basis set, def2/J, to accelerate the calculations without a noticeable compromise in accuracy. Energies of the optimized geometries were reevaluated through single-point calculations using a triple-(quality basis set, def2-TZVP. Harmonic vibrational frequencies were computed at the wB97X/def2-SVP level of theory to ensure proper convergence to well-defined minima for ground states or first-order saddle points for transition states. Zero-point energy (ZPE) and thermal vibrational corrections were derived from these vibrational frequency calculations, with the latter specifically determined at a temperature of 373K. Solvation effects were accounted for using the Conductor-like Polarizable Continuum Model (CPCM).sup.115,116 based on the optimized gas-phase geometries. A dielectric constant of 2.4 and a refractive index of 1.497 for toluene were incorporated into the calculations.

TABLE-US-00001 TABLE 1 Summary of Computed Energy Components E_el/(kcal/mol) ZPE/(kcal/mol) non-ZPE vib/(kcal/mol) def2-TZVP, CPCM(Tol) def2-SVP def2-SVP, T = 373K G_solv/(kcal/mol) MMA 217011.2796 78.18 4.99 216928.1096 1 217377.6753 84.05 5.78 217287.8453 M1 434411.423 165.65 13 434232.773 TS-M1 434385.7071 163.44 13.33 434208.9371 DOT 635652.7453 128.13 9.03 635515.5853 MeDOT 660327.9664 145.59 10.43 660171.9464 Me.sub.2DOT 684997.9265 162.97 11.8 684823.1565 PhDOT 780648.3448 179.35 13.53 780455.4648 D1 for DOT 853042.1541 214.34 17.5 852810.3141 D1 for MeDOT 877717.2748 232.03 18.83 877466.4148 D1 for Me.sub.2DOT 902388.1159 249.29 20.25 902118.5759 D1 for PhDOT 998038.0908 265.39 22.15 997750.5508 D2 for DOT 853038.4696 211.41 18.72 852808.3396 D2 for MeDOT 877717.2644 232.05 18.82 877466.3944 D2 for Me.sub.2DOT 902392.7139 247.21 21.42 902124.0839 D2 for PhDOT 998048.2099 263.67 22.87 997761.6699 TS-D1 for DOT 853027.9183 213.07 17.71 852797.1383 TS-D1 for MeDOT 877703.1711 230.33 19.18 877453.6611 TS-D1 for Me.sub.2DOT 902370.5572 248.2 20.26 902102.0972 TS-D1 for PhDOT 998025.694 264.11 22.26 997739.324 TS-D2 for DOT 853018.7575 212 17.72 852789.0375 TS-D2 for MeDOT 877695.5438 229.82 19.14 877446.5838 TS-D2 for Me.sub.2DOT 902370.5572 247.56 20.32 902102.6772 TS-D2 for PhDOT 998022.769 263.73 21.65 997737.389 DM1 1070084.223 293.64 26.17 1069764.413 TS-DM1 1070053.616 291.15 26.35 1069736.116 MM1 651439.5093 246.8 19.86 661172.8493 TS-MM1 651418.3992 244.93 20.74 651152.7292

Synthesis and Characterization of Monomers

Summary of Synthesis

[0327] FIGS. 25-30 summarize the synthesis of MeDOT and PhDOT (FIG. 25), Me.sub.2DOT (FIG. 26), p-MePhDOT (FIG. 27), p-CF.sub.3PhDOT (FIG. 28), F-p-CF.sub.3PhDOT (FIG. 29), and PFPhDOT (FIG. 30).

Synthetic Procedures

Synthesis and Characterization of 2-vinyl-[1,1-biphenyl]-2-carbaldehyde (S3)

##STR00035##

[0328] The following is a modified version of the procedure reported by the Buchwald group..sup.117 In an oven-dried 250 mL round-bottom flask equipped with a magnetic stir bar were sequentially added Sphos Pd G3 (780 mg, 1 mmol, 0.02 equiv), 2-formyl phenylboronic acid (9.75 g, 65 mmol, 1.3 equiv), and K.sub.2CO.sub.3 (20.7 g, 150 mmol, 3.0 equiv) inside a nitrogen-filled glovebox. The flask was tightly sealed with a rubber septum and removed from the glovebox. Separately, a mixture of THF (90 mL) and water (30 mL) was purged with argon for 40 minutes in a Schlenk flask to remove oxygen. This mixture was then transferred into the round-bottom flask via cannula transfer. Next, 2-bromostyrene (6.3 mL, 50 mmol, 1.0 equiv) was added to the flask via syringe under a nitrogen flow. The resulting mixture was stirred vigorously in an oil bath preheated to 60 C. overnight. Afterward, the flask was removed from the oil bath and allowed to cool to room temperature. The reaction mixture was then filtered through a silica pad, which was washed with additional ethyl acetate to elute the product. The combined filtrate was dried over Na.sub.2SO.sub.4 and concentrated under reduced pressure using a rotary evaporator. The crude residue was purified by column chromatography on silica gel using EA:Hex=1:30 as the eluent. The product was obtained as a pale-yellow oil, which solidified into a waxy form after being placed under vacuum overnight (10.27 g, 98.6% yield).

[0329] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.72 (d, J=0.8 Hz, 1H), 8.04 (dd, J=7.8, 1.4 Hz, 1H), 7.66 (ddd, J=16.8, 7.7, 1.4 Hz, 2H), 7.56-7.48 (m, 1H), 7.43 (td, J=7.6, 1.5 Hz, 1H), 7.40-7.31 (m, 2H), 7.28-7.22 (m, 1H), 6.41 (dd, J=17.5, 11.0 Hz, 1H), 5.68 (dd, J=17.4, 1.1 Hz, 1H), 5.17 (dd, J=11.0, 1.1 Hz, 1H).

[0330] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 192.24, 144.67, 137.09, 136.45, 134.78, 134.32, 133.68, 131.35, 130.81, 128.66, 128.15, 127.67, 127.20, 125.45, 116.40.

[0331] HRMS (DART-TOF) C.sub.15H.sub.12O [M+H].sup.+ calcd: 209.09609 found: 209.09623.

Synthesis and Characterization of 7-methyldibenzo[c,e]oxepin-5(7H)-one (S6, MeDOO)

##STR00036##

[0332] To a 40 mL scintillation vial equipped with a magnetic stir bar was added 2-vinyl-[1,1-biphenyl]-2-carbaldehyde (S3, 1.5 g, 7.2 mmol, 1.0 equiv). The vial was sealed with a penetrable cap, then evacuated and backfilled with nitrogen four times. Anhydrous THF (24 mL) was then added against a nitrogen flow, after which the vial was cooled in an ice bath. A 3 M solution of MeMgBr in Et.sub.2O (2.88 mL, 8.64 mmol, 1.2 equiv) was added dropwise into the vial at 0 C. Upon addition, a white insoluble solid formed in the vial. The resulting mixture was stirred at 0 C. for an additional 30 minutes and then at room temperature for 4 hours. The insoluble solid disappeared upon warming to room temperature, and the mixture turned yellow. The reaction was quenched by the addition of water (2 mL), followed by a saturated aqueous solution of NH.sub.4Cl (2 mL). The mixture was then transferred to a separatory funnel, to which additional saturated NH.sub.4Cl solution (60 mL) was added, and subsequently extracted three times with EtOAc (350 mL). The combined organic layers were dried over Na.sub.2SO.sub.4 and concentrated under reduced pressure using a rotary evaporator. The resulting pale-yellow oil was used for the subsequent reaction without further purification.

[0333] The pale-yellow oil was transferred to a 40 mL scintillation vial and kept under vacuum overnight. After the addition of Oxone (8.85 g, 28.8 mmol, 4.0 equiv), the vial was sealed with a penetrable cap, evacuated, and backfilled with nitrogen four times. Anhydrous DMF (8 mL) was then introduced into the vial against a nitrogen flow. The resulting mixture was vortexed for one minute. Subsequently, a 2.5 wt % OsO.sub.4 solution in t-BuOH (1.875 mL, 0.144 mmol, 0.02 equiv) was added dropwise to the vial while stirring vigorously. The mixture turned into a brown-black slurry and generated heat. It was allowed to stir at room temperature for 14 hours. Water (10 mL) was then added, and the mixture was transferred to a separatory funnel. Brine (50 mL) was added, followed by extractions with EtOAc (340 mL). The combined organic layers were washed thoroughly with an aqueous solution of Na.sub.2SO.sub.3 (280 mL) to quench residual OsO.sub.4 and then washed with brine (280 mL) to remove residual DMF. The mixture was dried over Na.sub.2SO.sub.4 and concentrated under reduced pressure using a rotary evaporator. The crude residue was purified by column chromatography on silica gel using EA:Hex=1:7 as the eluent. The product was obtained as a white solid (731.6 mg, 45.3% yield over 2 steps).

[0334] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.98 (dd, J=7.8, 1.4 Hz, 1H), 7.66 (td, J=7.6, 1.4 Hz, 1H), 7.59 (td, J=6.2, 3.2 Hz, 2H), 7.51 (dddd, J=18.7, 12.9, 7.4, 1.6 Hz, 4H), 5.28 (q, J=6.6 Hz, 1H), 1.84 (d, J=6.6 Hz, 3H).

[0335] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 170.04, 138.71, 137.60, 137.40, 132.60, 131.36, 130.94, 129.64, 129.02, 128.88, 128.63, 128.43, 124.00, 73.18, 16.94.

[0336] HRMS (DART-TOF) C.sub.15H.sub.12O.sub.2[M+H].sup.+ calcd: 225.09101 found: 225.09131.

Synthesis and Characterization of 7-methyldibenzo[c,e]oxepine-5(7H)-thione (S6, MeDOT)

##STR00037##

[0337] To a 20 mL scintillation vial equipped with a magnetic stir bar were added 7-methyldibenzo[c,e]oxepin-5(7H)-one (S6, 731.6 mg, 3.26 mmol, 1.0 equiv) and Lawesson's reagent (857.7 mg, 2.12 mmol, 0.65 equiv). The vial was sealed with a penetrable cap and evacuated, then backfilled with nitrogen four times. Anhydrous toluene (6 mL) was added via syringe, and the mixture was stirred at 100 C. for 6 hours, during which the color turned orange. The mixture was allowed to cool to room temperature and filtered through a short pad of silica gel. The pad was washed with additional EtOAc to collect the yellow product. The combined filtrates were concentrated under reduced pressure using a rotary evaporator and kept under vacuum for several hours to remove residual solvent. The crude residue was purified by column chromatography on silica gel, using a gradient from EA:Hex=1:30 to 1:20 (R.sub.f=0.25 for EA:Hex=1:20). The product was obtained as a yellow solid (430.2 mg, 54.9% yield).

[0338] .sup.1H NMR (400 MHz, CDCl.sub.3) 8.18 (dd, J=7.9, 1.4 Hz, 1H), 7.66-7.58 (m, 2H), 7.58-7.42 (m, 5H), 5.41 (q, J=6.6 Hz, 1H), 1.96 (d, J=6.6 Hz, 3H).

[0339] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 215.86, 139.59, 138.87, 137.35, 134.79, 133.47, 132.10, 129.93, 128.88, 128.79, 128.76, 128.20, 123.93, 78.74, 16.84.

[0340] HRMS (DART-TOF) C.sub.15H.sub.12OS [M+H].sup.+ calcd: 241.06816 found: 241.06874.

Synthesis and Characterization of 7-phenyldibenzo[c,e]oxepin-5(7H)-one (S7, PhDOO)

##STR00038##

[0341] 2-Vinyl-[1,1-biphenyl]-2-carbaldehyde (S3, 1.451 g, 6.97 mmol, 1.0 equiv) was weighed into a 40 mL scintillation vial equipped with a magnetic stir bar. The vial was sealed with a penetrable cap, then evacuated and backfilled with nitrogen four times. Anhydrous THF (23 mL) was added against a nitrogen flow to completely dissolve the starting material. The mixture was cooled to 0 C. in an ice bath. A 1.6 M solution of phenyl magnesium bromide in cyclopentyl methyl ether (5.23 mL, 8.36 mmol, 1.2 equiv) was added dropwise under stirring. The resulting mixture was stirred at 0 C. for an additional 30 minutes and then allowed to stir at room temperature for 4 hours. The reaction was quenched by the addition of water (5 mL), followed by a saturated aqueous solution of NH.sub.4Cl (60 mL). The aqueous layer was extracted with EtOAc (350 mL). The combined organic layers were dried over Na.sub.2SO.sub.4 and concentrated under reduced pressure using a rotary evaporator. The crude residue was purified by column chromatography on silica gel using EA:Hex=1:8 as the eluent (R.sub.f=0.20-0.34 for EA:Hex=1:7). All fractions containing the product were collected and the solvent was removed. The resulting colorless oil was used for the subsequent reaction.

[0342] The colorless oil was transferred into a 40 mL scintillation vial and kept under vacuum overnight. After the addition of Oxone (7.98 g, 26.0 mmol, 4.0 equiv), the vial was sealed with a penetrable cap and charged with nitrogen. Anhydrous DMF (20 mL) was added via syringe against a nitrogen flow, and the mixture was stirred vigorously until the colorless oil fully homogenized with the solvent. The mixture was then cooled to 0 C. in an ice bath. A 2.5 wt % OsO.sub.4 solution in t-BuOH (1.27 mL, 0.097 mmol, 0.015 equiv) was added dropwise into the vial at 0 C. The resulting mixture was allowed to warm slowly to room temperature and stirred for 13 hours, turning yellow in the process. Water (10 mL) was added, and the mixture was transferred to a separatory funnel. Brine (50 mL) was then added, and the mixture was extracted with EtOAc (340 mL). The combined organic layers were washed thoroughly with an aqueous solution of Na.sub.2SO.sub.3 (280 mL) to quench residual OsO.sub.4 and then washed with brine (280 mL) to remove residual DMF. The mixture was dried over Na.sub.2SO.sub.4 and concentrated under reduced pressure using a rotary evaporator. The crude residue was purified by column chromatography on silica gel, using a gradient from EA:Hex=1:10 to EA:Hex=1:7 (R.sub.f=0.28 for EA:Hex=1:7). The product was obtained as a foamy white solid (857.6 mg, 43.0% yield over 2 steps).

[0343] .sup.1H NMR (400 MHz, CDCl.sub.3) 8.03 (d, J=7.8 Hz, 1H), 7.70 (ddd, J=20.6, 14.0, 7.6 Hz, 3H), 7.61-7.54 (m, 1H), 7.54-7.39 (m, 6H), 7.29 (t, J=7.6 Hz, 1H), 6.80 (d, J=7.8 Hz, 1H), 6.25 (s, 1H).

[0344] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 169.56, 138.74, 138.64, 137.47, 135.92, 132.85, 131.63, 130.93, 129.71, 129.07, 128.95, 128.72, 128.69, 128.62, 128.57, 127.56, 127.14, 79.16.

[0345] HRMS (DART-TOF) C.sub.20H.sub.14O.sub.2[M+H].sup.+ calcd: 287.10666 found: 287.10901.

Synthesis and Characterization of 7-phenyldibenzo[c,e]oxepine-5(7H)-thione (S9, PhDOT)

##STR00039##

[0346] To a 40 mL scintillation vial equipped with a magnetic stir bar were added 7-phenyldibenzo[c,e]oxepin-5(7H)-one (S7, 857.6 mg, 3.00 mmol, 1.0 equiv) and Lawesson's reagent (787.4 mg, 1.95 mmol, 0.65 equiv). The vial was sealed with a penetrable cap, then evacuated and backfilled with nitrogen four times. After adding anhydrous toluene (5 mL), the mixture was stirred at 100 C. for 4 hours until the color of the mixture turned orange. The mixture was allowed to cool to room temperature and then filtered through a short pad of silica gel. The pad was washed with additional EtOAc to elute and collect the yellow product. The combined filtrates were concentrated under reduced pressure using a rotary evaporator and were kept under vacuum for a few hours to remove residual solvent. The crude residue was purified by column chromatography on silica gel, using a gradient from EA:Hex=1:40 to 1:30 (R.sub.f=0.25 for EA:Hex=1:20). All fractions containing the product were collected. The unreacted starting material was recovered (342 mg, 39.9% recovery yield) from the column using EA:Hex=1:7 as the eluent (R.sub.f=0.13 for EA:Hex=1:20). This recovered material was resubjected to the same thionation condition using Lawesson's reagent (289.9 mg, 0.717 mmol, 0.6 equiv) and toluene (4 mL) as the solvent. The resulting crude mixture was purified following the aforementioned workup procedure and a column chromatography using EA:Hex=1:30 as the eluent. Fractions containing the desired product were collected and combined with those from the first column. The combined fractions were concentrated under reduced pressure using a rotary evaporator and subjected to another round of column chromatography on silica gel, using a gradient from Hex:DCM=4:1 to Hex:DCM=2:1 (R.sub.f=0.28 for Hex:DCM=2:1). The product was obtained as a yellow crystalline solid (175 mg, 19.1% overall yield).

[0347] .sup.1H NMR (400 MHz, CDCl.sub.3) 8.22 (dd, J=7.9, 1.4 Hz, 1H), 7.67 (ddd, J=8.9, 4.8, 2.6 Hz, 2H), 7.59 (dt, J=7.4, 1.8 Hz, 3H), 7.54-7.42 (m, 5H), 7.31 (td, J=7.6, 1.2 Hz, 1H), 6.84 (d, J=7.8 Hz, 1H), 6.35 (s, 1H).

[0348] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 214.88, 139.49, 138.74, 138.42, 135.23, 134.75, 133.66, 132.25, 129.88, 128.91, 128.86, 128.79, 128.73, 128.65, 128.38, 127.74, 126.90, 84.30.

[0349] HRMS (DART-TOF) C.sub.20H.sub.14OS [M+H].sup.+ calcd: 303.08381 found: 303.08413.

Synthesis and Characterization of methyl 2-vinyl-[1,1-biphenyl]-2-carboxylate (S11)

##STR00040##

[0350] To an oven-dried 250 mL round-bottom flask were sequentially added Sphos Pd G3 (312.1 mg, 0.4 mmol, 0.021 equiv), 2-methoxycarbonyl phenylboronic acid (4.38 g, 24.34 mmol, 1.3 equiv), and K.sub.2CO.sub.3 (7.76 g, 56.16 mmol, 3.0 equiv) inside a nitrogen-filled glovebox. The flask was then tightly sealed with a rubber septum and removed from the glovebox. Anhydrous THF (45 mL) and 2-bromostyrene (2.35 mL, 18.72 mmol, 1.0 equiv) were added via syringe to the flask under a nitrogen atmosphere. The resulting mixture was stirred vigorously in a preheated oil bath at 60 C. for 24 hours. Afterward, the flask was removed from the oil bath and allowed to cool to room temperature. The resulting grey slurry was filtered through a pad of silica gel, which was subsequently washed with additional ethyl acetate to elute the product. The combined filtrate was dried over Na.sub.2SO.sub.4 and concentrated under reduced pressure using a rotary evaporator. The crude residue was then purified by column chromatography on silica gel, using EA:Hex=1:30 as the eluent (R.sub.f=0.22 for EA:Hex=1:30). The product was obtained as a colorless oil (3.80 g, 85.2% yield).

[0351] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.98 (dd, J=7.8, 1.4 Hz, 1H), 7.65 (dd, J=7.8, 1.5 Hz, 1H), 7.57 (td, J=7.5, 1.4 Hz, 1H), 7.46 (td, J=7.6, 1.3 Hz, 1H), 7.42-7.25 (m, 3H), 7.17 (dd, J=7.4, 1.6 Hz, 1H), 6.46 (dd, J=17.5, 11.0 Hz, 1H), 5.66 (dd, J=17.4, 1.3 Hz, 1H), 5.13 (dd, J=11.0, 1.2 Hz, 1H), 3.61 (s, 3H).

[0352] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 167.97, 141.94, 140.51, 135.82, 135.22, 131.61, 131.58, 131.15, 130.07, 129.23, 127.62, 127.47, 127.35, 124.82, 114.93, 52.09.

[0353] HRMS (DART-TOF) C.sub.16H.sub.14O.sub.2[M+H].sup.+ calcd: 239.10666 found: 239.10659.

Synthesis and Characterization of 2-(2-vinyl-[1,1-biphenyl]-2-yl)propan-2-ol (S12)

##STR00041##

[0354] Methyl 2-vinyl-[1,1-biphenyl]-2-carboxylate (S11, 3.25 g, 13.6 mmol, 1.0 equiv) was weighed into a flame-dried 250 mL round-bottom flask equipped with a magnetic stir bar. The flask was sealed with a rubber septum and then evacuated and backfilled with nitrogen four times. Anhydrous THF (48 mL) was added to the flask against a nitrogen flow. The flask was placed in an ice bath, and a 3 M solution of MeMgBr in diethyl ether (18.2 mL, 54.6 mmol, 4.0 equiv) was added dropwise via syringe at 0 C. The resulting light grey mixture was stirred at 0 C. for an additional 30 minutes, and then at room temperature for 7 hours and 30 minutes. To quench the reaction, water (10 mL) and a saturated solution of NH.sub.4Cl (20 mL) were added to the resulting yellow solution. The THF was evaporated to a minimal volume under reduced pressure using a rotary evaporator. The mixture was then transferred to a separatory funnel and further extracted with EtOAc (3100 mL), following the addition of a saturated aqueous solution of NH.sub.4Cl (80 mL). The combined organic layers were dried over Na.sub.2SO.sub.4 and subsequently concentrated using a rotary evaporator. The crude residue was purified by column chromatography on silica gel, using a gradient from EA:Hex=1:10 to 1:8 (R.sub.f=0.33 for EA:Hex=1:7). The product was obtained as a white waxy solid (2.56 g, 78.8% yield).

[0355] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.70 (dd, J=8.0, 1.3 Hz, 2H), 7.46-7.35 (m, 2H), 7.35-7.20 (m, 3H), 7.02 (dd, J=7.5, 1.5 Hz, 1H), 6.43 (dd, J=17.6, 11.0 Hz, 1H), 5.68 (dd, J=17.6, 1.2 Hz, 1H), 5.14 (dd, J=11.0, 1.2 Hz, 1H), 1.77 (s, 1H), 1.46 (d, J=28.0 Hz, 6H).

[0356] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 146.60, 142.26, 138.00, 136.24, 135.62, 132.20, 130.33, 127.74, 127.66, 127.04, 126.36, 126.32, 124.87, 114.68, 74.12, 32.42, 32.14.

[0357] HRMS (DART-TOF) C.sub.17H.sub.18O [M+H-H.sub.2O].sup.+ calcd: 221.13248 found: 221.13108.

Synthesis and Characterization of 7,7-dimethyldibenzo[c,e]oxepin-5(7H)-one (S13, Me.SUB.2.DOO)

##STR00042##

[0358] To a flame-dried 100 mL round-bottom flask were added 2-(2-vinyl-[1,1-biphenyl]-2-yl)propan-2-ol (S12, 2.56 g, 10.7 mmol, 1.0 equiv) and Oxone (13.2 g, 43.0 mmol, 4.0 equiv). The flask was sealed with a rubber septum, then evacuated and backfilled with nitrogen four times. Anhydrous DMF (30 mL) was subsequently added, and the mixture was cooled to 0 C. in an ice bath while being stirred vigorously. A 2.5 wt % OsO.sub.4 solution in t-BuOH (2.1 mL, 0.16 mmol, 0.015 equiv) was added dropwise to the flask at 0 C. The resulting black mixture was stirred at 0 C. for an additional 30 minutes before being allowed to slowly warm to room temperature. The mixture was stirred vigorously for 13 hours at room temperature, during which it eventually turned yellow. After addition of water (30 mL), the mixture was transferred to a separatory funnel. Brine was then added (90 mL), and the mixture was extracted with EtOAc (380 mL). The combined organic layers were washed thoroughly with an aqueous solution of Na.sub.2SO.sub.3 (2160 mL) to quench residual OsO.sub.4 and then washed with brine (2160 mL) to remove residual DMF. The mixture was dried over Na.sub.2SO.sub.4 and concentrated under reduced pressure using a rotary evaporator. The crude residue was purified by column chromatography on silica gel, using a gradient from EA:Hex=1:10 to 1:7. The product was obtained as a white solid (1.224 g, 47.8%).

[0359] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.97 (dd, J=7.7, 1.4 Hz, 1H), 7.66 (td, J=7.6, 1.5 Hz, 1H), 7.57 (dd, J=7.4, 1.4 Hz, 2H), 7.54 (dd, J=7.7, 1.4 Hz, 1H), 7.51-7.45 (m, 2H), 7.42 (td, J=7.6, 1.5 Hz, 1H), 1.70 (s, 6H).

[0360] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 169.28, 141.52, 139.01, 137.44, 132.93, 131.65, 131.61, 130.92, 129.35, 129.20, 128.57, 128.27, 125.15, 81.82.

[0361] HRMS (DART-TOF) C.sub.16H.sub.14O.sub.2[M+H].sup.+ calcd: 239.10666 found: 239.10696.

Synthesis and Characterization of 7,7-dimethyldibenzo[c,e]oxepine-5(7H)-thione (S14, M e.SUB.2.DOT)

##STR00043##

[0362] To a 40 mL scintillation vial equipped with a magnetic stir bar were added 7,7-dimethyldibenzo[c,e]oxepin-5(7H)-one (S13, 1.008 g, 4.23 mmol, 1.0 equiv) and Lawesson's reagent (1.027 g, 2.54 mmol, 0.6 equiv). The vial was sealed with a penetrable cap, then evacuated and backfilled with nitrogen four times. After adding anhydrous THF (14 mL), the mixture was stirred at 60 C. for 10 hours. The mixture turned yellow after 10 hours of reaction. The reaction mixture was allowed to cool to room temperature and then filtered through a short pad of silica gel. The pad was washed with additional EtOAc to elute and collect the yellow product. The combined filtrates were concentrated under reduced pressure using a rotary evaporator. The crude residue was purified by column chromatography on silica gel, using EA:Hex=1:20 as the eluent (R.sub.f=0.41 for EA:Hex=1:7). All fractions containing the product were collected. The unreacted starting material was recovered (776.7 mg, 77.0% recovery yield) from the column using EA:Hex=1:7 as the eluent (R.sub.f=0.24 for EA:Hex=1:7). This recovered material was resubjected to the same thionation condition using Lawesson's reagent (791 mg, 1.96 mmol, 0.6 equiv) and THF (10.5 mL) as the solvent. The resulting crude mixture was purified following the aforementioned workup procedure and column chromatography using EA:Hex=1:20 as the eluent. The unreacted starting material was again recovered (552.4 mg, 54.8% overall recovery yield) from the column using EA:Hex=1:7 as the eluent. Fractions containing the desired product were collected and combined with those from the first column. The combined fractions were concentrated under reduced pressure using a rotary evaporator. The residue was then subjected to another round of column chromatography on silica gel, using a gradient from Hex:DCM=4:1 to 2:1 (R.sub.f=0.49 for Hex:DCM=1:1). The product was obtained as a yellow solid (72.8 mg, 6.8% overall yield).

[0363] .sup.1H NMR (400 MHz, CDCl.sub.3) 8.18 (dd, J=7.9, 1.4 Hz, 1H), 7.62-7.54 (m, 2H), 7.54-7.37 (m, 5H), 2.06 (s, 3H), 1.46 (s, 3H).

[0364] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 215.77, 141.19, 139.60, 137.31, 136.04, 133.74, 132.28, 130.55, 129.49, 128.90, 128.56, 127.88, 124.89, 87.97, 29.78.

[0365] HRMS (DART-TOF) C.sub.16H.sub.14OS [M+H].sup.+ calcd: 255.08381 found: 255.08401.

Synthesis and Characterization of 7-(p-tolyl)dibenzo[c,e]oxepin-5(7H)-one (516, p-MePhDOO)

##STR00044##

[0366] To a flame-dried 250 mL round-bottom flask equipped with a magnetic stir bar was added 2-vinyl-[1,1-biphenyl]-2-carbaldehyde (S3, 10.95 g, 52.6 mmol, 1.0 equiv). The flask was sealed with a rubber septum, then evacuated and backfilled with nitrogen four times. Anhydrous THF (80 mL) was added, and the mixture was stirred at room temperature until the starting material had fully dissolved. The mixture was then cooled to 0 C. in an ice bath. 0.5 M p-Tolylmagnesium bromide solution in Et.sub.2O (126.2 mL, 63.1 mmol, 1.2 equiv) was added dropwise while stirring over a period of 30 minutes. The resulting mixture was allowed to stir at 0 C. for an additional 30 minutes, and then stirred at room temperature for 8 hours. The reaction was quenched by the addition of water (10 mL), followed by a saturated aqueous solution of NH.sub.4Cl (150 mL). The aqueous layer was extracted with EtOAc (3100 mL). The combined organic layers were dried over Na.sub.2SO.sub.4 and concentrated under reduced pressure using a rotary evaporator. The crude residue was purified by column chromatography on silica gel, using a gradient from EA:Hex=10:1 to 7:1. All fractions containing the product were collected and the solvent was removed. The resulting viscous, colorless oil was used for the subsequent reaction.

[0367] The viscous, colorless oil was transferred into a 250 mL round-bottom flask equipped with a magnetic stir bar and kept under vacuum overnight. After the addition of Oxone (64.6 g, 210.3 mmol, 4.0 equiv), the flask was sealed with a rubber septum and charged with nitrogen. Anhydrous DMF (79 mL) was added via syringe against a nitrogen flow, and the resulting mixture was stirred vigorously until the colorless oil had fully homogenized with the solvent. The mixture was then cooled to 0 C. in an ice bath. A 2.5 wt % OsO.sub.4 solution in t-BuOH (5.48 mL, 0.42 mmol, 0.008 equiv) was added dropwise to the flask at 0 C. The resulting black mixture was stirred at 0 C. for an additional 30 minutes and then allowed to stir overnight at room temperature. The mixture eventually turned yellow. After the addition of water (50 mL), the mixture was transferred to a separatory funnel, brine (100 mL) was added, and the aqueous layer was extracted with EtOAc (3100 mL). The combined organic layers were thoroughly washed with an aqueous solution of Na.sub.2SO.sub.3 (2200 mL) to quench residual OsO.sub.4 and then washed with water (2200) and brine (2200 mL) to remove residual DMF. The mixture was dried over Na.sub.2SO.sub.4 and then concentrated under reduced pressure using a rotary evaporator. The crude residue was purified by column chromatography on silica gel, using a gradient from EA:Hex=1:10 to 1:9. The product was obtained as a foamy white solid. (5.275 g, 33.4% yield over 2 steps)

[0368] .sup.1H NMR (400 MHz, CDCl.sub.3) 8.03 (d, J=7.7 Hz, 1H), 7.77-7.62 (m, 3H), 7.60-7.53 (m, 1H), 7.48 (t, J=7.6 Hz, 1H), 7.40 (d, J=7.7 Hz, 2H), 7.28 (d, J=7.8 Hz, 3H), 6.83 (d, J=7.8 Hz, 1H), 6.23 (s, 1H), 2.43 (s, 3H).

[0369] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 169.61, 138.84, 138.53, 138.33, 137.43, 132.84, 132.77, 131.54, 130.92, 129.60, 129.31, 129.01, 128.86, 128.62, 128.49, 127.42, 127.10, 79.13, 21.35.

[0370] HRMS (DART-TOF) C.sub.21H.sub.16O.sub.2[M+H].sup.+ calcd: 301.12231 found: 301.12200.

Synthesis and Characterization of 7-(p-tolyl)dibenzo[c,e]oxepine-5(7H)-thione (S17, p-MePhDOT)

##STR00045##

[0371] To a flame-dried 250 mL round-bottom flask equipped with a magnetic stir bar were added 7-(p-tolyl)dibenzo[c,e]oxepin-5(7H)-one (S16, 5.275 g, 17.6 mmol, 1.0 equiv) and Lawesson's reagent (4.262 g, 10.5 mmol, 0.6 equiv). The flask was sealed with a rubber septum and purged with nitrogen. Anhydrous THF (40 mL) was then added, and the resulting mixture was stirred in an oil bath preheated to 65 C. for 42 hours. The flask was removed from the oil bath and allowed to cool to room temperature. The resulting mixture was then filtered through a pad of Celite, which was washed with additional EtOAc to fully elute the yellow-colored product. The combined filtrates were concentrated under reduced pressure using a rotary evaporator and kept under high vacuum for a few hours to ensure complete removal of the solvent. The crude residue was purified by column chromatography on silica gel, using a gradient from DCM:Hex=1:4 to 1:3. The product was isolated as a foamy yellow solid (451.0 mg, 8.1% yield).

[0372] .sup.1H NMR (400 MHz, CDCl.sub.3) 8.14 (dd, J=7.9, 1.3 Hz, 1H), 7.60 (ddd, J=8.7, 4.2, 2.8 Hz, 2H), 7.51 (d, J=8.2 Hz, 1H), 7.47-7.36 (m, 4H), 7.23 (q, J=10.2, 9.2 Hz, 3H), 6.79 (d, J=7.8 Hz, 1H), 6.23 (s, 1H), 2.36 (s, 3H).

[0373] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 215.01, 139.52, 138.67, 138.57, 134.76, 133.61, 132.19, 132.18, 129.80, 129.44, 128.87, 128.68, 128.60, 128.32, 127.66, 126.91, 84.38, 21.42.

[0374] HRMS (DART-TOF) C.sub.21H.sub.16OS [M+H].sup.+ calcd: 317.09946 found: 317.10037.

Synthesis and Characterization of 7-(4-(trifluoromethyl)phenyl)dibenzo[c,e]oxepin-5(7H)-one (S19, p-CF.SUB.3.PhDOO)

##STR00046##

[0375] To a flame-dried 100 mL round-bottom flask, equipped with a magnetic stir bar, were added magnesium turnings (1.604 g, 66 mmol, 1.1 equiv) and LiCl (2.543 g, 60 mmol, 1.0 equiv) inside a nitrogen-filled glovebox. The flask was sealed with a rubber septum and then removed from the glovebox. Anhydrous Et.sub.2O (60 mL) was added to the flask via syringe, against a flow of nitrogen. After adding a small portion of 4-bromobenzotrifluoride (0.2 mL out of 8.4 mL total), the mixture was stirred at 50 C. until the magnesium was activated and the color of the solution changed to brown. The mixture was subsequently cooled to 0 C., after which the remaining 4-bromobenzotrifluoride (8.2 mL out of the initial 8.4 mL, 60 mmol, 1.0 equiv) was added dropwise. The mixture was stirred for an additional 30 minutes at 0 C., followed by 1.5 hours at room temperature. The resulting dark brown solution of 1 M 4-(trifluoromethyl) phenylmagnesium bromide in Et.sub.2O was used for the subsequent reaction.

[0376] To a flame-dried 250 mL round-bottom flask equipped with a magnetic stir bar was added 2-vinyl-[1,1-biphenyl]-2-carbaldehyde (S3, 8.0 g, 38.4 mmol, 1.0 equiv). The flask was sealed with a rubber septum, then evacuated and backfilled with nitrogen four times. Anhydrous THF (100 mL) was added via syringe, and the mixture was stirred at room temperature until the starting material had fully dissolved. The mixture was then cooled to 0 C. in an ice bath. 1M 4-(trifluoromethyl)phenylmagnesium bromide solution in Et.sub.2O (60 mL, 60 mmol, 1.56 equiv) was added dropwise while stirring over a period of 30 minutes. The resulting mixture was allowed to stir at 0 C. for an additional 30 minutes, and then stirred at room temperature overnight. The reaction was quenched by the addition of water (10 mL), followed by a saturated aqueous solution of NH.sub.4Cl (150 mL). The aqueous layer was extracted with EtOAc (3100 mL). The combined organic layers were dried over Na.sub.2SO.sub.4 and concentrated under reduced pressure using a rotary evaporator. The crude residue was purified by column chromatography on silica gel, using a gradient from EA:Hex=1:10 to 1:8. All fractions containing the product were collected and the solvent was removed. The resulting viscous, colorless oil was used for the subsequent reaction.

[0377] The viscous, colorless oil was transferred into a 250 mL round-bottom flask equipped with a magnetic stir bar and kept under vacuum overnight. After the addition of Oxone (49.15 g, 160 mmol, 4.0 equiv), the flask was sealed with a rubber septum and charged with nitrogen. Anhydrous DMF (60 mL) was added via syringe against a nitrogen flow, and the resulting mixture was stirred vigorously until the colorless oil had fully homogenized with the solvent. The mixture was then cooled to 0 C. in an ice bath. A 2.5 wt % OsO.sub.4 solution in t-BuOH (4.17 mL, 0.32 mmol, 0.008 equiv) was added dropwise to the flask at 0 C. The resulting black mixture was stirred at 0 C. for an additional 30 minutes and then allowed to stir overnight at room temperature. After the addition of water (50 mL), the mixture was transferred to a separatory funnel, brine (100 mL) was added, and the aqueous layer was extracted with EtOAc (3100 mL). The combined organic layers were thoroughly washed with an aqueous solution of Na.sub.2SO.sub.3 (2200 mL) to quench residual OsO.sub.4 and then washed with water (2200) and brine (2200 mL) to remove residual DMF. The mixture was dried over Na.sub.2SO.sub.4 and then concentrated under reduced pressure using a rotary evaporator. The crude residue was purified by column chromatography on silica gel, using a gradient from EA:Hex=1:10 to 1:9. The product was obtained as a white solid (3.00 g, 21.2% yield over 2 steps).

[0378] .sup.1H NMR (400 MHz, CDCl.sub.3) 8.04 (d, J=7.8 Hz, 1H), 7.70 (dt, J=25.1, 8.0 Hz, 7H), 7.59 (t, J=7.5 Hz, 1H), 7.52 (t, J=7.6 Hz, 1H), 7.31 (t, J=7.6 Hz, 1H), 6.71 (d, J=7.8 Hz, 1H), 6.31 (s, 1H).

[0379] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 169.14, 140.01, 138.76, 137.98, 137.33, 133.07, 131.77, 131.05, 130.73, 130.69, 130.06, 129.19, 129.15, 128.92, 128.74, 128.19, 127.92, 126.83, 125.76, 125.72, 125.68, 125.65, 125.48, 122.78, 120.08, 78.38.

[0380] .sup.19F{.sup.1H}NMR (376 MHz, CDCl.sub.3) 62.57.

[0381] HRMS (DART-TOF) C.sub.21H.sub.13F.sub.3O.sub.2 [M+H].sup.+ calcd: 355.09404 found: 355.09592.

Synthesis and Characterization of 7-(4-(trifluoromethyl)phenyl)dibenzo[c,e]oxepine-5(7H)-thione (S20, p-CF.SUB.3.PhDOT)

##STR00047##

[0382] To a flame-dried 250 mL round-bottom flask equipped with a magnetic stir bar were added 7-(4-(trifluoromethyl)phenyl)dibenzo[c,e]oxepin-5(7H)-one (S19, 3.00 g, 8.47 mmol, 1.0 equiv) and Lawesson's reagent (2.055 g, 5.08 mmol, 0.6 equiv). The flask was sealed with a rubber septum and purged with nitrogen. Anhydrous toluene (30 mL) was then added, and the resulting mixture was stirred in an oil bath preheated to 100 C. for 28 hours. The flask was removed from the oil bath and allowed to cool to room temperature. The reaction mixture was filtered through a pad of Celite, which was then washed with additional EtOAc to fully elute and collect the yellow-colored product. The combined filtrates were concentrated under reduced pressure using a rotary evaporator and then kept under high vacuum for several hours to ensure complete removal of the solvent (Note: Residual toluene can affect the purification). The crude residue was purified by column chromatography on silica gel, using a gradient from DCM:Hex=1:6 to 1:4. The product was isolated as a yellow solid (1.52 g, 48.5% yield).

[0383] .sup.1H NMR (400 MHz, CDCl.sub.3) 8.27-8.16 (m, 1H), 7.81-7.65 (m, 6H), 7.60 (d, J=7.7 Hz, 1H), 7.52 (td, J=7.2, 4.1 Hz, 2H), 7.33 (t, J=7.6 Hz, 1H), 6.74 (d, J=7.8 Hz, 1H), 6.40 (s, 1H).

[0384] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 214.16, 139.21, 139.19, 138.73, 137.55, 134.45, 133.66, 132.33, 131.44, 131.12, 130.79, 130.47, 130.10, 128.84, 128.83, 128.67, 128.44, 128.03, 127.97, 126.44, 125.72, 125.69, 125.65, 125.61, 125.33, 122.62, 119.92, 83.16.

[0385] .sup.19F{.sup.1H}NMR (376 MHz, CDCl.sub.3) 62.57.

[0386] HRMS (DART-TOF) C.sub.21H.sub.13F.sub.3OS [M+H].sup.+ calcd: 371.07120 found: 371.07364.

Synthesis and Characterization of 5-fluoro-2-vinyl-[1,1-biphenyl]-2-carbaldehyde (S22)

##STR00048##

[0387] To an oven-dried 250 mL round-bottom flask were sequentially added Sphos Pd G3 (715 mg, 0.92 mmol, 0.02 equiv), 5-fluoro-2-formyl phenylboronic acid (10 g, 59.6 mmol, 1.3 equiv), and K.sub.2CO.sub.3 (19 g, 137.4 mmol, 3.0 equiv) inside a nitrogen-filled glovebox. The flask was then sealed with a rubber septum and removed from the glovebox. Separately, a mixture of THF (90 mL) and water (30 mL) was purged with argon for 40 minutes in a Schlenk flask to remove oxygen. Subsequently, 110 mL of this degassed solvent mixture was transferred into the reaction flask via syringe. 2-Bromostyrene (5.74 mL, 45.8 mmol, 1.0 equiv) was added to the flask against a nitrogen flow. The resulting mixture was stirred vigorously in an oil bath preheated to 60 C. for 8 hours. The flask was removed from the oil bath and allowed to cool to room temperature. The reaction mixture was then filtered through a silica pad, which was further washed with additional ethyl acetate to completely elute the product. The combined filtrates were dried over Na.sub.2SO.sub.4 and concentrated under reduced pressure using a rotary evaporator. The crude residue was purified by column chromatography on silica gel using EA:Hex=1:30 as the eluent. The product was obtained as a colorless liquid (9.08 g, 87.6% yield).

[0388] .sup.1H NMR (400 MHz, CDCl.sub.3) 9.62 (s, 1H), 8.06 (dd, J=8.7, 5.9 Hz, 1H), 7.66 (dd, J=7.9, 1.3 Hz, 1H), 7.42 (td, J=7.6, 1.4 Hz, 1H), 7.34 (td, J=7.5, 1.3 Hz, 1H), 7.22 (dd, J=7.6, 1.4 Hz, 1H), 7.18 (td, J=8.4, 2.6 Hz, 1H), 7.01 (dd, J=9.1, 2.6 Hz, 1H), 6.40 (dd, J=17.4, 11.0 Hz, 1H), 5.68 (dd, J=17.5, 1.0 Hz, 1H), 5.19 (dd, J=10.9, 1.0 Hz, 1H).

[0389] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 190.25, 166.72, 164.16, 147.41, 147.32, 136.85, 135.08, 135.06, 134.29, 130.95, 130.92, 130.40, 130.12, 130.02, 128.98, 127.69, 125.52, 118.11, 117.90, 116.79, 115.67, 115.45, 30.31.

[0390] .sup.19F{.sup.1H}NMR (376 MHz, CDCl.sub.3) 103.41 (q, J=7.8 Hz, 1F).

[0391] HRMS (DART-TOF) C.sub.15H.sub.11FO [M+H].sup.+ calcd: 227.08667 found: 227.08650.

Synthesis and Characterization of 10-fluoro-7-(4-(trifluoromethyl)phenyl)dibenzo[c,e]oxepin-5(7H)-one (S24, F-p-CF.SUB.3.PhDOO)

##STR00049##

[0392] To a flame-dried 100 mL round-bottom flask, equipped with a magnetic stir bar, were added magnesium turnings (1.07 g, 44 mmol, 1.1 equiv) and LiCl (1.7 g, 40 mmol, 1.0 equiv) inside a nitrogen-filled glovebox. The flask was sealed with a rubber septum and then removed from the glovebox. Anhydrous THF (40 mL) was added to the flask via syringe, against a flow of nitrogen. After adding a small portion of 4-bromobenzotrifluoride (0.2 mL out of 5.6 mL total), the mixture was stirred at 50 C. until the magnesium was activated and the color of the solution changed to brown. The mixture was subsequently cooled to 0 C., after which the remaining 4-bromobenzotrifluoride (5.4 mL out of the initial 5.6 mL, 40 mmol, 1.0 equiv) was added dropwise. The mixture was stirred for an additional 30 minutes at 0 C., followed by 2 hours at room temperature. The resulting dark brown solution of 1 M 4-(trifluoromethyl) phenyl magnesium bromide in THF was used for the subsequent reaction.

[0393] A flame-dried 250 mL round-bottom flask equipped with a magnetic stir bar was sealed with a rubber septum and charged with nitrogen. Then, 5-fluoro-2-vinyl-[1,1-biphenyl]-2-carbaldehyde (5.29 g, 23.4 mmol, 1.0 equiv) and anhydrous THF (35 mL) were added into the flask via syringes. The resulting solution was cooled to 0 C. in an ice bath under a nitrogen atmosphere. 1M 4-(trifluoromethyl)phenylmagnesium bromide solution in THF (35 mL, 35 mmol, 1.5 equiv) was added dropwise while stirring over a period of 30 minutes. The resulting mixture was allowed to stir at 0 C. for an additional 30 minutes, and then stirred at room temperature overnight. The reaction was quenched by the addition of water (10 mL), followed by a saturated aqueous solution of NH.sub.4Cl (100 mL). The aqueous layer was extracted with EtOAc (370 mL). The combined organic layers were dried over Na.sub.2SO.sub.4 and concentrated under reduced pressure using a rotary evaporator. The crude residue was purified by column chromatography on silica gel using EA:Hex=1:10 as the eluent. All fractions containing the product were collected and the solvent was removed. The resulting colorless oil was used for the subsequent reaction.

[0394] The colorless oil was transferred into a 250 mL round-bottom flask equipped with a magnetic stir bar and kept under vacuum overnight. After the addition of Oxone (28.7 g, 93.5 mmol, 4.0 equiv), the flask was sealed with a rubber septum and charged with nitrogen. Anhydrous DMF (40 mL) was added via syringe against a nitrogen flow, and the resulting mixture was stirred vigorously until the colorless oil had fully homogenized with the solvent. The mixture was then cooled to 0 C. in an ice bath. A 2.5 wt % OsO.sub.4 solution in t-BuOH (2.44 mL, 0.187 mmol, 0.008 equiv) was added dropwise to the flask at 0 C. The resulting black mixture was stirred at 0 C. for an additional 30 minutes and then allowed to stir overnight at room temperature. After the addition of water (40 mL), the mixture was transferred to a separatory funnel, brine (100 mL) was added, and the aqueous layer was extracted with EtOAc (3100 mL). The combined organic layers were thoroughly washed with an aqueous solution of Na.sub.2SO.sub.3 (2200 mL) to quench residual OsO.sub.4 and then washed with water (2200) and brine (2200 mL) to remove residual DMF. The organic layer was dried over Na.sub.2SO.sub.4 and then concentrated under reduced pressure using a rotary evaporator. The crude residue was purified by column chromatography on silica gel, using a gradient from EA:Hex=1:9 to 1:8. The product was obtained as a white solid (2.845 g, 32.7% yield over 2 steps).

[0395] .sup.1H NMR (400 MHz, CDCl.sub.3) 8.04 (d, J=7.7 Hz, 1H), 7.76 (dd, J=14.5, 7.6 Hz, 3H), 7.70-7.57 (m, 4H), 7.38 (dd, J=9.3, 2.6 Hz, 1H), 6.99 (td, J=8.4, 2.6 Hz, 1H), 6.69 (dd, J=8.7, 5.5 Hz, 1H), 6.26 (s, 1H).

[0396] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 168.77, 164.68, 162.20, 140.96, 140.87, 139.85, 136.16, 136.14, 134.10, 134.07, 133.24, 131.94, 131.52, 131.20, 130.87, 130.72, 130.55, 129.50, 129.09, 129.03, 129.01, 128.12, 127.83, 125.86, 125.82, 125.79, 125.75, 125.42, 122.71, 120.00, 116.18, 115.95, 115.59, 115.37, 77.72.

[0397] .sup.19F{.sup.1H}NMR (376 MHz, CDCl.sub.3) 62.61 (s, 3F), 110.82 (q, J=8.3 Hz, 1F).

[0398] HRMS (DART-TOF) C.sub.21H.sub.12F.sub.4O.sub.2 [M+H].sup.+ calcd: 373.08462 found: 373.08487.

Synthesis and Characterization of 10-fluoro-7-(4-(trifluoromethyl)phenyl)dibenzo[c,e]oxepine-5(7H)-thione (S25, F-p-CF.SUB.3.PhDOT)

##STR00050##

[0399] To a flame-dried 100 mL round-bottom flask equipped with a magnetic stir bar were added 10-fluoro-7-(4-(trifluoromethyl)phenyl)dibenzo[c,e]oxepin-5(7H)-one (S24, 2.845 g, 7.64 mmol, 1.0 equiv) and Lawesson's reagent (1.854 g, 4.59 mmol, 0.6 equiv). The flask was sealed with a rubber septum and charged with nitrogen. Anhydrous toluene (20 mL) was then added to the flask, and the resulting mixture was stirred in an oil bath preheated to 100 C. for 28 hours. After this period, the flask was removed from the oil bath and allowed to cool to room temperature. It was then further cooled in a refrigerator to approximately 2 C. The reaction mixture was filtered through a silica pad, which was subsequently washed with additional EtOAc to completely elute and collect the yellow-colored product. The combined filtrate was concentrated under reduced pressure using a rotary evaporator and then kept under high vacuum for several hours to ensure complete removal of solvent (Note: Residual toluene can affect the purification process). The crude residue was purified by column chromatography on silica gel, using a gradient from DCM:Hex=1:6 to 1:4. The product was isolated as a yellow solid (1.34 g, 45.2% yield).

[0400] .sup.1H NMR (400 MHz, CDCl.sub.3) 8.21 (dd, J=7.8, 1.3 Hz, 1H), 7.82-7.66 (m, 5H), 7.61-7.49 (m, 2H), 7.39 (dd, J=9.2, 2.6 Hz, 1H), 7.01 (td, J=8.4, 2.7 Hz, 1H), 6.72 (dd, J=8.7, 5.5 Hz, 1H), 6.34 (s, 1H).

[0401] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 213.57, 164.64, 162.16, 140.95, 140.86, 139.22, 139.06, 133.78, 133.68, 133.65, 133.25, 133.23, 132.43, 131.60, 131.28, 130.95, 130.63, 129.00, 128.73, 128.67, 128.65, 127.96, 127.87, 125.83, 125.79, 125.75, 125.72, 125.26, 122.55, 119.85, 115.82, 115.59, 115.57, 115.35, 82.43.

[0402] .sup.19F{.sup.1H}NMR (376 MHz, CDCl.sub.3) 62.63 (s, 3F), 110.46 (td, J=8.6, 5.3 Hz, 1F).

[0403] HRMS (DART-TOF) C.sub.21H.sub.12F.sub.4OS [M+H].sup.+ calcd: 389.06177 found: 389.06178.

Synthesis and Characterization of 7-(perfluorophenyl)dibenzo[c,e]oxepin-5(7H)-one (S27, PFPhDOO)

##STR00051##

[0404] To a flame-dried 250 mL round-bottom flask equipped with a magnetic stir bar was added 2-vinyl-[1,1-biphenyl]-2-carbaldehyde (S3, 10.27 g, 49.3 mmol, 1.0 equiv). The flask was sealed with a rubber septum, then evacuated and backfilled with nitrogen four times. Anhydrous THF (60 mL) was added, and the mixture was stirred at room temperature until S3 had fully dissolved. The mixture was then cooled to 0 C. in an ice bath. 0.5 M pentafluorophenyl magnesium bromide solution in Et.sub.2O (100 mL, 50 mmol, 1.014 equiv) was added dropwise while stirring over a period of 30 minutes. The resulting mixture was allowed to stir at 0 C. for an additional 20 minutes, and then stirred at room temperature overnight. The reaction was quenched by the addition of water (10 mL), followed by a saturated aqueous solution of NH.sub.4Cl (150 mL). The aqueous layer was extracted with EtOAc (3100 mL). The combined organic layers were dried over Na.sub.2SO.sub.4 and concentrated under reduced pressure using a rotary evaporator. The crude residue was purified by column chromatography on silica gel, using a gradient from EA:Hex=1:10 to 1:8. All fractions containing the product were collected and the solvent was removed. The resulting viscous, colorless oil was used for the subsequent reaction.

[0405] The viscous, colorless oil was transferred into a 250 mL round-bottom flask equipped with a magnetic stir bar and kept under vacuum overnight. After the addition of Oxone (60.6 g, 197.2 mmol, 4.0 equiv), the flask was sealed with a rubber septum and charged with nitrogen. Anhydrous DMF (80 mL) was added via syringe against a nitrogen flow, and the resulting mixture was stirred vigorously until the colorless oil had fully homogenized with the solvent. The mixture was then cooled to 0 C. in an ice bath. A 2.5 wt % OsO.sub.4 solution in t-BuOH (5.0 mL, 0.394 mmol, 0.008 equiv) was added dropwise to the flask at 0 C. The resulting mixture was stirred at 0 C. for an additional 30 minutes and then allowed to stir overnight at room temperature. After the addition of water (50 mL), the mixture was transferred to a separatory funnel, brine (100 mL) was added, and the aqueous layer was extracted with EtOAc (3100 mL). The combined organic layers were thoroughly washed with an aqueous solution of Na.sub.2SO.sub.3 (2200 mL) to quench residual OsO.sub.4 and then washed with water (2200) and brine (2200 mL) to remove residual DMF. The organic layer was dried over Na.sub.2SO.sub.4 and then concentrated under reduced pressure using a rotary evaporator. The purification of the crude residue required two sequential column chromatographies on silica gel. After the first chromatography using EA:Hex=1:8 as the eluent, all fractions containing the product were collected and concentrated under reduced pressure using a rotary evaporator. The residue was then subjected to a second column chromatography, with a gradient from DCM:Hex=1:5 to 1:3. The product was isolated as a white solid (2.373 g, 12.8% yield over 2 steps).

[0406] .sup.1H NMR (400 MHz, CDCl.sub.3) 8.06 (dd, J=7.9, 1.4 Hz, 1H), 7.81-7.65 (m, 3H), 7.60 (qd, J=7.7, 1.2 Hz, 2H), 7.42 (td, J=7.6, 1.3 Hz, 1H), 7.04 (dd, J=7.4, 2.1 Hz, 1H), 6.54 (s, 1H).

[0407] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 168.54, 146.46, 143.96, 143.15, 140.59, 139.20, 138.52, 136.98, 136.68, 133.75, 133.31, 132.11, 130.63, 129.65, 129.50, 129.46, 129.04, 128.80, 125.61, 109.94, 71.30.

[0408] .sup.19F{.sup.1H}NMR (376 MHz, CDCl.sub.3) 151.42 (t, J=22.7 Hz, 2F), 160.44 (t, J=27.6 Hz, 3F).

[0409] Note: The .sup.13C NMR peaks at 146.46, 143.96, 143.15, 140.59, 139.20, 136.68, and 109.94 appear as multiplets due to the coupling with fluorine.

[0410] HRMS (DART-TOF) C.sub.20H.sub.9F.sub.5O.sub.2[M+H].sup.+ calcd: 377.05955 found: 377.06006.

Synthesis and Characterization of 7-(perfluorophenyl)dibenzo[c,e]oxepine-5(7H)-thione (S28, PFPhDOT)

##STR00052##

[0411] To a flame-dried 250 mL round-bottom flask, equipped with a magnetic stir bar, were added 7-(perfluorophenyl)dibenzo[c,e]oxepin-5(7H)-one (S27, 2.373 g, 6.31 mmol 1.0 equiv) and Lawesson's reagent (1.53 g, 3.78 mmol, 0.6 equiv). The flask was sealed with a rubber septum and charged with nitrogen. Anhydrous toluene (25 mL) was then added, and the resulting mixture was stirred in an oil bath preheated to 100 C. for 48 hours. The flask was removed from the oil bath and allowed to cool to room temperature before being further cooled in a refrigerator to approximately 2 C. The reaction mixture was then filtered through a pad of silica, which was subsequently washed with additional EtOAc to completely elute and collect the yellow-orange product. The combined filtrate was concentrated under reduced pressure using a rotary evaporator and was kept under high vacuum for several hours to ensure complete removal of solvent (Note: Residual toluene can affect the purification process). The crude residue was purified by column chromatography on silica gel, using a gradient from DCM:Hex=1:6 to 2:5. The product was isolated as a foamy yellow-orange solid (1.23 g, 49.7% yield).

[0412] .sup.1H NMR (400 MHz, CDCl.sub.3) 8.24 (dd, J=8.0, 1.4 Hz, 1H), 7.77-7.65 (m, 2H), 7.64-7.49 (m, 3H), 7.44 (td, J=7.7, 1.3 Hz, 1H), 7.06 (d, J=7.8 Hz, 1H), 6.62 (s, 1H).

[0413] .sup.13C{.sup.1H}NMR (101 MHz, CDCl.sub.3) 213.44, 146.58, 144.06, 143.35, 140.79, 139.26, 138.70, 138.34, 136.76, 134.20, 134.15, 133.54, 132.64, 130.77, 129.38, 129.27, 128.83, 128.68, 125.44, 109.48, 75.70.

[0414] .sup.19F{.sup.1H}NMR (376 MHz, CDCl.sub.3) 150.99 (t, J=22.4 Hz), 160.09 (d, J=29.2 Hz).

[0415] Note: The .sup.13C NMR peaks at 146.58, 144.06, 143.35, 140.79, 139.26, 136.76, and 109.48 appear as multiplets due to the coupling with fluorine.

[0416] HRMS (DART-TOF) C.sub.20H.sub.9F.sub.5OS [M+H].sup.+ calcd: 393.03670 found: 393.03794.

Discussion about the Side Products in Synthesis

[0417] The side products formed from the thionation of PhDOO to synthesize PhDOT were characterized as the isomerized thiolactone 7-phenyldibenzo[c,e]thiepin-5(7H)-one (PhDTO) and the overthionated 7-phenyldibenzo[c,e]thiepine-5(7H)-thione (PhDTT). The HRMS results matched well with the assignments.

[0418] The quantities of the four major species, PhDOO, PhDOT, PhDTT, and PhDTO, in the reaction mixture were assessed using a small-scale test reaction (200 mol). After the reaction, the mixture was filtered through a pad of celite, the solvent was then evaporated, and the residue was analyzed by NMR, using either 200 mol of 1,1,2,2-tetrachloroethane (21 L) or dibromomethane (14 L) as an internal standard.

[0419] Following 4 hours of thionation, the crude mixture comprised 52 mol of PhDOO, 109 mol of PhDOT, 14 mol of PhDTT, and 8 mol of PhDTO, indicating a 74% conversion and a 55% crude yield. The stability of the species on silica was assessed by applying the crude mixture onto a silica pad, eluting it after a 3-hour period, and subsequently reanalyzing it using NMR. No notable change in integrations was observed, suggesting that the products neither decompose nor interconvert on silica.

[0420] Prolonging the reaction time to 10 hours did not appreciably increase the yield; the mixture formed 115 mol of PhDOT (57% crude yield), while further consumption of the starting material PhDOO (87% conversion) led to increased production of the side products PhDTT and PhDTO.

[0421] Scaling up this reaction resulted in a decrease in the yield of PhDOT synthesis. This reduction is presumably due to the decreased efficiency of the reaction that converts PhDOO to PhDOT, while the efficiency of the isomerization process from PhDOT to PhDTO remained unchanged.

Synthesis and Characterization of Polymers

Evaluation of the Reactivity of MeDOT, Me.SUB.2.DOT, and PhDOT

[0422] Stock solutions of ACHN (1.22 mg/1000 L, 5 mM), 2-cyano-2-propyl benzodithioate (11.1 mg/1000 L, 50 mM), and 1,4-bis(trimethylsilyl)benzene (55.5 mg/1000 L, 250 mM) in Tol-d8 were prepared under ambient atmosphere and used for the following reactions.

Evaluation of the Reactivity of MeDOT

##STR00053##

[0423] To a 4 mL scintillation vial, 12.0 mg of MeDOT (50 mol, 10 equiv.), 153 L of Tol-d8, 100 L of 1,4-bis(trimethylsilyl)benzene stock (25 mol, 5.0 equiv.), 100 L of 2-cyano-2-propyl benzodithioate stock (5 mol, 1.0 equiv.), and 100 L of ACHN stock (0.5 mol, 0.1 equiv.) solutions were added sequentially. Following the addition of 47.9 L MMA (450 mol, 90 equiv.), the resulting mixture was vortexed and then transferred into a J-Young NMR tube. The solution was degassed by four careful freeze-pump-thaw cycles. The tube was then placed in an oil bath pre-heated to 100 C. At each time point, the tube was removed from the oil bath, rapidly cooled to room temperature in a water bath, and subsequently subjected to NMR analysis to measure the conversion of the monomers. No consumption of MeDOT was observed, while MMA polymerized to form PMMA (FIG. 31A).

Evaluation of the Reactivity of Me.SUB.2.DOT

##STR00054##

[0424] To a 4 mL scintillation vial, 6.4 mg of Me.sub.2DOT (25 mol, 5.0 equiv.), 153 L of Tol-d8, 100 L of 1,4-bis(trimethylsilyl)benzene stock (25 mol, 5.0 equiv.), 100 L of 2-cyano-2-propyl benzodithioate stock (5 mol, 1.0 equiv.), and 100 L of ACHN stock (0.5 mol, 0.1 equiv.) solutions were added sequentially. Following the addition of 50.6 L MMA (475 mol, 95 equiv.), the resulting mixture was vortexed and then transferred into a J-Young NMR tube. The solution was degassed by four careful freeze-pump-thaw cycles. The tube was then placed in an oil bath pre-heated to 100 C. At each time point, the tube was removed from the oil bath, rapidly cooled to room temperature in a water bath, and subsequently subjected to NMR analysis to measure the conversion of the monomers. Me.sub.2DOT gradually converted into an unknown species but did not copolymerize with MMA The polymerization of MMA was significantly retarded in the presence of Me.sub.2DOT (FIG. 31B).

Evaluation of the Reactivity of PhDOT

##STR00055##

[0425] To a 4 mL scintillation vial, 15.1 mg of PhDOT (50 mol, 10 equiv.), 153 L of Tol-d8, 100 L of 1,4-bis(trimethylsilyl)benzene stock (25 mol, 5.0 equiv.), 100 L of 2-cyano-2-propyl benzodithioate stock (5 mol, 1.0 equiv.), and 100 L of ACHN stock (0.5 mol, 0.1 equiv.) solutions were added sequentially. Following the addition of 47.9 L MMA (450 mol, 90 equiv.), the resulting mixture was vortexed and then transferred into a J-Young NMR tube. The solution was degassed by four careful freeze-pump-thaw cycles. The tube was then placed in an oil bath pre-heated to 100 C. At each time point, the tube was removed from the oil bath, rapidly cooled to room temperature in a water bath, and subsequently subjected to NMR analysis to measure the conversion of the monomers. PhDOT was consumed throughout its copolymerization with MMA (FIG. 32).

Synthesis of P(MMA-Co-bDOT)

##STR00056##

[0426] Stock solutions of ACHN (1.22 mg/1000 L, 5 mM), 2-cyano-2-propyl benzodithioate (11.1 mg/1000 L, 50 mM), and 1,4-bis(trimethylsilyl)benzene (55.5 mg/1000 L, 250 mM) in Tol-d8 were prepared in a glovebox and used for the following reactions for consistency.

[0427] To a 4 mL scintillation vial, 15.1 mg of PhDOT (50 mol, 10 equiv.), 153 L of Tol-d8, 100 L of 1,4-bis(trimethylsilyl)benzene stock (25 mol, 5.0 equiv.), 100 L of 2-cyano-2-propyl benzodithioate stock (5 mol, 1.0 equiv.), and 100 L of ACHN stock (0.5 mol, 0.1 equiv.) solutions were added sequentially. Following the addition of 47.9 L MMA (450 mol, 90 equiv.), the resulting mixture was vortexed and then transferred into an NMR tube. The tube was securely sealed with a cap, reinforced with electrical tape, and then removed from the glovebox. Subsequently, the NMR tube was submerged in an oil bath preheated to 100 C. After heating for 60 hours at 100 C., the tube was removed from the oil bath and allowed to cool to room temperature. The reaction was quenched by exposure to air. .sup.1H NMR analysis was conducted before and after the reaction to measure the conversion of monomers. The solvent was removed with the aid of a rotary evaporator, and the residue was subjected to preparative SEC to remove small molecules. The resulting polymer was analyzed by analytical SEC and NMR (FIGS. 33-36, Table 2).

[0428] The analogous experiments were done for aryl bDOTs, p-MePhDOT (63.3 mg, 200 mol, 10 equiv.), p-CF.sub.3PhDOT (74.1 mg, 200 mol, 10 equiv.), F-p-CF.sub.3PhDOT (77.7 mg, 200 mol, 10 equiv.), and PFPhDOT (78.4 mg, 200 mol, 10 equiv.).

Deconstruction of P(MMA-Co-bDOT) into O(MMA-Co-bDOT)

[0429] To a 4 mL scintillation vial containing P(MMA-co-bDOT) was added a magnetic stir bar. The vial was added 950 L propylamine and 50 L 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU). The vial was capped with a screw-thread cap fitted with Teflon septa. The reaction mixture was stirred in an aluminum heating block preheated to 50 C. After stirring for 24 hours at 50 C., the vial was removed from the heating block and allowed to cool to room temperature. The reaction mixture was diluted with EtOAc (30 mL) and washed with 1 M aqueous solution of HCl (430 mL). The organic layer was dried over Na.sub.2SO.sub.4, and the solvent was removed with the aid of a rotary evaporator. The resulting O(MMA-co-bDOT) was analyzed by analytical SEC (FIG. 36 and Table 2).

TABLE-US-00002 TABLE 2 Summary of the molecular weight and dispersity of the polymers Name M.sub.n M.sub.W Before degradation P(MMA-co-PhDOT) 5108 7543 1.477 P(MMA-co-p-MePhDOT) 5312 8084 1.522 P(MMA-co-p-CF.sub.3PhDOT) 4802 7462 1.554 P(MMA-co-F-p-CF.sub.3PhDOT) 4442 7124 1.604 P(MMA-co-PFPhDOT) 2857 8279 1.812 After degradation O(MMA-co-PhDOT) 2590 6438 2.486 O(MMA-co-p-MePhDOT) 2430 6026 2.480 O(MMA-co-p-CF.sub.3PhDOT) 2078 5707 2.746 O(MMA-co-F-p-CF.sub.3PhDOT) 1735 4440 2.558 O(MMA-co-PFPhDOT) 742 2534 3.414
Synthesis of vPMMA and dPMMA(f.sub.bDOT)

##STR00057##

[0430] A stock solution of ACHN in MMA (53.6 mg in 7020 L, 31.3 mM) was prepared in a glovebox and used for the following polymerizations to ensure consistency in the amount of the initiator.

Synthesis of vPMMA

[0431] 200 L of MMA and 300 L of ACHN stock solution were added to each of the five 4 mL scintillation vials. This amounts to 500 L of MMA (4.69 mmol, 100.0 equiv.) and 2.29 mg of ACHN (9.39 mol, 0.2 equiv.) per vial. The vials were securely sealed with screw-thread caps fitted with Teflon septa and reinforced using electrical tape, and then removed from the glovebox. Subsequently, the vials were placed in an aluminum heating block preheated to 100 C. and maintained at this temperature for 8 hours.

[0432] The vials were removed from the heating block and allowed to cool to room temperature. The reaction mixture in one of the vials was diluted with CDCl.sub.3 to obtain a total solution volume of 10 mL. From this, 500 L was transferred to an NMR tube and subjected to quantitative .sup.1H NMR analysis to measure the amount of unreacted starting materials. 1,1,2,2-Tetrachloroethane was added as an internal standard for quantification. It was determined that 99.6% of the MMA had reacted.

[0433] The reaction mixtures from the five vials were dissolved in chloroform and combined to form a total solution volume of 40 mL. This solution was then added dropwise over 5 minutes into vigorously stirred MeOH (500 mL) to precipitate the polymer. The precipitated polymer was collected and purified through three successive precipitations in MeOH. The resulting white solid was pulverized and dried under high vacuum for approximately 24 hours until no further mass loss was observed, yielding vPMMA (2.004 g, 85.3%) as a white powder.

Synthesis of dPMMA(2.5)

[0434] 45.6 mg of F-p-CF.sub.3PhDOT (117.4 mol, 2.5 equiv.), 187.5 L of MMA, and 300 L of ACHN stock solution were added to each of the five 4 mL scintillation vials. This resulted in each vial containing 45.6 mg of F-p-CF.sub.3PhDOT (117.4 mol, 2.5 equiv.), 487.5 L of MMA (4.58 mmol, 97.5 equiv.) and 2.29 mg of ACHN (9.39 mol, 0.2 equiv.). The vials were securely sealed with screw-thread caps fitted with Teflon septa and reinforced using electrical tape, and then removed from the glovebox. Subsequently, the vials were placed in an aluminum heating block preheated to 100 C. and maintained at this temperature for 8 hours.

[0435] The vials were removed from the heating block and allowed to cool to room temperature. The reaction mixture in one of the vials was diluted with CDCl.sub.3 to obtain a total solution volume of 10 mL. From this, 500 L was transferred to an NMR tube and subjected to quantitative .sup.1H NMR analysis to measure the amount of unreacted starting materials. 1,1,2,2-Tetrachloroethane was added as an internal standard for quantification. It was determined that 99.6% of the MMA and 98.6% of F-p-CF.sub.3PhDOT has reacted.

[0436] The reaction mixtures from the five vials were dissolved in chloroform and combined to form a total solution volume of 40 mL. This solution was then added dropwise over 5 minutes into vigorously stirred MeOH (500 mL) to precipitate the polymer. The precipitated polymer was collected and purified through three successive precipitations in MeOH. The resulting white solid was pulverized and dried under high vacuum for approximately 24 hours until no further mass loss was observed, yielding dPMMA(2.5) (2.138 g, 84.9%) as a white powder.

Synthesis of dPMMA(5.0)

[0437] 91.2 mg of F-p-CF.sub.3PhDOT (234.7 mol, 5.0 equiv.), 175 L of MMA, and 300 L of ACHN stock solution were added to each of the five 4 mL scintillation vials. This resulted in each vial containing 91.2 mg of F-p-CF.sub.3PhDOT (234.7 mol, 5.0 equiv.), 475 L of MMA (4.46 mmol, 95.0 equiv.) and 2.29 mg of ACHN (9.39 mol, 0.2 equiv.). The vials were securely sealed with screw-thread caps fitted with Teflon septa and reinforced using electrical tape, and then removed from the glovebox. Subsequently, the vials were placed in an aluminum heating block preheated to 100 C. and maintained at this temperature for 8 hours.

[0438] The vials were removed from the heating block and allowed to cool to room temperature. The reaction mixture in one of the vials was diluted with CDCl.sub.3 to obtain a total solution volume of 10 mL. From this, 500 L was transferred to an NMR tube and subjected to quantitative .sup.1H NMR analysis to measure the amount of unreacted starting materials. 1,1,2,2-Tetrachloroethane was added as an internal standard for quantification. It was determined that 99.5% of the MMA and 98.6% of F-p-CF.sub.3PhDOT has reacted.

[0439] The reaction mixtures from the five vials were dissolved in chloroform and combined to form a total solution volume of 40 mL. This solution was then added dropwise over 5 minutes into vigorously stirred MeOH (500 mL) to precipitate the polymer. The precipitated polymer was collected and purified through three successive precipitations in MeOH. The resulting white solid was pulverized and dried under high vacuum for approximately 24 hours until no further mass loss was observed, yielding dPMMA(5.0) (2.091 g, 77.8%) as a white powder.

Synthesis of dPMMA(10)

[0440] 182.3 mg of F-p-CF.sub.3PhDOT (469.4 mol, 10.0 equiv.), 150 L of MMA, and 300 L of ACHN stock solution were added to a 4 mL scintillation vial. This amounts to 182.3 mg of F-p-CF.sub.3PhDOT (469.4 mol, 10.0 equiv.), 450 L of MMA (4.22 mmol, 90.0 equiv.) and 2.29 mg of ACHN (9.39 mol, 0.2 equiv.). The vial was securely sealed with a screw-thread cap fitted with Teflon septa and reinforced using electrical tape, and then removed from the glovebox. Subsequently, the vial was placed in an aluminum heating block preheated to 100 C. and maintained at this temperature for 8 hours.

[0441] The vial was removed from the heating block and allowed to cool to room temperature. The reaction mixture was diluted with CDCl.sub.3 to obtain a total solution volume of 10 mL. From this, 500 L was transferred to an NMR tube and subjected to quantitative .sup.1H NMR analysis to measure the amount of unreacted starting materials. 1,1,2,2-Tetrachloroethane was added as an internal standard for quantification. It was determined that 99.2% of the MMA and 96.1% of F-p-CF.sub.3PhDOT has reacted.

[0442] The solution was then added dropwise over 5 minutes into vigorously stirred MeOH (100 mL) to precipitate the polymer. The precipitated polymer was collected and purified through three successive precipitations in MeOH. The resulting white solid was pulverized and dried under high vacuum for approximately 24 hours until no further mass loss was observed, yielding dPMMA(10) (0.438 g, 72.4%) as a white powder.

Deconstruction of dPMMA(f.sub.bDoT) into OMMA(f.sub.bDoT)

General Deconstruction Procedure

##STR00058##

[0443] 30 mg dPMMA(f.sub.bDOT) was weighed into a 4 mL scintillation vial equipped with a magnetic stir bar. The vial was added 950 L propylamine and 50 L DBU. The vial was capped with a screw-thread cap fitted with Teflon septa. The reaction mixture was stirred in an aluminum heating block preheated to 50 C. After stirring for 24 hours at 50 C., the vial was removed from the heating block and allowed to cool to room temperature. The reaction mixture was diluted with EtOAc (30 mL) and washed with 1 M aqueous solution of HCl (420 mL). The organic layer was dried over Na.sub.2SO.sub.4, and the solvent was removed with the aid of a rotary evaporator.

Control Deconstruction Experiment

[0444] 30 mg of vPMMA was subjected to the general deconstruction procedure. The polymer obtained after the treatments was analyzed by analytical SEC. The SEC trace showed no difference compared to that of vPMMA (FIG. 37).

Deconstruction Condition Screening

[0445] 30 mg dPMMA(2.5) was subjected to the following four different deconstruction conditions. [0446] 1) 100% Propylamine (1000 L propylamine), RT, 24 hours [0447] 2) 100% Propylamine (1000 L propylamine), 50 C., 24 hours [0448] 3) 95% Propylamine+5% DBU (950 L propylamine+50 L DBU), RT, 24 hours [0449] 4) 95% Propylamine+5% DBU (950 L propylamine+50 L DBU), 50 C., 24 hours

[0450] The resulting reaction mixtures were worked-up following the general procedure. The polymer obtained after the treatments was analyzed by analytical SEC. The SEC trace showed no difference compared to that of OMMA(2.5), indicating that the addition of DBU and heating are unnecessary (FIG. 38).

.SUP.1.H NMR Studies

[0451] .sup.1H NMR experiments were conducted to confirm the estimated molecular weight of OMMA(5.0). dPMMA(5.0) was deconstructed in neat p-methoxy benzylamine (chosen for its 0-CH.sub.3 signal not overlapping with that of PMMA) at room temperature. The resulting crude OMMA(5.0) was dissolved in EtOAc (20 mL) and washed thoroughly with a 1N aqueous solution of HCl (20 mL8 times) to remove excess p-methoxy benzylamine. .sup.1H NMR analysis of the resulting OMMA(5.0) suggested an average of 25.1 MMA per end group, which aligns well with F.sub.bDOT of 3.8% in the absence of CC diads. The calculated M.sub.n from .sup.1H NMR integration was 3.0 kDa (525.62+25.1100.11=3038.4), which is smaller than the 5.4 kDa measured from SEC. This discrepancy may be due to the slight inaccuracy of SEC in the low molar mass region; nevertheless, this confirms that F-p-CF.sub.3PhDOT allows for the deconstruction of PMMA into small molar mass fragments.

Discussion about Bulk Polymerization

Reactivity Ratios in Bulk Polymerization

[0452] The distribution of bDOTs can differ between RAFT polymerization and bulk FRP. These differences likely arise due to the reactivity ratios changing depending on the chemical environment. Reactivity ratios were not measured for bulk FRP, as MMA polymerization is known to autoaccelerate under these conditions, resulting in changes in reaction temperature and, accordingly, the reactivity ratios over the course of the polymerization.

[0453] The monomer conversions versus time for bulk free-radical copolymerization evidently shows autoacceleration. The fact that bDOT conversion closely parallels MMA conversion indicates, albeit not conclusively, that bDOT is being inserted into PMMA with a favorable distribution. The distribution of bDOT can change to some extent depending on the reaction scale and efficiency of heat transfer.

Comparison of bDOTs in Bulk Polymerization

[0454] dPMMAs with F.sub.bDOT=1.25% were synthesized using both PhDOT and F-p-CF.sub.3PhDOT as cleavable comonomers and were tested their degradation. The selection of an F.sub.bDOT of 1.25% was due to the limited solubility of PhDOT in MMA.

[0455] The SEC results revealed that the molar masses of the dPMMAs are almost indistinguishable, while the molar mass of the OMMA is >1.5 times larger when PhDOT is used as a cleavable comonomer (FIG. 41). This demonstrates that F-p-CF.sub.3PhDOT is indeed a more efficient cleavable comonomer than PhDOT in bulk FRP.

Discussion about Initiators

[0456] The use of AIBN as an initiator and conducting polymerization at a lower temperature (70 C.) did not alter the fact that the copolymer undergoes a significant (>16-fold) molar mass decrease upon deconstruction, as can be seen in FIG. 42.

Determination of Reactivity Ratios

Kinetic Experiments for Aryl bDOTs

##STR00059##

[0457] Stock solutions of ACHN (3.9 mg/3200 L, 5 mM), 2-cyano-2-propyl benzodithioate (26.6 mg/2400 L, 50 mM), and 1,4-bis(trimethylsilyl)benzene (133.2 mg/2400 L, 250 mM) in Tol-d8 were prepared inside a nitrogen-filled glovebox.

[0458] 60.5 mg of PhDOT (200 mol, 10 equiv.), 400 L of 1,4-bis(trimethylsilyl)benzene stock (100 mol, 5.0 equiv.), 400 L of 2-cyano-2-propyl benzodithioate stock (20 mol, 1.0 equiv.), and 400 L of ACHN stock (2 mol, 0.1 equiv.) solutions were sequentially added to a 4 mL scintillation vial inside the glovebox. After the additions, 192 L of MMA (1800 mol, 90 equiv.) and approximately 600 L of Tol-d8 were added to adjust the total volume of the mixture to 2 mL. The resulting orange solution was divided into 11 oven-dried NMR tubes (182 L each). The tubes were securely sealed with caps, reinforced with electrical tape, and then removed from the glovebox. Subsequently, the NMR tubes were submerged in an oil bath preheated to 100 C., with vigorous stirring to maintain a homogeneous temperature. At each timepoint, ranging between 0 to 60 hours, one of the NMR tubes was removed from the oil bath, and the reaction was quenched by rapid cooling in an ice bath followed by exposure to air. The NMR spectra were evaluated after adding 300 L of Tol-d8. The conversion of the monomers was measured using 1,4-bis(trimethylsilyl)benzene as the internal standard.

[0459] The analogous experiments were done for aryl bDOTs, p-MePhDOT (63.3 mg, 200 mol, 10 equiv.), p-CF.sub.3PhDOT (74.1 mg, 200 mol, 10 equiv.), F-p-CF.sub.3PhDOT (77.7 mg, 200 mol, 10 equiv.), and PFPhDOT (78.4 mg, 200 mol, 10 equiv.).

Fitting Details

[0460] The Meyer-Lowry model was selected because of its known accuracy from low to high initial feed ratios, essential for measuring reactivity ratios in low CC feed..sup.92 The experimental data were fitted to the following Meyer-Lowry equation:

[00003]$\mathrm{conv}=1-{\left(\frac{f_A}{f_A^0}\right)}^{\frac{r_B}{1-r_B}}{\left(\frac{1-f_A}{1-f_A^0}\right)}^{\frac{r_A}{1-r_A}}{\left(\frac{f_A\left(2-r_A-r_B\right)-r_B-1}{f_A^0\left(2-r_A-r_B\right)-r_B-1}\right)}^{\frac{\left(r_A{r}_B-1\right)}{\left(1-r_A\right)\left(1-r_B\right)}}$

[0461] In the given equation, f.sub.A.sup.0 represents the initial feed composition of A, f.sub.A denotes the feed composition at a specific time point, conv is the conversion rate for the copolymerization at that time, and r.sub.A and r.sub.B are the reactivity ratios, with A and B corresponding to MMA and DOT, respectively.

[0462] An optimization algorithm, employing MATLAB's lsqnonlin function, was used to perform nonlinear least squares optimization to find the set of parameters that minimally deviate from the given experimental data, in terms of the sum of squared residuals.

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EQUIVALENTS AND SCOPE

[0580] In the claims articles such as a, an, and the may mean one or more than one unless indicated to the contrary or otherwise evident from the context. Claims or descriptions that include or between one or more members of a group are considered satisfied if one, more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process unless indicated to the contrary or otherwise evident from the context. The invention includes embodiments in which exactly one member of the group is present in, employed in, or otherwise relevant to a given product or process. The invention includes embodiments in which more than one, or all of the group members are present in, employed in, or otherwise relevant to a given product or process.

[0581] Furthermore, the invention encompasses all variations, combinations, and permutations in which one or more limitations, elements, clauses, and descriptive terms from one or more of the listed claims is introduced into another claim. For example, any claim that is dependent on another claim can be modified to include one or more limitations found in any other claim that is dependent on the same base claim. Where elements are presented as lists, e.g., in Markush group format, each subgroup of the elements is also disclosed, and any element(s) can be removed from the group. It should it be understood that, in general, where the invention, or aspects of the invention, is/are referred to as comprising particular elements and/or features, certain embodiments of the invention or aspects of the invention consist, or consist essentially of, such elements and/or features. For purposes of simplicity, those embodiments have not been specifically set forth in haec verba herein. It is also noted that the terms comprising and containing are intended to be open and permits the inclusion of additional elements or steps. Where ranges are given, endpoints are included. Furthermore, unless otherwise indicated or otherwise evident from the context and understanding of one of ordinary skill in the art, values that are expressed as ranges can assume any specific value or sub-range within the stated ranges in different embodiments of the invention, to the tenth of the unit of the lower limit of the range, unless the context clearly dictates otherwise.

[0582] This application refers to various issued patents, published patent applications, journal articles, and other publications, all of which are incorporated herein by reference. If there is a conflict between any of the incorporated references and the instant specification, the specification shall control. In addition, any particular embodiment of the present invention that falls within the prior art may be explicitly excluded from any one or more of the claims. Because such embodiments are deemed to be known to one of ordinary skill in the art, they may be excluded even if the exclusion is not set forth explicitly herein. Any particular embodiment of the invention can be excluded from any claim, for any reason, whether or not related to the existence of prior art.

[0583] Those skilled in the art will recognize or be able to ascertain using no more than routine experimentation many equivalents to the specific embodiments described herein. The scope of the present embodiments described herein is not intended to be limited to the above Description, but rather is as set forth in the appended claims. Those of ordinary skill in the art will appreciate that various changes and modifications to this description may be made without departing from the spirit or scope of the present invention, as defined in the following claims.