Gold catalyzed polymerization reactions of unsaturated substrates

Abstract

The present invention provides novel methods and processes for polymerizing unsaturated substrates, such as alkyne bearing monomers, with arenes. The polymerizations are catalyzed by gold (Au) catalysts/complexes and/or other cocatalysts. The invention further provides novel structurally complex polymers prepared in high yield via an intermolecular polyhydroarylation mechanism. Such resulting products comprise oligomeric and polymeric materials with novel molecular architectures and microstructures, which subsequently impart unique properties. The invention includes both the synthesis methods and processes and the resulting compounds and compositions of matter.

Claims

1. A polymer having the structure: ##STR00013## where Ar is an arene group; R is selected from the group consisting of unsubstituted arylene, substituted arylene, unsubstituted heteroarylene, substituted heteroarylene, unsubstituted hydrocarbylene, substituted hydrocarbylene, R.sub.2, SR.sub.2, OR.sub.2, COOR.sub.2, NHR.sub.2, and NR.sub.2R.sub.3, where R.sub.2 is a hydrocarbylene group and R.sub.3 is a hydrocarbyl group; and n is an integer between about 5 and about 10,000.

2. A polymer having the structure: ##STR00014## where Ar is an arene group; R is selected from the group consisting of unsubstituted arylene, substituted arylene, unsubstituted heteroarylene, substituted heteroarylene, unsubstituted hydrocarbylene, substituted hydrocarbylene, R.sub.2, SR.sub.2, OR.sub.2, COOR.sub.2, NHR.sub.2, and NR.sub.2R.sub.3, where R.sub.2 is a hydrocarbylene group and R.sub.3 is a hydrocarbyl group; R′ and R″ are selected from the group consisting of unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, F, Cl, Br, I, CN, R.sub.2, SR.sub.2, OH, OR.sub.2, COOH, COOR.sub.2, NH.sub.2, NHR.sub.2, and NR.sub.2R.sub.3, where R.sub.2 and R.sub.3 are independently selected from a hydrocarbyl group; and n is an integer between about 5 and about 10,000.

3. A cross conjugated polymer having the structure: ##STR00015## where Ar.sub.1 is one arene group; Ar.sub.2 is another arene group, either the same as or different from Ar.sub.1; and n is an integer between about 5 and about 10,000.

4. A polymer having the structure: ##STR00016## where Ar.sub.1 is one arene group; Ar.sub.2 is another arene group, either the same as or different from Ar.sub.1: R″ is selected from the group consisting of unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, F, Cl, Br, I, CN, R.sub.2, SR.sub.2, OH, OR.sub.2, COOH, COOR.sub.2, NH.sub.2, NHR.sub.2, and NR.sub.2R.sub.3, where R.sub.2 and R.sub.3 are independently selected from a hydrocarbyl group; and where n is an integer between about 5 and about 10,000.

5. A polymer having a structure selected from the group consisting of structures of the formulae P1, P2, P3, P4, P5, P6 and P7, in which n is an integer between about 5 and about 10,000: ##STR00017## wherein each R is independently selected from the group consisting of unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, F, Cl, Br, I, CN, R.sub.2, SR.sub.2, OH, OR.sub.2, COOH, COOR.sub.2, NH.sub.2, NHR.sub.2, and NR.sub.2R.sub.3, where R.sub.2 and R.sub.3 are independently selected from a hydrocarbyl group; ##STR00018##

6. The polymer of claim 5, wherein the polymer has the formula: ##STR00019## wherein each R is independently selected from the group consisting of unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, F, Cl, Br, I, CN, R.sub.2, SR.sub.2, OH, OR.sub.2, COOH, COOR.sub.2, NH.sub.2, NHR.sub.2, and NR.sub.2R.sub.3, where R.sub.2 and R.sub.3 are independently selected from a hydrocarbyl group, and n is an integer between about 5 and about 10,000.

7. The polymer of claim 5, wherein the polymer has the formula: ##STR00020## wherein n is an integer between about 5 and about 10,000.

8. The polymer of claim 5, wherein the polymer has the formula: ##STR00021## wherein n is an integer between about 5 and about 10,000.

9. The polymer of claim 5, wherein the polymer has the formula: ##STR00022## wherein n is an integer between about 5 and about 10,000.

10. The polymer of claim 5, wherein the polymer has the formula: ##STR00023## wherein n is an integer between about 5 and about 10,000.

11. The polymer of claim 5, wherein the polymer has the formula: ##STR00024## wherein n is an integer between about 5 and about 10,000.

12. The polymer of claim 5, wherein the polymer has the formula: ##STR00025## wherein n is an integer between about 5 and about 10,000.

13. The polymer of claim 1, wherein R is selected from the group consisting of unsubstituted hydrocarbylene, substituted hydrocarbylene, R.sub.2, SR.sub.2, OR.sub.2, COOR.sub.2, NHR.sub.2, and NR.sub.2R.sub.3.

14. The polymer of claim 2, wherein R is selected from the group consisting of unsubstituted hydrocarbylene, substituted hydrocarbylene, R.sub.2, SR.sub.2, OR.sub.2, COOR.sub.2, NHR.sub.2, and NR.sub.2R.sub.3.

15. The polymer of claim 1, wherein R is selected from the group consisting of unsubstituted hydrocarbylene and substituted hydrocarbylene.

16. The polymer of claim 2, wherein R is selected from the group consisting of unsubstituted hydrocarbylene and substituted hydrocarbylene.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The drawings, which are incorporated in and form a portion of the specification, illustrate certain claims of the invention and, together with the entire specification, are meant to explain preferred embodiments of the present invention to those skilled in the art. The drawings supplement the specification and are intended to illustrate further the invention and its advantages. The figures and drawings shown or described in this disclosure and in the Detailed Description of the Invention are as follows:

(2) FIG. 1 shows a representation of the catalyst structures utilized in the present invention.

(3) FIG. 2 shows a graphical representation of the .sup.1H NMR of small molecule 1 of the present invention, wherein the horizontal axis represents chemical shift (ppm), and the vertical axis represents signal intensity.

(4) FIG. 3 shows a graphical representation of the GPC chromatogram of polymer P1 of the present invention.

(5) FIG. 4 shows a graphical representation of the .sup.1H NMR of polymer P2 of the present invention, wherein the horizontal axis represents chemical shift (ppm), and the vertical axis represents signal intensity.

(6) FIG. 5 shows a graphical representation of the GPC chromatogram of polymer P2 of the present invention.

(7) FIG. 6 shows a graphical representation of the .sup.1H NMR of polymer P3 of the present invention, wherein the horizontal axis represents chemical shift (ppm), and the vertical axis represents signal intensity.

(8) FIG. 7 shows a graphical representation of the GPC chromatogram of polymer P3 of the present invention.

(9) FIG. 8 shows a graphical representation of the .sup.1H NMR of polymer P4 of the present invention, wherein the horizontal axis represents chemical shift (ppm), and the vertical axis represents signal intensity.

(10) FIG. 9 shows a graphical representation of the GPC chromatogram of polymer P4 of the present invention.

(11) FIG. 10 shows a graphical representation of the GPC chromatogram of polymer P5 of the present invention.

(12) FIG. 11 shows a graphical representation of the GPC chromatogram of polymer P6 of the present invention.

(13) FIG. 12 shows a graphical representation of the GPC chromatogram of polymer P7 of the present invention.

(14) FIG. 13 shows a graphical representation of the GPC chromatogram of polymer P8 of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

(15) The present invention provides novel processes for polymerizing unsaturated substrates, for example, alkyne bearing monomers, with arenes. The invention further provides novel polymers through the sequential polyhydroarylation of multifunctional monomers.

(16) The present invention overcomes two major long-standing issues associated with conjugated polymers: 1) Common synthetic methodologies require harsh reaction conditions, air/moisture-free conditions, and functionalization of monomers with toxic and expensive metalation procedures. The polyhydroarylation of the invention provides a facile mechanism tolerating air and water to directly couple aryl monomers to access cross-conjugated and non-conjugated polymers; and 2) Current synthetic methodologies are limited in terms of structures that can be readily synthesized from available starting materials. The polyhydroarylation of the invention provides a pathway to access novel macromolecular architectures that have potential in the areas of specialty polymers (i.e. fluorinated polymers, elastomers, for example), high performance and engineering polymers, coatings, polymers for optoelectronics and energy applications, and a wide range of other applications.

(17) 1. In one embodiment, the invention provides processes for polymerizing alkyne bearing monomers with arenes. The process comprises mixing one, or more than one, monomer with a gold (Au) catalyst or initiator, and sometimes other cocatalysts, coinitiators, or coactivators derived from silver (Ag), copper (Cu), at least one acid, or a combination thereof, for example, to produce a polymer that comprises one or more than one type of monomer. In other embodiments, the polymerization process utilizes two or more monomers, resulting in copolymerization.

(18) “Alkyne” is intended to embrace a linear, branched, cyclic, or a combination of linear and/or branched and/or cyclic, hydrocarbon chain(s) and/or ring(s) having at least one carbon-carbon triple bond. “Alkynylene” is intended to embrace a linear, branched, cyclic, or a combination of linear and/or branched and/or cyclic, hydrocarbon chain(s) and/or ring(s) having at least one carbon-carbon triple bond.

(19) “Arene (Ar)” is defined as an optionally substituted aromatic ring system, such as phenyl or naphthyl. Arene groups include monocyclic aromatic rings and polycyclic aromatic ring systems. In other embodiments, arene groups can be unsubstituted. In other embodiments, arene groups can be substituted.

(20) “Heteroarene” is defined as an optionally substituted aromatic ring system where heteroatoms include, but are not limited to, oxygen, nitrogen, sulfur, selenium, phosphorus, etc. In other embodiments, heteroaryl groups can be unsubstituted.

(21) 2. In one embodiment, the invention provides polymers of the formula (I):

(22) ##STR00001##
where Ar is an arene group; R is selected from the group consisting of unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted hydrocarbylene, hydrocarbyl, substituted hydrocarbylene, hydrocarbyl, F, Cl, Br, I, CN, R.sub.2, SR.sub.2, OH, OR.sub.2, COOH, COOR.sub.2, NH.sub.2, NHR.sub.2, or NR.sub.2R.sub.3, where R.sub.2 and R.sub.3 are independently selected from a hydrocarbyl group; R can be any functional group; and n is an integer between about 5 and about 10,000.

(23) 3. In another embodiment, the invention provides polymers of the formula (II):

(24) ##STR00002##
where Ar is an arene group; R, R′, and R″ are selected from the group consisting of unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted hydrocarbylene, hydrocarbyl, substituted hydrocarbylene, hydrocarbyl, F, Cl, Br, I, CN, R.sub.2, SR.sub.2, OH, OR.sub.2, COOH, COOR.sub.2, NH.sub.2, NHR.sub.2, or NR.sub.2R.sub.3, where R.sub.2 and R.sub.3 are independently selected from a hydrocarbyl group; R can be any functional group; and n is an integer between about 5 and about 10,000.

(25) 4. In another embodiment, the invention provides cross conjugated polymers of the formula (III):

(26) ##STR00003##
where Ar.sub.1 is one arene group; Ar.sub.2 is another arene group, either the same as or different from Ar.sub.1; and n is an integer between about 5 and about 10,000.

(27) Cross-conjugated molecules are molecules with three unsaturated groups, two of which although conjugated to a third unsaturated center are not conjugated to each other. Electron communication via cross conjugation has been observed and provides for molecular systems with unique optoelectronic properties of fundamental and practical importance.

(28) 5. In one embodiment, the invention provides polymers of the formula (IV):

(29) ##STR00004##
where Ar.sub.1 is one arene group; Ar.sub.2 is another arene group, either the same as or different from Ar.sub.1; R″ is selected from the group consisting of unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted aryl, substituted aryl, unsubstituted heteroaryl, substituted heteroaryl, unsubstituted hydrocarbylene, hydrocarbyl, substituted hydrocarbylene, hydrocarbyl, F, Cl, Br, I, CN, R.sub.2, SR.sub.2, OH, OR.sub.2, COOH, COOR.sub.2, NH.sub.2, NHR.sub.2, or NR.sub.2R.sub.3, where R.sub.2 and R.sub.3 are independently selected from a hydrocarbyl group; and n is an integer between about 5 and about 10,000.

(30) For Nos. (2) through (5) above (formulas I through IV), the size of the polymers can vary widely, depending on the properties desired. In some embodiments, n is an integer of at least about 10, at least about 20, at least about 50, or at least about 100. In some embodiments, n is an integer between about 5 and about 10,000, between about 10 and about 10,000, between about 10 and about 5,000, between about 10 and about 2,500, between about 10 and about 1,000, between about 10 and about 500, between about 50 and about 10,000, between about 50 and about 5,000, between about 50 and about 2,500, between about 50 and about 1,000, between about 50 and about 500, between about 100 and about 10,000, between about 100 and about 5,000, between about 100 and about 2,500, between about 100 and about 1,000, or between about 100 and about 500. Other intervals, combining any of the above numerical parameters to form a new interval, can also be used (e.g., n between about 500 and 2,500).

(31) 6. In additional embodiments, the invention provides polymer compound(s) ten (10) units long and below, i.e., oligomer(s), wherein the oligomer(s) is(are) of size n, wherein n is an integer between 1 and 10.

(32) Some embodiments described herein are recited as “comprising” or “comprises” with respect to their various elements. In alternative embodiments, those elements can be recited with the transitional phrase “consisting essentially of” or “consists essentially of” as applied to those elements. In further alternative embodiments, those elements can be recited with the transitional phrase “consisting of” or “consists of” as applied to those elements. Thus, for example, if a composition or method is disclosed herein as comprising A and B, the alternative embodiment for that composition or method of “consisting essentially of A and B” and the alternative embodiment for that composition or method of “consisting of A and B” are also considered to have been disclosed herein. Likewise, embodiments recited as “consisting essentially of” or “consisting of” with respect to their various elements can also be recited as “comprising” as applied to those elements.

Examples

(33) General Comments. All manipulations were performed under an inert atmosphere using standard glove box and Schlenk techniques. Reagents, unless otherwise specified, were purchased from Sigma-Aldrich and used without further purification. (Acetonitrile)[(2-biphenyl)di-tert-butylphosphine]gold(I) hexafluoroantimonate and [1,3-Bis(2,6-diisopropylphenyl)imidazol-2-ylidene] [bis(trifluoromethanesulfonyl)imide]gold(I), referred to as Au-1 and Au-2 respectively, were obtained from Strem and used as received. FIG. 1 shows the structures of Au-1 and Au-2. 1,2-dichloroethane and dichloromethane were degassed and dried over 4 Å molecular sieves. Deuterated solvents (CDCl.sub.3 and C.sub.2D.sub.2Cl.sub.4) were purchased from Cambridge Isotope Labs and used as received. .sup.1H NMR spectra were collected on a Bruker Ascend 600 MHz spectrometer and chemical shifts, δ (ppm) were referenced to the residual solvent impurity peak of the given solvent. Data reported as: s=singlet, d=doublet, t=triplet, m=multiplet, br=broad; coupling constant(s), J, are given in Hz. Microwave assisted reactions were performed in a CEM Discover microwave reactor. The peak molecular weight (M.sub.p), number average molecular weight (M.sub.n), weight average molecular weight (M.sub.w), and dispersity (Ð) were determined by gel permeation chromatography (GPC) relative to polystyrene standards at 160° C. in 1,2,4-trichlorobenzene (stabilized with 125 ppm of BHT) in an Agilent PL-GPC 220 High Temperature GPC/SEC system using a set of four PLgel 10 μm MIXED-B columns. Polymer samples were pre-dissolved at a concentration of 1.00-2.00 mg mL.sup.−1 in 1,2,4-trichlorobenzene with stirring for 4 h at 150° C.

Example 1. This Example Involved the Synthesis of the Polymer P1

(34) ##STR00005##

(35) 1,4-didodecyl-2,5-dimethylbenzene (1). Pd—PEPPSI—IPr (0.273 g, 3.5 mol %) and 1,4-dibromo-2,5-dimethylbenzene (3.52 g, 8.2 mmol) were added to an oven-dried flask equipped with a stir bar. Toluene (PhMe) (30 mL) was added and the reaction mixture was stirred at room temperature to dissolve the contents. A solution of n-dodecylzinc bromide (80.0 mL, 40.3 mmol) in tetrahydrofuran (THF) (0.50 M) was then added dropwise over a period of 0.5 h using a dropping funnel. After stirring for 16 h at room temperature, the reaction was heated to 60° C. and stirred at that temperature for 2 h. Upon cooling, the reaction mixture was precipitated with methanol and filtered through a Buchner funnel. The solid was then passed through a silica plug with ethyl acetate. Volatiles were removed in vacuo to afford a white crystalline solid (4.67 g, 82%). .sup.1H NMR (600 MHz, CDCl.sub.3) δ 6.90 (s, 2H), 2.51 (t, J=7.0, 4H), 2.24 (s, 6H), 1.54 (m, 4H), 1.40-1.20 (m, 36H), 0.89 (t, J=7.0 Hz, 6H). FIG. 2 shows the .sup.1H NMR of small molecule 1.

(36) Synthesis of P1. A 1 dram vial with a stir bar was loaded with 1 (0.050 g, 0.113 mmol) and 1,4-diethynylbenzene (0.014 g, 0.113 mmol) in a nitrogen filled glove box. Approximately 8 mol AuCl.sub.3, 16 mol % AgSbF.sub.6, and 400 μL of dichloromethane (DCM), i.e., CH.sub.2Cl.sub.2, were added. The vial was sealed and stirred at room temperature overnight. The mixture was precipitated into methanol and collected via filtration. The residual solid was loaded into an extraction thimble and washed successively with methanol (4 h), and acetone (4 h). The polymer was dried in vacuo to give 0.045 g (70%) of a black solid. GPC (160° C., 1,2,4-trichlorobenzene)=17.5 kg mol.sup.−1, Mn=10.8 kg mol.sup.−1, Mw=19.5 kg mol.sup.−1, Ð=1.8. .sup.1H NMR (600 MHz, CDCl.sub.3, 313 K) δ 7.15 (s, 2H), 6.91 (s, 1H), 6.88 (s, 1H), 5.94 (br, 2H), 5.04 (br, 2H), 2.27 (s, 3H), 2.24 (s, 3H), 1.54 (m, 4H), 1.40-1.20 (m, 36H), 0.89 (t, J=6.8 Hz, 6H). FIG. 3 shows the GPC chromatogram of P1.

Example 2. This Example Involved the Synthesis of the Polymer P2

(37) ##STR00006##

(38) Synthesis of P2. A 1 dram vial with a stir bar was loaded with 1,2,4,5-tetramethylbenzene (0.050 g, 0.373 mmol) and 1,4-diethynylbenzene (0.047 g, 0.373 mmol) in a nitrogen filled glove box. Approximately 2 mol % Au-1 and 400 μL of 1,2-dichloroethane (DCE) were added. The vial was sealed and stirred at room temperature for 6 h. The mixture was precipitated into methanol and collected via centrifugation. The residual solid was loaded into an extraction thimble and washed successively with methanol (4 h), and acetone (4 h). The polymer was dried in vacuo to give 0.039 g (40%) of a brown solid. GPC (160° C., 1,2,4-trichlorobenzene) M.sub.p=23.5 kg mol.sup.−1, M.sub.n=10.0 kg mol.sup.−1, M.sub.w=47.5 kg mol.sup.−1, Ð=4.71. .sup.1H NMR (600 MHz, C.sub.2D.sub.2Cl.sub.4, 393 K) δ 8.0-7.0 (Br, 4H), 7.0-6.3 (Br, 4H), 2.5-1 (Br, 12H). FIG. 4 shows the .sup.1H NMR of P2 and FIG. 5 shows the GPC chromatogram of P2.

Example 3. This Example Involved the Synthesis of the Polymer P3

(39) ##STR00007##

(40) Synthesis of P3. A 1 dram vial with a stir bar was loaded with 1,3,5-trimethylbenzene (0.050 g, 0.416 mmol) and 1,4-diethynylbenzene (0.052 g, 0.416 mmol) in a nitrogen filled glove box. Approximately 2 mol % Au-1 and 400 μL of 1,2-dichloroethane (DCE) were added. The vial was sealed and stirred at room temperature for 6 h. The mixture was precipitated into methanol and collected via centrifugation. The residual solid was loaded into an extraction thimble and washed successively with methanol (4 h), and acetone (4 h). The polymer was dried in vacuo to give 0.041 g (38%) of a brown solid. GPC (160° C., 1,2,4-trichlorobenzene) M.sub.p=25.3 kg mol.sup.−1, M.sub.n=13.2 kg mol.sup.−1, M.sub.w=119.8 kg mol.sup.−1, Ð=9.0. .sup.1H NMR (600 MHz, CDCl.sub.3 313 K) δ 8.0-7.2 (Br, 5H), 7.2-6.3 (Br, 4H), 2.5-1.6 (Br, 9H). FIG. 6 shows the .sup.1H NMR of P3 and FIG. 7 shows the GPC chromatogram of P3.

Example 4. This Example Involved the Synthesis of the Polymer P4

(41) ##STR00008##

(42) Synthesis of P4. A 1 dram vial with a stir bar was loaded with thiophene (0.050 g, 0.594 mmol) and 1,4-diethynylbenzene (0.075 g, 0.594 mmol) in a nitrogen filled glove box. Approximately 2 mol % Au-1 and 400 μL of 1,2-dichloroethane (DCE) were added. The vial was sealed and stirred at room temperature for 24 h. The mixture was precipitated into methanol and collected via centrifugation. The residual solid was loaded into an extraction thimble and washed successively with methanol (4 h), and acetone (4 h). The polymer was dried in vacuo to give 0.025 g (20%) of a brown solid. GPC (160° C., 1,2,4-trichlorobenzene) M.sub.p=4.5 kg mol.sup.−1, M.sub.n=1.5 kg mol.sup.−1, M.sub.w=6.9 kg mol.sup.−1, Ð=4.5. .sup.1H NMR (600 MHz, CDCl.sub.3 313 K) δ 8.0-7.5 (Br, 4H), 7.5-7.2 (Br, 2H), 7.2-6.5 (Br, 2H). FIG. 8 shows the .sup.1H NMR of P4 and FIG. 9 shows the GPC chromatogram of P4.

Example 5. This Example Involved the Synthesis of the Polymer P5

(43) ##STR00009##

(44) Synthesis of P5. A 1 dram vial with a stir bar was loaded with methyl 4-bromobenzoate (0.050 g, 0.233 mmol) and 1,4-diethynylbenzene (0.029 g, 0.233 mmol) in a nitrogen filled glove box. Approximately 2 mol % Au-1 and 400 μL of 1,2-dichloroethane (DCE) were added. The vial was sealed and stirred at room temperature for 4 h. The mixture was precipitated into methanol and collected via centrifugation. The residual solid was loaded into an extraction thimble and washed successively with methanol (4 h), and acetone (4 h). The polymer was dried in vacuo to give 0.028 g (36%) of a brown solid. GPC (160° C., 1,2,4-trichlorobenzene) M.sub.p=8.2 kg mol.sup.−1, M.sub.n=1.4 kg mol.sup.−1, M.sub.w=12.5 kg mol.sup.−1, Ð=8.7. FIG. 10 shows the GPC chromatogram of P5.

Example 6. This Example Involved the Synthesis of the Polymer P6

(45) ##STR00010##

(46) Synthesis of P6. A 1 dram vial with a stir bar was loaded with methyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) benzoate (0.050 g, 0.191 mmol) and 1,4-diethynylbenzene (0.024 g, 0.191 mmol) in a nitrogen filled glove box. Approximately 2 mol % Au-1 and 400 μL of 1,2-dichloroethane (DCE) were added. The vial was sealed and stirred at room temperature for 4 h. The mixture was precipitated into methanol and collected via centrifugation. The residual solid was loaded into an extraction thimble and washed successively with methanol (4 h), and acetone (4 h). The polymer was dried in vacuo to give 0.030 g (41%) of a brown solid. GPC (160° C., 1,2,4-trichlorobenzene) M.sub.p=2.6 kg mol.sup.1, Mn=2.0 kg mol.sup.1, M.sub.w=6.6 kg mol.sup.−1, Ð=3.2. FIG. 11 shows the GPC chromatogram of P6.

Example 7. This Example Involved the Synthesis of the Polymer P7

(47) ##STR00011##

(48) Synthesis of P7. A microwave tube (10 mL) with a stir bar was loaded with 1-methyl-4-nitrobenzene (0.050 g, 0.365 mmol) and 1,4-diethynylbenzene (0.046 g, 0.365 mmol) in a nitrogen filled glove box. Approximately 2 mol Au-2 and 400 μL of 1,2-dichloroethane (DCE) were added. The tube was sealed and heated at 110° C. for 20 min in a microwave reactor. The mixture was precipitated into methanol and collected via centrifugation. The residual solid was loaded into an extraction thimble and washed successively with methanol (4 h), and acetone (4 h). The polymer was dried in vacuo to give 0.034 g (35%) of a brown solid. GPC (160° C., 1,2,4-trichlorobenzene) M.sub.p=7.4 kg mol.sup.−1, M.sub.n=4.5 kg mol.sup.−1, M.sub.w=8.0 kg mol.sup.−1, Ð=1.8. FIG. 12 shows the GPC chromatogram of P7.

Example 8. This Example Involved the Synthesis of the Polymer P8

(49) ##STR00012##

(50) Synthesis of P8. A microwave tube (10 mL) with a stir bar was loaded with 1,2,4,5-tetramethylbenzene (0.050 g, 0.373 mmol) and deca-1,9-diyne (0.050 g, 0.375 mmol) in a nitrogen filled glove box. Approximately 2 mol % Au-1 and 400 μL of 1,2-dichloroethane (DCE) were added. The tube was sealed and heated at 110° C. for 20 min in a microwave reactor. The mixture was precipitated into methanol and collected via centrifugation. The residual solid was loaded into an extraction thimble and washed successively with methanol (4 h), and acetone (4 h). The polymer was dried in vacuo to give 0.047 g (46%) of a waxy brown solid. GPC (160° C., 1,2,4-trichlorobenzene) M.sub.p=7.7 kg mol.sup.−1, M.sub.n=4.3 kg mol.sup.−1, M.sub.w=21.7 kg mol.sup.−1, Ð=5.0. .sup.1H NMR FIG. 13 shows the GPC chromatogram of P8.

(51) All parameters presented herein including, but not limited to, temperatures, pressures, volumes, dimensions, times, sizes, amounts, quantities, ratios, weights, and/or percentages, and the like, for example, represent approximate values. Further, references to ‘a’ or ‘an’ concerning any particular item, component, material, or product is defined as at least one and could be more than one.

(52) The above detailed description is presented to enable any person skilled in the art to make and use the invention. Specific details have been revealed to provide a comprehensive understanding of the present invention and are used for explanation of the information provided. These specific details, however, are not required to practice the invention, as is apparent to one skilled in the art. Descriptions of specific applications, analyses, configurations, and calculations are meant to serve only as representative examples. Various modifications to the preferred embodiments may be readily apparent to one skilled in the art, and the general principles defined herein may be applicable to other embodiments and applications while still remaining within the scope of the invention. There is no intention for the present invention to be limited to the embodiments shown and the invention is to be accorded the widest possible scope consistent with the principles and features disclosed herein.

(53) While various embodiments of the present invention have been described above, it should be understood that they have been presented by way of example and not limitation. It will be apparent to persons skilled in the relevant art(s) that various changes in form and detail can be made therein without departing from the spirit and scope of the present invention. In fact, after reading the above description, it will be apparent to one skilled in the relevant art(s) how to implement the invention in alternative embodiments. Thus, the present invention should not be limited by any of the above-described exemplary embodiments.

(54) The compositions, processes, compounds, products, configurations, systems, and methods of the present invention are often best practiced by empirically determining the appropriate values of the operating parameters, or by conducting simulations to arrive at best design for a given application. Accordingly, all suitable modifications, combinations, and equivalents should be considered as falling within the spirit and scope of the invention.

REFERENCES

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