AN APPROACH TO A BOTTOM-UP SYNTHESIS OF NANOCARBONS

Abstract

Provided is a method for the synthesis of a -conjugated system from oligofurans, under conditions involving cycloaddition.

Claims

1.-79. (canceled)

80. A method for the synthesis of a -conjugated system, the method comprising reacting an oligofuran with at least one aryne or heteroaryne to convert each furan moiety in said oligofuran to a cycloadduct and reacting said cycloadduct to yield the n-conjugated system.

81. The method according to claim 80, wherein the cycloadduct is an extended cycloadduct prepared by reacting the cycloadduct with at least one diene, prior to conversion to the -conjugated system.

82. The method according to claim 80, wherein the cycloadduct is an oxo- or syn-cycloadduct, such that each cycloadduct is in the form of an oxo-cyclocadduct or a syn-cycloadduct.

83. The method according to claim 80, wherein the aryne or heteroaryne is a multicyclic-aryne or multicyclic-heteroaryne.

84. The method according to claim 80, wherein the n-conjugated system is selected amongst oligoarenes, oligoacenes, graphene segments and carbon nanobelts.

85. The method according to claim 80, wherein the oligofuran is selected amongst linear oligofurans and cyclic oligofurans.

86. The method according to claim 80, wherein the oligofuran is of the structure: ##STR00038## wherein n is an integer defining the number of furan moieties that are bonded to each other; each of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is independently selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; C.sub.6-C.sub.10aryl; C.sub.5-C.sub.10 heteroaryl comprising between 1 and 5 heteroatoms selected from N, O and S; an alkyl stannyl; CN; CO.sub.2H; OH; SH; NRRR; NO.sub.2; (C.sub.1-C.sub.10alkyl).sub.3Si; (C.sub.1-C.sub.10alkyl).sub.3Sn; trifluoromethanesulfonate (triflate) and halogen, wherein each of R, R and R is the same or different and is selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; and C.sub.6-C.sub.10aryl; or R.sub.1 and R.sub.2, or R.sub.2 and R.sub.3, or R.sub.3 and R.sub.4, together with the carbon atoms to which they are bonded form a 4-8-membered ring comprising between 0 and 3 double bonds, and/or between 0 and 3 heteroatoms selected from O, N, and S; the 4-8 membered ring system being optionally substituted by at least one group selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; C.sub.6-C.sub.10aryl; C.sub.5-C.sub.10 heteroaryl comprising between 1 and 5 heteroatoms selected from N, O and S; an alkyl stannyl; CN; CO.sub.2H; OH; SH; NRRR; NO.sub.2; (C.sub.1-C.sub.10alkyl).sub.3Si; (C.sub.1-C.sub.10alkyl).sub.3Sn; trifluoromethanesulfonate (triflate) and halogen, wherein each of R, R and R is the same or different and is selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; and C.sub.6-C.sub.10aryl; wherein at least one of R.sub.1, R.sub.2, R.sub.3 and R.sub.4 is a furan ring moiety of the oligofuran chain.

87. The method according to claim 86, wherein at least one of R.sub.1 and R.sub.4 is a furan ring moiety.

88. The method according to claim 86, wherein one of R.sub.1 and R.sub.4 is a furan ring moiety and the other of R.sub.1 and R.sub.4 is selected from hydrogen; C.sub.1-C.sub.10alkyl; CN; CO.sub.2H; (C.sub.1-C.sub.10alkyl).sub.3Sn; and a halogen.

89. The method according to claim 86, wherein one of R.sub.1 and R.sub.4 is a furan ring moiety and the other of R.sub.1 and R.sub.4 is selected from hydrogen; an alkyl stannyl and a halogen.

90. The method according to claim 80, wherein the oligofuran is linear, each end-of-chain furan having an a-carbon substituted by a group selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; C.sub.6-C.sub.10aryl; C.sub.5-C.sub.10 heteroaryl comprising between 1 and 5 heteroatoms selected from N, O and S; an alkyl stannyl; CN; CO.sub.2H; OH; SH; NRRR; NO.sub.2; (C.sub.1-C.sub.10alkyl).sub.3Si; (C.sub.1-C.sub.10alkyl).sub.3Sn; trifluoromethanesulfonate (triflate) and halogen, wherein each of R, R and R is the same or different and is selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; and C.sub.6-C.sub.10aryl.

91. The method according to claim 86, wherein the cyclic oligofuran is of the structure: ##STR00039## wherein each of n, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are as defined in claim 86.

92. The method according to claim 80, wherein the -conjugated system is of the structure: ##STR00040## wherein each peripheral carbon atom is substituted with a group or an atom selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; C.sub.6-C.sub.10aryl; C.sub.5-C.sub.10 heteroaryl comprising between 1 and 5 heteroatoms selected from N, O and S; CN; CO.sub.2H; OH; SH; NRRR; NO.sub.2; (C.sub.1-C.sub.10alkyl).sub.3Si; (C.sub.1-C.sub.10alkyl).sub.3Sn; trifluoromethanesulfonate (triflate) and halogen, wherein each of R, R and R is the same or different and is selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; C.sub.6-C.sub.10aryl; and n is an integer between 2 and 100; or ##STR00041## wherein each peripheral carbon atom is substituted with a group or an atom selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; C.sub.6-C.sub.10aryl; C.sub.5-C.sub.10 heteroaryl comprising between 1 and 5 heteroatoms selected from N, O and S; CN; CO.sub.2H; OH; SH; NRRR; NO.sub.2; (C.sub.1-C.sub.10alkyl).sub.3Si; (C.sub.1-C.sub.10alkyl).sub.3Sn; trifluoromethanesulfonate (triflate) and halogen, wherein each of R, R and R is the same or different and is selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; C.sub.6-C.sub.10aryl; and n is an integer between 2 and 100; or ##STR00042## wherein each peripheral carbon atom is substituted with a group or an atom selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; C.sub.6-C.sub.10aryl; C.sub.5-C.sub.10 heteroaryl comprising between 1 and 5 heteroatoms selected from N, O and S; CN; CO.sub.2H; OH; SH; NRRR; NO.sub.2; (C.sub.1-C.sub.10alkyl).sub.3Si; (C.sub.1-C.sub.10alkyl).sub.3Sn; trifluoromethanesulfonate (triflate) and halogen, wherein each of R, R and R is the same or different and is selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; C.sub.6-C.sub.10aryl; and n is an integer between 2 and 100.

93. A compound having the structure: ##STR00043## wherein each peripheral carbon atom is substituted with a group or an atom selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; C.sub.6-C.sub.10aryl; C.sub.5-C.sub.10 heteroaryl comprising between 1 and 5 heteroatoms selected from N, O and S; CN; CO.sub.2H; OH; SH; NRRR; NO.sub.2; (C.sub.1-C.sub.10alkyl).sub.3Si; (C.sub.1-C.sub.10alkyl).sub.3Sn; trifluoromethanesulfonate (triflate) and halogen, wherein each of R, R and R is the same or different and is selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; C.sub.6-C.sub.10aryl; and n is an integer between 2 and 100; or a compound of the structure: ##STR00044## wherein each peripheral carbon atom is substituted with a group or an atom selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; C.sub.6-C.sub.10aryl; C.sub.5-C.sub.10 heteroaryl comprising between 1 and 5 heteroatoms selected from N, O and S; CN; CO.sub.2H; OH; SH; NRRR; NO.sub.2; (C.sub.1-C.sub.10alkyl).sub.3Si; (C.sub.1-C.sub.10alkyl).sub.3Sn; trifluoromethanesulfonate (triflate) and halogen, wherein each of R, R and R is the same or different and is selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; C.sub.6-C.sub.10aryl; and n is an integer between 2 and 100; or a compound of the structure: ##STR00045## wherein each peripheral carbon atom is substituted with a group or an atom selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; C.sub.6-C.sub.10aryl; C.sub.5-C.sub.10 heteroaryl comprising between 1 and 5 heteroatoms selected from N, O and S; CN; CO.sub.2H; OH; SH; NRRR; NO.sub.2; (C.sub.1-C.sub.10alkyl).sub.3Si; (C.sub.1-C.sub.10alkyl).sub.3Sn; trifluoromethanesulfonate (triflate) and halogen, wherein each of R, R and R is the same or different and is selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; C.sub.6-C.sub.10aryl; and n is an integer between 3 and 100.

94. A method for the synthesis of a cyclic oligofuran, the method comprising: reacting an alkyne-substituted oligofuran in the presence of a metal complex to afford an alkyne-metal macrocycle, treating said macrocycle to obtain a di-acetylene macrocycle and oxidizing said di-acetylene macrocycle to afford the cyclic oligofuran.

95. A method for the synthesis of a cyclic oligofuran, the method comprising: reacting furan with succinyl chloride to afford a linear furan dimer, wherein each furan is separated by a succinyl moiety, optionally repeating the reaction to afford higher homologs of the furan dimer, reacting the furan dimer or higher homolog thereof with succinyl chloride under conditions permitting cyclization into a cyclic macrocycle, and transforming each succinyl moiety of the cyclic macrocycle to a furan, thereby providing the cyclic oligofuran.

96. A method for the synthesis of a cyclic oligofuran, the method comprising: reacting a linear oligofuran with succinyl chloride to afford a linear oligofuran dimer, wherein each oligofuran is separated by a succinyl moiety, optionally repeating the reaction to afford higher homologs of the dimer, reacting the dimer or higher homolog thereof with succinyl chloride under conditions permitting cyclization into a cyclic macrocycle, and transforming each succinyl moiety of the cyclic macrocycle to a furan, thereby providing the cyclic oligofuran.

97. A cyclic oligofuran comprising between 4 and 20 furan ring moieties, each furan ring moiety being covalently associated to another via the furan a-carbon atoms.

98. The cyclic oligofuran according to claim 97, having the structure ##STR00046## wherein each of R.sub.1 and R.sub.4 is a point of connectivity to another furan of the cyclic oligofuran ring system, R.sub.2 and R.sub.3 is selected from hydrogen; C.sub.1-C.sub.10alkyl; C.sub.2-C.sub.10alkenyl; C.sub.2-C.sub.10alkynyl; C.sub.6-C.sub.10aryl; C.sub.5-C.sub.10 heteroaryl comprising between 1 and 5 heteroatoms selected from N, O, S; CN; CO.sub.2H; OH; SH; NRRR; NO.sub.2; (C.sub.1-C.sub.10alkyl).sub.3Si; (C.sub.1-C.sub.10alkyl).sub.3Sn; trifluoromethanesulfonate (triflate) and halogen, wherein each of R, R and R may be the same or different and may be selected from hydrogen, C.sub.1-C.sub.10alkyl, C.sub.2-C.sub.10alkenyl, C.sub.2-C.sub.10alkynyl and C.sub.6-C.sub.10aryl; and wherein n is an integer between 4 and 20.

99. The cyclic oligofuran according to claim 97, comprising 6 furan ring moieties, wherein each of the furan ring moieties is optionally substituted.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0224] In order to better understand the subject matter that is disclosed herein and to exemplify how it may be carried out in practice, embodiments will now be described, by way of non-limiting example only, with reference to the accompanying drawings, in which:

[0225] FIGS. 1A-G provide structures of compounds A-G discussed in the present application.

[0226] FIG. 2 is a schematic representation of certain embodiments of the methodology of the invention.

[0227] FIG. 3 depicts conversion of oligofurans to oligoacenes and GNRs, wherein the various R groups may be the same or different or are selected as disclosed herein.

[0228] FIG. 4 provides an exemplary pathway for the production of cycloarenes and carbon nanobelts according to the invention.

[0229] FIG. 5 provides a schematic representation of substituted arene synthesis from oligofurans, using different types of dienophiles. The letters m and s in parentheses stand for moderate and strong dienophile strength, respectively.

[0230] FIG. 6 depicts synthesis of substituted arenes from oligofuran DM-3F and dienophiles: 2-(trimethylsilyl)phenyl trifluoromethanesulfonate (1) as the benzyne precursor; 5 and 6 are N-methylmaleimide and N-ethylmaleimide, respectively.

[0231] FIG. 7 demonstrates regioselective transformation of long oligofurans to oligoarenes as described herein.

[0232] FIGS. 8A-B are synthetic procedures for the transformation of oligofurans to oligonaphthalenes. For both Figures, reagents and conditions: (a) 1, acetonitrile, CsF, RT; (b) Trimethylsilylchloride, NaI, acetonitrile, 0 C..fwdarw.RT. DM=dimethyl. For DM-3F n=2, 3, 4, 6. For nF: n=2, 6.

[0233] FIGS. 9A-B present exemplary synthesis of bis(triphenylene) from DM-2F (FIG. 9A). Reagents and conditions: (a) CsF, acetonitrile, RT; (b) Trimethylsilylchloride, NaI, acetonitrile, 0 C..fwdarw.RT. FIG. 9B demonstrates conversion of nF to graphene nanoribbos. Reagents and conditions: (a) i. CsF. ii. NaI, SiMe.sub.3Cl. (b) Dehydrogenative coupling (K.sup.0; FeCl.sub.3; AlCl.sub.3). (c) [Ni(cod).sub.2], 1,5-cyclooctadiene, 2,2-bipyridyl. cod=1,5-cyclooctadiene. Groups X are equivalent to variants R as used herein, and integers n are as defined herein.

[0234] FIG. 10 provides exemplary routes for the synthesis of cyclic oligofurans.

[0235] FIG. 11 provides reaction of oligofurans, similarly applicable to linear and cyclic oligofurans, with benzyne, demonstrating their conversion to oligonaphthyls via cycloadduct 1. Reagents and conditions: (a) 2-(trimethylsilyl)phenyl trifluoromethanesulfonate, CsF, acetonitrile. (b) NaI, SiMe.sub.3Cl. R=n-hexyl.

[0236] FIGS. 12A-B provide synthetic pathways to oligoacenes and graphene nanoribbons fromoligofurans. FIG. 12A provides general synthetic pathways and FIG. 12B provides synthetic pathway to oligoacenes and graphene nanoribbons from nF. Variants R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are selected as recited herein regarding the equivalent variants in oligofurans of the invention. Reagents and conditions: (a) i. CsF. ii. NaI, SiMe.sub.3Cl. (b) Dehydrogenative coupling (K.sup.0 or FeCl.sub.3 or AlCl.sub.3). (c) i. DMAD. ii. MeONa, MeOH. iii. Cu, heat (decarboxylation). (d) Grubbs' second-generation catalyst, PhMe, reflux. DMAD=dimethyl acetylenedicarboxylate.

[0237] FIG. 13 demonstrates conversion of a terafuran 4F to graphene nanoribbon 4. Reagents and conditions: (a) i. CsF. ii. NaI, SiMe.sub.3Cl. (b) AlCl.sub.3, H.sup.+. Various substituting groups are as recited herein with respect to the oligofuran.

[0238] FIG. 14 demonstrates synthesis of oligotetracene 8 by the reaction of cycloadduct 6 with isobenzofuran 5. Reagents and conditions: (a) Acetonitrile, heat. (b) p-toluenesulfonic acid, toluene.

[0239] FIG. 15 provides synthetic pathways for 8CF; reagents and conditions: (a) Pt(dppp).sub.2Cl.sub.2, CuI (10% mol), NEt.sub.3; (b) I.sub.2 (2 equiv.), THF, 60 C. (c) CuI, 1,10-phenanathroline, KOH, H.sub.2O, DMSO. (d) AlCl.sub.3, ClC(O)CH.sub.2CH.sub.2C(O)Cl. (e) AlCl.sub.3, ClC(O)CH.sub.2CH.sub.2C(O)Cl, high dilution. (f) HCl, heat. dppp=1,3-Bis(diphenylphosphino)propane, THF=tetrahydrofuran, DMSO=dimethylsulfoxide, NEt.sub.3=trimethylamine The various substituting groups are as recited herein with reference to the oligofuran.

[0240] FIG. 16 demonstrates conversion of cyclic oligofuran 6CF to 6-cyclonapthalene 16, and to a soluble Vogtle's belt 17. Reagents and conditions: (a) i. CsF. ii. NaI, SiMe.sub.3Cl. (b) AlCl.sub.3, H.sup.+. The various substituting groups are as recited herein with reference to oligofuran.

[0241] FIG. 17 demonstrates conversion of macrocyclic furans to carbon nanobelts. Reagents and conditions: (a) i. CsF. ii. NaI, SiMe.sub.3Cl. (b) AlCl.sub.3, H.sup.+.

[0242] FIG. 18 is a schematic representation of growth of 20 to long CNTs by the cycloaddtion of 15 with 6CF.

[0243] FIG. 19 provides synthesis of DM-6F-2C8 (utilized as depicted in FIG. 8B).

[0244] FIGS. 20A-D provide calculated (FIG. 20A) HOMO-LUMO gaps and (FIG. 20B) inter-ring CC bond lengths for nCF and nCT. FIG. 20C provides calculated structures of 6CF and 6CT. FIG. 20D provides the value for the exo angles of furan (125) is closer to that of a hexagon and octagon, compared with that of thiophene (150). All calculations were performed at the (DFT/B3LYP/6-311G(d)) level of theory.

DETAILED DESCRIPTION OF EMBODIMENTS

[0245] In a study leading to the technology disclosed herein, linear oligofurans were reacted with a benzyne precursor, resulting in direct conversion to the cycloadduct 1. Consequent deoxygenation of the cycloadduct resulted in clean conversion to oligonaphthalene 6N. This one-pot reaction demonstrated the direct conversion of one long conjugated system to another. As oligoarenes can undergo dehydrogenation to yield graphene nanoribbons, these results highlight the potential contribution of oligofurans to the field of nanocarbons.

[0246] Combining the conversion of linear furans to graphene-based materials with the introduction of macrocyclic furans yields a new bottom-up synthetic approach in which macrocyclic oligofurans are reacted with arynes to produce cycloarenes, eventually leading to the synthesis of the first carbon nanobelts and carbon nanotubes.

[0247] The disadvantage of the current synthetic approach to CPPs, which employs reductive aromatization of a cyclohexadiene moiety, is its limited versatility. For example, in order to obtain different substituted cycloarenes, one must initiate the synthesis with a different arene macrocycles each time. In this respect, the introduction of a divergent approach using a single intermediate from which various cycloarenes can be easily obtained is highly desirable.

[0248] The method of the invention possesses two great advantages over the commonly applied pathway for obtaining CPPs. Whereas different-sized macrocycles are required to synthesize different cycloarenes over multiple steps, a single cyclic furan can serve as a starting point for various cycloarenes in a single step (cycloaddition and deoxygenation), in this way enabling the rapid development of different cycloarenes that can be converted to a variety of carbon nanobelts.

[0249] The synthesis of very large graphene nanoribbons commonly involves a significant number of steps, and is often limited by the insolubility of the reaction intermediates. The use of different aryne precursors allows the introduction of different oligoarenes with various sizes, eventually leading to GNRs having specific and controllable sizes and shapes. An example for such a procedure is demonstrated by the cycloaddition reaction between 4F and a phenanthryne precursor to afford oligoaryl 3, whose oxidative dehydrogenation will afford GNR 4 (FIG. 13). In general, by using larger aryne precursors, one can gain access to a large variety of GNRs by simply applying these three synthetic steps. Importantly, the GNR may be endowed with functional groups to increase solubility and reduce aggregation such as alkyls, or removable trialkylsilyls groups.

[0250] Introducing oligomers of substituted tetracenes and pentacenes can make a significant contribution. The cycloadduct itself can react as a dienophile with various dienes, which enables a lateral expansion of the conjugated system (via an extended cycloadduct). A diene that can very plausibly undergo this cycloaddition is diphenyl-isobenzofuran 5 (FIG. 14). Indeed, the reaction of such a diene with a monomeric analogue of 6 is known to result in the synthesis of various tetracenes. Thus, cycloaddition of 6 with 5 esults in ditetracene 8. A two-cycloaddition/deoxegenation process yields rubrene-like oligomers (FIG. 14).

[0251] In many cases, the physical properties of linear oligomers are influenced by undesired chain-end effects. In this respect, corresponding fully -conjugated macrocycles represent model systems that combine the infinite defect-free -conjugated chain of an idealized polymer with the advantage of a structurally well-defined oligomer, while excluding perturbing end-effects. This renders them interesting candidates for various future applications in organic and molecular electronics and for the study of hostguest interactions, aggregation, and self-assembly on surfaces.

[0252] In order to synthesize macrocyclic oligofurans, several synthetic pathways are explored, beginning with the two shown in FIG. 15 for the synthesis of 8CF. The first pathway, which was introduced by Bauerle involves the formation of alkyne-Pt macrocycles followed by reductive elimination to obtain diacetylene macrocycles. The diacetylene moiety is consequently oxidized to yield macrocyclic oligofuran 8CF. An alternative pathway involves the Friedel-Crafts acylation of terfuran 12 with acetyl chloride followed by an additional acylation at high dilution to yield macrocycle 14. A Paal-Knorr reaction will transform the diketone moieties to furans, eventually resulting in 8CF.

[0253] The macrocyclic oligofurans synthesized is reacted with various aryne precursors to form macrocyclic cycloadducts. The simplest example involves cycloaddition with benzyne and results in cycloadduct 15 (FIG. 16), which can be deoxygenated to form n-cyclonaphthalene 16, in a manner similar to that successfully applied to liner oligofurans in the previously-described cycloaddition-deoxegenation procedure. The R groups on 6CF are as selected herein, and may particularly be selected amongst alkyls, for increased solubility of the resulting CNB 17.

[0254] Importantly, this synthetic strategy provides easy access to a wide variety of cycloarenes, by simply introducing the macrocyclic oligofurans to different aryl precursors. While macrocyclic arene 19 obtained from the addition of phenanthryne precursor 18 was expected to result in the anti-conformation, the oxidative dehydrogenation in this case was expected to be favorable because of the vicinity of the phenyl rings, as depicted in FIG. 17.

[0255] In a similar manner as previously observed for monomeric furans, cycloadduct 15 exhibited affinity towards dienes, thus resulting in further expansion of the carbon nanobelts. The reactivity of 15 was studied through its reaction with various dienes. Cycloaddition results in compound 20, which can again react with an additional segment of 6CF, resulting in a tandem Diels-Alder cycloaddition and eventually growing long CNTs in a bottom-up approach (FIG. 18). In order to increase the reactivity of 6CF, electron-donating groups such as methoxy may be added to the position, which are expected to significantly increase its reactivity towards dienophiles.

[0256] The resulting CNBs may be endowed with soluble groups, resulting from either the macrocycle or from the benzyne precursors. Alkyl groups should increase the solubility of the CNBs.

Experimental Section

[0257] .sup.1H and .sup.13C NMR spectra were recorded in solution on a Briicker-AVIII 400 MHz and 500 MHz spectrometer using tetramethylsilane (TMS) as the external standard. Chemical shifts are expressed in units. High resolution mass spectra were measured on a HR Q-TOF LCMS and Waters Micromass GCT Premier Mass Spectrometer using ESI and field desorption (FD) ionization. The spectra were recorded using chloroform-d, 1,1,2,2-tetrachloroethane-d.sub.2, DMSO-d.sub.6 as solvents. Flash chromatography (FC) was performed using CombiFlash SiO.sub.2 columns. N-methyl maleimide, N-ethyl maleimide and 2-methylfuran were purchased from Sigma-Aldrich. 2-(Trimethylsilyl)phenyl trifluoromethanesulfonate and 10-trimethylsilylphenanthryl 9-trifluoromethanesulfonate were purchased from Alfa Aesar and abcr respectively. Compounds DM-3F, 2,8-dibromobifuran and 3,3-octyl-2,2-bifuran were synthesized according to literature procedure.

Synthetic Procedure

[0258] 5,5-dimethyl-2,2-bifuran (DM-2F)

##STR00016##

[0259] A three neck RB was charged with 2-methylfuran (5 g, 60.90 mmol) and THF (90 mL) (freshly distilled). After it was cooled to 78 C., a solution of n-BuLi (38.0 mL, 1.6 M, 60.90 mmol) was added dropwise. After addition, the mixture was warmed slowly to room temperature and stirred for 1 h. Again the mixture was cooled to 78 C. and anhydrous CuCl.sub.2 (8.1 g, 60.90 mmol) was added in one portion, then it was warmed to room temperature and stirred overnight. After completion of reaction, the reaction mixture was quenched with water (50 mL) at 0 C., and it was subsequently extracted with hexane (3100 mL). The organic phase was washed twice with water and the solvent was carefully removed to obtained crude DM-2F, which was purified by column separation (n-hexane) to afford a white crystalline solid (1.8 g, 72% yield).

[0260] .sup.1H NMR (400 MHz, CDCl.sub.3): 6.38 (d, J=3.2 Hz, 2H; HC(2)), 6.03 (dd, J=3.3 Hz, 1.2 Hz, 2H; HC(3)), 2.36 (d, J=1 Hz, 6H; HC(5)); .sup.13C NMR (101 MHz, CDCl.sub.3): 151.3 (2 C(4)), 145.2 (2 C(1)), 107.2 (2 C(2)), 105.1 (2 C(3)), 13.6 (2 C(5)); HRMS (ESI): m/z calcd for C.sub.10H.sub.10O.sub.2 (M+H).sup.+: 163.0759, found: 163.0680.

4,4-dimethyl-4H,4H-1,1.sup.1-bi(1,4-epoxynaphthalene) (DM-2CA)

##STR00017##

[0261] Finely powdered anhydrous CsF (0.937 g, 6.17 mmol) was added to a solution of 2-(Trimethylsilyl)phenyl trifluoromethanesulfonate 1 (0.278 mL, 1.35 mmol) and DM-2F (0.1 g, 0.617 mmol) in MeCN (2 mL), and the mixture was stirred at r.t. for 12 h. Then, the reaction mixture was filtered and solvent was removed under reduced pressure. The residue was purified by column chromatography (SiO.sub.2; 9:1 hexane/EtOAc), affording DM-2CA as white crystalline solid (0.150 g, 77% yield).

[0262] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.26 (dd, J=3.2 Hz, 4H), 7.12 (d, J=5.4 Hz, 2H), 7.06 (t, J=7.4 Hz, 2H), 7.00-6.91 (m, 4H), 2.03 (s, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) 152.7, 149.7, 147.1, 143.6, 125.0, 124.7, 121.1, 118.6, 90.4, 90.0, 15.3; HRMS (ESI): m/z calcd for C.sub.22H.sub.18O.sub.2 (M+H).sup.+: 315.1385, found: 315.1412.

4,4-dimethyl-1,1-binaphthalene (DM-2Nap)

##STR00018##

[0263] A solution of DM-2CA (0.02 g. 0.067 mmol) and anhydrous sodium iodide (0.048 g, 0.318 mmol) in 3 mL of dry acetonitrile was treated with trimethylsilyl chloride (0.04 mL, 0.318 mmol) at 0 C. under argon and stirred for 30 min. The reaction was quenched with the addition of 1 mL of 5% aqueous Na.sub.2S.sub.2O.sub.3. The resulting mixture was then extracted with diethyl ether (50 mL). The organic layer was washed with 5% aqueous Na.sub.2S.sub.2O.sub.3 (2 mL) and brine (5 mL) and dried over anhydrous MgSO.sub.4 and the solvent was evaporated under reduced pressure. The residue thus obtained was purified by flash column chromatography on silica gel with hexanes as the eluent to give DM-2Nap (10 mg, 56% yield) as white solid.

[0264] .sup.1H NMR (400 MHz, CDCl.sub.3): =8.10 (dd, J=8.5, 0.6 Hz, 2H; HC(5)), 7.51 (ddd, J=8.3, 6.7, 1.4 Hz, 2H; HC(6)), 7.43 (ddd, J=7.1, 6.3, 0.8 Hz, 4H; HC(3 & 8)), 7.38 (d, J=7.1 Hz, 2H; HC(2)), 7.28 (ddd, J=8.3, 6.7, 1.3 Hz, 2H; HC(7)), 2.81 (d, J=0.9 Hz, 6H; HC(9)); .sup.13C NMR (126 MHz, CDCl.sub.3) 137.0 (2 C(4)), 134.0 (2 C(1)), 133.0 (2 C(4a)), 132.6 (2 C(8a)), 127.6(2 C(2)), 127.3(2 C(8)), 126.2(2 C(3)), 125.6(2 C(6)), 125.5(2 C(7)), 124.2(2 C(5)), 19.6(2 C(9)); HRMS (FD): m/z calcd for C.sub.22H.sub.18: 282.1409 [M].sup.+, found:282.1398.

4,4-dimethyl-4H,4H-1,1:4,1-ter(1,4-epoxynaphthalene) (DM-3CA)

##STR00019##

[0265] Finely powdered anhydrous CsF (0.665 g, 6.57 mmol) was added to a solution of 2-(Trimethylsilyl)phenyl trifluoromethanesulfonate 1 (0.296 mL, 1.44 mmol) and DM-3F (0.1 g, 0.438 mmol) in MeCN (3 mL), and the mixture was stirred at r.t. for 12 h. Then, the reaction mixture was filtered and solvent was removed under reduced pressure. The residue was purified by column chromatography (SiO.sub.2; 9:1 hexane/EtOAc), affording DM-3CA as white solid (0.2 g, 80% yield).

[0266] .sup.1H NMR (400 MHz, CDCl.sub.3) 7.42 (dd, J=19.1, 6.6 Hz, 1H), 7.29-7.20 (m, 9H), 7.05-6.89 (m, 8H), 2.06 (d, J=2.4 Hz, 6H);.sup.13C NMR (101 MHz, CDCl.sub.3) 152.5, 152.4, 150.2, 149.7, 149.6, 149.4, 149.3, 147.1, 146.9, 146.4, 144.5, 144.3, 144.2, 144.2, 143.8, 125.1, 125.0, 125.0, 125.0, 124.9, 124.8, 124.6, 124.7, 121.7, 118.6, 118.5, 15.4; HRMS (ESI): calcd for C.sub.32H.sub.24O.sub.3 (M+H).sup.+: 457.1804, found: 457.1804.

4,4-dimethyl-1,1:4,1-terbenzobenzene (DM-3Nap)

##STR00020##

[0267] A solution of DM-3CA (0.036 g, 0.079 mmol) and anhydrous sodium iodide (0.059 g, 0.395 mmol) in 2 mL of dry acetonitrile was treated with trimethylsilyl chloride (0.03 mL, 0.236 mmol) at 0 C. under argon and stirred for 1 h. The reaction was quenched with the addition of 2 mL of 5% aqueous Na.sub.2S.sub.2O.sub.3. The resulting mixture was then extracted with diethyl ether (30 mL). The organic layer was washed with 5% aqueous Na.sub.2S.sub.2O.sub.3 (2 mL) and brine (5 mL) and dried over anhydrous MgSO.sub.4 and the solvent was evaporated under reduced pressure. The residue thus obtained was purified by flash column chromatography on silica gel with hexanes as the eluent to give DM-3Nap (20 mg, 63% yield) as a white solid.

[0268] .sup.1H NMR (400 MHz, CDCl.sub.3) .sup.1H NMR (500 MHz, Chloroform-d) 8.16-8.12 (m, 2H), 7.62 (ddd, J=8.5, 1.3, 0.7 Hz, 1H), 7.59 (d, J=1.8 Hz, 2H), 7.57-7.48 (m, 9H), 7.41 (ddd, J=8.3, 6.7, 1.3 Hz, 1H), 7.36 (ddd, J=8.3, 6.8, 1.2 Hz, 1H), 7.26-7.24 (m, 2H), 2.84 (d, J=0.6 Hz, 6H);.sup.13C NMR (126 MHz, CDCl.sub.3) 138.47, 138.44, 136.93, 134.21, 134.19, 133.06, 133.04, 132.67, 132.65, 127.70, 127.69, 127.50, 127.35, 126.91, 126.26, 126.24, 125.72, 125.69, 125.67, 124.37, 124.33, 19.66; HRMS (FD): m/z calcd for C.sub.32H.sub.24: 408.1878, found: 408.1882.

5,5-dimethyl-2,2:5,2:5,2-quaterfuran (DM-4F)

##STR00021##

[0269] Pd(PPh.sub.3).sub.4 (0.079 g, 5 mol %, 0.069 mmol) was added to a solution of 2,8-dibromobifuran (0.4 g, 1.37 mmol) and 2-methyl-5-stannyl furan (1.017 g, 2.74 mmol) in dry toluene (10 mL), and the reaction mixture was refluxed under nitrogen overnight and then cooled to room temperature. The mixture was quenched with water, extracted with hexane, dried (MgSO.sub.4), and evaporated. Column chromatography on a silica column, using hexane as eluent gave DM-4F (0.260 g, 65% yield) as yellow colored solid.

[0270] .sup.1H NMR (400 MHz, CDCl.sub.3): 6.66 (d, J=3.5 Hz, 2H), 6.56 (d, J=3.5 Hz, 2H), 6.53 (d, J=3.3 Hz, 2H), 6.08 (dt, J=3.3, 1.0 Hz, 2H), 2.39 (d, J=1.0 Hz, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3): 152.1, 107.6, 107.0, 106.5, 106.1, 76.7, 13.7; HRMS (ESI): m/z calcd for C.sub.18H.sub.14O.sub.4: 294.0892, found: 294.0890.

4,4-dimethyl-4H,4H-1,1:4,1:4,1-quater(1,4-epoxynaphthalene) (DM-4CA)

##STR00022##

[0271] Finely powdered anhydrous CsF (1.029 g, 6.78 mmol) was added to a solution of 2-(Trimethylsilyl)phenyl trifluoromethanesulfonate 1 (0.296 mL, 1.44 mmol) and DM-4F (0.334 mL, 1.6 mmol) in MeCN (2 mL) and ethyl acetate (1 mL), and the mixture was stirred at r.t. for 16 h. Then, the reaction mixture was filtered and solvent was removed under reduced pressure. The residue was purified by column chromatography (9:1 hexane/EtOAc), affording DM-4CA as white solid (0.203 g, 88% yield).

[0272] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.60-7.19 (m, 14 H), 7.11-6.86 (m, 10 H), 2.09 (d, J=1.7 Hz, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3): 152.5, 152.4, 152.4, 150.0, 149.7, 149.7, 149.7, 149.2, 149.1, 147.1, 144.2, 144.0, 125.1, 125.1, 125.0, 124.9, 124.87, 124.8, 121.4, 118.6, 91.4, 90.3, 90.3, 90.0, 15.4; HRMS (ESI): m/z calcd for C.sub.42H.sub.30O.sub.4: 598.2144, found: 598.2151.

4,4-dimethyl-1,1:4,1:4,1-quaternaphthalene (DM-4Nap)

##STR00023##

[0273] A solution of DM-4CA (0.05 g. 0.083 mmol) and anhydrous sodium iodide (0.116 g, 0.773 mmol) in 3 mL of dry acetonitrile was treated with trimethylsilyl chloride (0.071 mL, 0.560 mmol) at 0 C. under argon and stirred for 1 h. The reaction was quenched with the addition of 2 mL of 5% aqueous Na.sub.2S.sub.2O.sub.3. The resulting mixture was then extracted with diethyl ether (20 mL). The organic layer was washed with 5% aqueous Na.sub.2S.sub.2O.sub.3 (2 mL) and brine (5 mL) and dried over anhydrous MgSO.sub.4 and the solvent was evaporated under reduced pressure. The residue thus obtained was purified by flash column chromatography on silica gel with 5% hexane/ethyl acetate eluent to give DM-4Nap (27 mg, 61% yield) as a white solid.

[0274] .sup.1H NMR (400 MHz, CDCl.sub.3): 8.18 (dd, J=8.5, 4.2 Hz, 2H), 7.77-7.64 (m, 8H), 7.62-7.53 (m, 8H), 7.44-7.37 (m, 3H), 7.36-7.30 (m, 3H), 2.88 (s, 6H); .sup.13C NMR (126 MHz, CDCl.sub.3): 138.65, 138.64, 138.32, 138.28, 138.25, 136.88, 136.87, 136.85, 134.26, 134.24, 133.12, 133.11, 133.09, 133.02, 133.00, 132.99, 132.66, 132.65, 127.73, 127.71, 127.54, 127.35, 126.93, 126.27, 126.25, 125.84, 125.81, 125.79, 125.75, 125.71, 124.39, 124.35, 19.7; HRMS (FD): m/z calcd for C.sub.42H.sub.30: 534.2348, found: 534.2325

Synthesis of 5,5-dimethyl-3,4-diortyl-2,2:5,2:5,2:5,2:5, 2-sexifuran (DM-6F-2C8)
5-methyl-2,2-bifuran

##STR00024##

[0275] Pd(PPh.sub.3).sub.4 (0.41 g, 0.36 mmol) was added to a solution of 2-methyl-5-iodofuran (1.5 g, 7.11 mmol) and 2-tributyltinfuran (2.27 mL, 7.11 mmol) in dry toluene (20 mL), and the reaction mixture was refluxed under nitrogen overnight and then cooled to room temperature. The mixture was quenched with water, extracted with hexane, dried (MgSO.sub.4), and evaporated. Column chromatography on a silica column, using hexane as eluent gave 5-methyl-2,2-bifuran (0.5 g, 74% yield) as colorless oil.

[0276] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.40 (dd, J=1.8, 0.8 Hz, 1H), 6.50 (dd, J=3.4, 0.8 Hz, 1H), 6.46 (dd, J=3.4, 1.8 Hz, 2H), 6.09-6.03 (m, 1H), 2.37 (d, J=0.6 Hz, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3): 151.7, 146.9, 145.0, 141.3, 111.3, 107.3, 106.0, 104.1, 13.6.

Tributyl(5-methyl-[2,2-bifuran]-5-yl)stannane

##STR00025##

[0277] A solution of n-BuLi (4.81 mL, 1.6 M in hexanes, 7.70 mmol) was added dropwise to a solution of 5-methyl-2,2-bifuran (0.88 g, 5.93 mmol) in dry tetrahydrofuran (20 mL) at 78 C. under N.sub.2. The reaction mixture was allowed to reach room temperature and stirred for 1 h. The resulting mixture was cooled to 78 C., Bu.sub.3SnCl (1.92 mL, 6.53 mmol) was added dropwise, and the reaction mixture was allowed to reach room temperature and stirred for 2 h. The mixture was quenched with water, extracted with hexane, dried (MgSO.sub.4), and evaporated. Hash chromatography on basified (NEt.sub.3) silica, using hexane as eluent gave tributyl(5-methyl[2,2-bifuran]-5-yl)stannane (1.1 g, 42% yield) as a pale yellow oil.

[0278] .sup.1H NMR (400 MHz, Chloroform-d): 6.59 (d, J=3.2 Hz, 1H), 6.52 (d, J=3.2 Hz, 1H), 6.43 (d, J=3.2 Hz, 1H), 6.04 (dd, J=3.2, 1.0 Hz, 1H), 2.37-2.36 (d, J=1.0 Hz, 3H), 1.64-1.58 (m, 6H), 1.41-1.35 (m, 6H), 1.15-1.08 (m, 6H), 0.91 (d, J=7.3 Hz, 9H); .sup.13C NMR (126 MHz, Chloroform-d) 160.1, 151.3, 145.9, 122.9, 107.2, 105.6, 104.1, 28.9, 27.1, 13.7, 13.6, 13.6, 10.2.

5,5-dimethyl-3,4-dioctyl-2,2:5,2:5:2:5,2:5,2-sexifuran (DM-6F-2C8)

##STR00026##

[0279] Pd(PPh3)4 (0.034 g, 0.029 mmol) was added to a solution of 5,5-dibromo-3,3-dioctyl-2,2-bifuran (0.3 g, 0.580 mmol) and tributyl(5-methyl-[2,2-bifuran]-5-yl)stannane (0.508 g, 1.16 mmol) in dry toluene (5 mL), and the reaction mixture was refluxed under nitrogen overnight and then cooled to room temperature. The mixture was quenched with water, extracted with hexane, dried (MgSO.sub.4), and evaporated. Column chromatography on a silica column, using hexane as eluent gave DM-6F-2C.sub.8 (0.150 g, 40% yield) as yellow solid.

[0280] .sup.1H NMR (400 MHz, CDCl.sub.3): 6.62 (s, 2H), 6.57 (d, J=3.3 Hz, 4H), 6.54-6.49 (m, 2H), 6.08 (dd, J=3.2, 1.0 Hz, 2H), 2.86-2.74 (m, 4H), 2.39 (s, 6H), 1.75-1.67 (m, 4H), 1.45-1.27 (m, 20H), 0.90 (d, J=6.7 Hz, 6H);.sup.13C NMR (101 MHz, CDCl.sub.3) 152.0, 145.3, 144.7, 141.7, 124.7, 108.8, 107.6, 106.7, 106.4, 106.1, 31.9, 31.9, 30.3, 29.6, 29.5, 29.3, 25.4, 22.7, 14.1, 13.7; HRMS (ESI): m/z calcd for C.sub.42H.sub.50O.sub.6: 650.3607, found: 650.3623.

Synthesis of 4,4-dimethyl-2,3-dioctyl-4H,4H-1,1:4,1:4,1:4,1:4,1-sexi(1,4-epoxynaphthalene) (DM-6CA-2C8)

##STR00027##

[0281] Finely powdered anhydrous CsF (0.350 g, 2.31 mmol) was added to a solution of 2-(Trimethylsilyl)phenyl trifluoromethanesulfonate 1 (0.113 mL, 0.553 mmol) and DM-6F-2C.sub.8 (0.334 mL, 0.077 mmol) in MeCN (2 mL) and ethyl acetate (2 mL), and the mixture was stirred at r.t. for 12 h. Then, the reaction mixture was filtered and solvent was removed under reduced pressure. The residue was purified by column chromatography (7:3 hexane/EtOAc), affording DM-6CA-C8 as white glassy solid (0.07 g, 82% yield).

[0282] .sup.1H NMR (400 MHz, CDCl.sub.3): 7.43-7.30 (m, 10H), 7.27-7.19 (m, 4H), 7.11-6.83 (m, 20H), 2.87-2.29 (m, 4H), 2.11 (s, 6H), 1.57-1.43 (m, 4H), 1.31-1.14 (m, 20H), 0.87 (t, J=5.9 Hz, 6H); .sup.13C NMR (101 MHz, Chloroform-d) 152.5, 152.4, 150.5, 149.7, 149.4, 149.3, 146.9, 144.8, 144.2, 144.0, 125.1, 125.0, 124.9, 124.8, 124.7, 124.6, 122.1, 122.0, 121.9, 121.6, 121.5, 118.6, 118.5, 91.6, 90.5, 90.3, 90.2, 90.0, 31.8, 31.7, 29.4, 29.3, 29.2, 29.1, 26.8, 22.6, 15.4, 15.3, 14.1; HRMS (ESI): m/z calcd for C.sub.78H.sub.74O.sub.6: 1106.5485, found: 1106.5525.

DM-6F-Ar (DM-6Nap-2C8)

[0283] ##STR00028##

[0284] A solution of DM-6CA (0.08 g. 0.07 mmol) and anhydrous sodium iodide (0.151 g, 1.0 mmol) in 2 mL of dry acetonitrile and 2 mL of ethyl acetate was treated with trimethylsilyl chloride (0.1 mL, 0.722 mmol) at 0 C. under argon and stirred for 1 h. The reaction was quenched with the addition of 3 mL of 5% aqueous Na.sub.2S.sub.2O.sub.3. The resulting mixture was then extracted with diethyl ether (20 mL). The organic layer was washed with 5% aqueous Na.sub.2S.sub.2O.sub.3 (2 mL) and brine (5 mL) and dried over anhydrous MgSO.sub.4 and the solvent was evaporated under reduced pressure. The residue thus obtained was purified by flash column chromatography on silica gel with hexanes as the eluent to give DM-6Nap (38 mg, 52% yield) as a white solid.

[0285] .sup.1H NMR (500 MHz, Chloroform-d) 8.20-8.10 (m, 4H), 7.83-7.77 (m, 2H), 7.72-7.63 (m, 8H), 7.60-7.52 (m, 12H), 7.40-7.29 (m, 12H), 2.87-2.85 (m, 6H), 2.85-2.77 (m, 4H), 1.79-1.68 (m, 5H), 1.29 (m, 6H), 1.20 (d, J=16.4 Hz, 15H), 0.91-0.86 (t, J=7.1 Hz, 6H); .sup.13C NMR (126 MHz, Chloroform-d) 134.27, 134.26, 134.24, 133.19, 133.07, 133.05, 133.01, 127.76, 127.74, 127.72, 127.59, 127.55, 126.98, 126.93, 126.28, 126.26, 125.90, 125.87, 125.84, 125.82, 125.79, 125.75, 125.71, 124.46, 124.40, 124.35, 29.72, 29.39, 22.72, 22.66, 19.68, 14.14.

4,4-dimethyl-4H,4H-1,1-bi(1,4-epoxytriphenylene) (3)

##STR00029##

[0286] Finely powdered anhydrous CsF (0.468 g, 3.08 mmol) was added to a solution of phenanthrene precursor (10-trimethylsilylphenanthryl 9-trifluoromethanesulfonate) 2 (0.246 g, 0.617 mmol) and DM-2F (0.05 g, 0.308 mmol) in MeCN (2 mL) and ethyl acetate (2 mL), and the mixture was stirred at r.t. for 12 h. After completion of the reaction, mixture was filtered and solvent was removed under reduced pressure. The residue was purified by column chromatography (7:2 hexane/EtOAc), affording phenanthrene cyclo-adduct 3 as a white solid (0.07 g, 44% yield).

[0287] .sup.1H NMR (500 MHz, Chloroform-d) 8.70 (J=8.3, 1.4, 0.6 Hz, 2H; HC(8)), 8.46 (dd, J=16.9, 8.2 Hz, 4H; HC(9 & 12)), 8.37 (ddd, J=8.3, 1.4, 0.6 Hz, 2H; HC(5)), 7.68 (ddd, J=8.3, 7.0, 1.4 Hz, 2H); HC(6), 7.63 (ddd, J=8.3, 7.0, 1.4 Hz, 2H; HC(1)), 7.59 (d, J=5.1 Hz, 2H; HC(2)), 7.22 (ddd, J=8.3, 7.0, 1.2 Hz, 2H; HC(10)), 7.18 (d, J=5.1 Hz, 2H; HC(3)), 6.91 (ddd, J=8.3, 6.9, 1.2 Hz, 2H; HC(11)), 2.63 (s, 6H; HC(13)); .sup.13C NMR (126 MHz, Chloroform-d) 149.3 (2 C(12b)), 147.9 (2 C(4a)), 147.8 (2 C(3)), 147.4 (2 C(2)), 129.8(2 C(8a)), 128.9 (2 C(8b)), 127.6 (2 C(4a)), 127.5 (2 C(12a)), 126.3 (2 C(12)), 126.2 (2 C(11)), 126.1 (2 C(6)), 125.6 (2 C(7)), 125.5 (2 C(10)), 123.8 (2 C(8)), 123.2 (2 C(5)), 122.4 (2 C(9)), 93.1 (2 C(1)), 92.2 (2 C(4)), 19.7 (2 C(13)); HRMS (ESI): m/z calcd for C.sub.38H.sub.26O.sub.2 (M+H).sup.+: 515.2011, found: 515.2024.

4,4-dimethyl-1,1-bitriphenylene (4)

##STR00030##

[0288] A solution of phenanthrene cyclo-adduct 3 (0.02 g. 0.039 mmol) and anhydrous sodium iodide (0.06 g, 0.388 mmol) in dry acetonitrile (2 mL) and dry dichloromethane (2 mL) was treated with trimethylsilyl chloride (0.05 mL, 0.388 mmol) at 0 C. under argon and stirred for 6 h. The reaction was quenched with the addition of 2 mL of 5% aqueous Na.sub.2S.sub.2O.sub.3. The resulting mixture was then extracted with diethyl ether (20 mL). The organic layer was washed with 5% aqueous Na.sub.2S.sub.2O.sub.3 (2 mL) and brine (5 mL) and dried over anhydrous MgSO.sub.4 and the solvent was evaporated under reduced pressure. The residue thus obtained was purified by flash column chromatography on silica gel (9:1 hexanes/EtOAc) to give 4,4-dimethyl-1,1-bitriphenylene 4 (12 mg; 64% yield) as a white solid.

[0289] .sup.1H NMR (500 MHz, Chloroform-d) 8.62 (dd, J=8.1, 1.4 Hz, 2H; HC(8)), 8.55 (dd, J=8.1, 1.3 Hz, 2H; HC(9)), 8.50 (dd, J=8.2, 1.3 Hz, 2H; HC(5)), 8.28 (dd, J=8.6, 0.8 Hz, 2H; HC(12)), 7.67 (ddd, J=8.2, 7.1, 1.3 Hz, 2H; HC(7)), 7.60 (ddd, J=8.4, 7.1, 1.4 Hz, 2H; HC(6)), 7.45 (ddd, J=8.2, 7.0, 1.2 Hz, 2H; HC(10)), 7.27 (d, J=0.7 Hz, 2H; HC(3)), 7.08 (d, J=7.5 Hz, 4H; HC(2)), 7.06 (ddd, J=8.4, 7.0, 1.4 Hz, 4H; HC(11)), 3.02 (s, 6H; HC(13)); .sup.13C NMR (126 MHz, Chloroform-d) .sup.13C NMR (126 MHz, Chloroform-d) 140.0 (2 C(4)), 133.3 (2 C(4a)), 133.3 (2 C(1)), 131.2 (2 C(8a)), 131.1(2 C(8b)), 131.0 (2 C(2)), 130.9 (2 C(4b)), 130.7 (2 C(12a)), 130.7 (2 C(3)), 129.6 (2 C(12b)), 129.0 (2 C(12)), 128.5 (2 C(5)), 126.9(2 C(7)), 126.6 (2 C(10)), 126.2 (2 C(11)), 125.9 (2 C(6)), 123.5(2 C(8)), 123.2 (2 C(9)), 25.5(2 C(13)). HRMS (FD): m/z calcd for C.sub.38H.sub.26: 482.2035, found: 482.2030.

[1,1-binaphthalene]-4,4-diol

##STR00031##

[0290] A solution of DM-2CA (0.05 g, 0.175 mmol) and anhydrous sodium iodide (0.078 g, 0.525 mmol) in 2 mL of dry acetonitrile was treated with trimethylsilyl chloride (0.05 mL, 0.384 mmol) at 0 C. under argon and stirred for 1 h. The reaction was quenched with the addition of 2 mL of 5% aqueous Na.sub.2S.sub.2O.sub.3. The resulting mixture was then extracted with diethyl ether (20 mL). The organic layer was washed with 5% aqueous Na.sub.2S.sub.2O.sub.3 (2 mL) and brine (5 mL) and dried over anhydrous MgSO.sub.4 and the solvent was evaporated under reduced pressure. Then the residue was purified by flash column chromatography on silica gel with 20% hexane/ethyl acetate eluent to give 1,1-binaphthalene-4,4-diol (35 mg, 70% yield) as a white solid.

[0291] .sup.1H NMR (400 MHz, DMSO-d.sub.6) 10.24 (s, 2H), 8.23 (ddd, J=8.4, 1.4, 0.7 Hz, 2H), 7.42 (ddd, J=8.3, 6.7, 1.3 Hz, 2H), 7.28 (ddd, J=8.2, 6.7, 1.4 Hz, 2H), 7.23 (d, J=7.7 Hz, 2H), 7.18-7.15 (m, 2H), 6.98 (d, J=7.7 Hz, 2H); .sup.13C NMR (101 MHz, DMSO-d6) 153.2, 134.2, 129.2, 128.9, 126.5, 126.3, 125.0, 124.8, 122.8, 108.2; HRMS (ESI): m/z calcd for C.sub.29H.sub.14O.sub.2: 286.0994, found: 286.1010.

2,4-dimethyl-7-(5-methyl-[2,2-bifuran]-5-yl)isoindoline-1,3-dione

##STR00032##

[0292] DM-3F (44 mg, 0.192 mmol), N-methyl maleimide 5 (32 mg, 0.289 mmol) and p-toluene sulfonyl anhydride (73 mg, 0.384 mmol) were added to ethyl acetate (0.5 ml) and stirred for 12 h at 60 C. After cooled to room temperature, the reaction was stopped by adding sat. aq. NaHCO.sub.3 (1 mL). The products were extracted with EtOAc (10 mL), and the combined organic extracts were washed with brine, dried (Na.sub.2SO.sub.4), and concentrated in vacuo. The residue was purified by silica-gel flash column chromatography (7:3 hexane/ethyl acetate) to give 2,4-dimethyl-7-(5-methyl-[2,2-bifuran]-5-yl)isoindoline-1,3-dione (30 mg, remaining starting material) as yellow solid.

[0293] .sup.1H NMR (400 MHz, Chloroform-d) 8.11 (d, J=8.3 Hz, 1H), 8.03 (d, J=3.7 Hz, 1H), 7.46 (dd, J=8.3, 0.8 Hz, 1H), 6.66 (d, J=3.7 Hz, 1H), 6.60 (d, J=3.3 Hz, 1H), 6.10 (dd, J=3.3, 1.0 Hz, 1H), 3.19 (s, 3H), 2.72 (s, 3H), 2.40 (d, J=0.5 Hz, 3H);); .sup.13C NMR (200 MHz, CDCl.sub.3) 152.6, 147.6, 147.0, 144.6, 136.5, 136.1, 130.8, 129.8, 126.6, 124.4, 116.3, 107.7, 107.3, 106.9, 23.8, 17.7, 13.7; HRMS (ESI): m/z calcd for C.sub.19H.sub.15NO.sub.4 (M+H).sup.+: 322.1079, found: 322.1034.

2,4-dimethyl-7-(4-methyl-[1,1-binaphthalen]-4-yl)isoindoline-1,3-dione (8)

##STR00033##

[0294] In a vial, finely powdered anhydrous CsF (109 mg, 0.716 mmol) was added to a solution of 2-(Trimethylsilyl)phenyl trifluoromethanesulfonate 1 (0.03 mL, 0.150 mmol) and 2,4-dimethyl-7-(5-methyl-[2,2-bifuran]-5-yl)isoindoline-1,3-dione (0.024 g, 0.0716 mmol) in acetonitrile (0.5 mL) and ethyl acetate (0.5 mL), and the mixture was stirred at r.t. for 12 h. After completion of the reaction, mixture was filtered and solvent was removed under reduced pressure. The residue was dried under high vacuo, affording cyclo-adduct as a white solid (30 mg, 86% yield). HRMS (ESI): m/z calcd for C.sub.31H.sub.23N.sub.2O.sub.5 (M+Na).sup.+: 496.1525, found: 496.1501.

[0295] Further, the solution of crude cyclo-adduct (20 mg, 0.042 mmol) and anhydrous sodium iodide (29 mg, 0.196 mmol) in acetonitrile (05 mL) and ethyl acetate (0.5 mL) was treated with trimethylsilyl chloride (0.018 mL, 0.139 mmol) at 0 C. under argon and stirred for 6 h. The reaction was quenched with the addition of 2 mL of 5% aqueous Na.sub.2S.sub.2O.sub.3. The resulting mixture was then extracted with diethyl ether (20 mL). The organic layer was washed with 5% aqueous Na.sub.2S.sub.2O.sub.3 (2 mL) and brine (5 mL) and dried over anhydrous MgSO.sub.4 and the solvent was evaporated under reduced pressure. The residue thus obtained was purified by flash column chromatography on silica gel (8:2 hexanes/EtOAc) to give oligoarene 8 (12 mg, 65% yield) as a white solid.

[0296] .sup.1H NMR (500 MHz, Chloroform-d) 8.14-8.09 (m, 1H), 7.68 (d, J=7.8 Hz, 1H), 7.61-7.56 (m, 3H), 7.55-7.51 (m, 3H), 7.50-7.41 (m, 3H), 7.39-7.33 (m, 2H), 7.32-7.26 (m, 1H), 3.10 (d, J=8.2 Hz, 3H), 2.83 (d, J=5.6 Hz, 6H);); .sup.13C NMR (126 MHz, Chloroform-d) 169.09, 167.72, 167.65, 139.36, 139.29, 137.24, 137.22, 136.71, 136.66, 136.54, 136.51, 136.04, 135.99, 134.59, 134.39, 134.28, 134.20, 133.06, 133.00, 132.90, 132.89, 132.58, 132.57, 131.85, 131.79, 129.95, 129.92, 129.52, 129.47, 127.85, 127.55, 127.41, 127.25, 127.17, 127.13, 126.63, 126.54, 126.30, 126.06, 126.02, 125.98, 125.91, 125.87, 125.80, 125.59, 125.56, 125.47, 125.43, 124.35, 124.15, 29.69, 23.67, 23.65, 19.63, 19.60, 17.68; HRMS (ESI): m/z calcd for C.sub.25H.sub.20N.sub.2O.sub.5(M+H).sup.+: 442.1807, found: 442.1805.

4-(5-(2,7-dimethyl-1,3-dioxoisoindolin-4-yl)furan-2-yl)-2-ethyl-7-methylisoindoline-1,3-dione

##STR00034##

[0297] 2,4-dimethyl-7-(5-methyl-[2,2-bifuran]-5-yl)isoindoline-1,3-dione (20 mg, 0.06 mmol), N-ethyl maleimide 6 (8 mg, 0.06 mmol) and p-toluene sulfonyl anhydride (17 mg, 0.09 mmol) were added to ethyl acetate (0.5 ml) and stirred for 12 h at 60 C. After cooled to room temperature, the reaction was quenched by adding sat. aq. NaHCO.sub.3 (1 mL). The products were extracted with EtOAc (10 mL), and the combined organic extracts were washed with brine, dried over Na.sub.2SO.sub.4, and concentrated in vacuo. The residue was purified by silica-gel flash column chromatography (7:3 hexane/ethyl acetate) to give 4-(5-(2,7-dimethyl-1,3-dioxoisoindolin-4-yl)furan-2-yl)-2-ethyl-7-methylisoindoline-1,3-dione (15 mg, 58% yield) as yellow solid.

[0298] .sup.1-11 NMR (400 MHz, Chloroform-d) 8.17 (d, J=8.2 Hz, 2H), 8.00 (s, 2H), 7.51 (dd, J=8.2, 0.8 Hz, 2H), 3.77 (q, J=7.2 Hz, 2H), 3.20 (s, 3H), 2.74 (s, 6H), 1.29 (t, J=7.3 Hz, 3H); .sup.13C NMR (101 MHz, Chloroform-d) 168.7, 168.4, 167.9, 167.6, 149.3, 149.3, 136.9, 136.9, 136.6, 136.6, 131.3, 130.0, 130.0, 126.4, 126.3, 125.5, 125.5, 116.5, 32.8, 23.9, 17.8, 17.8, 13.9; HRMS (ESI): m/z calcd for C.sub.31H.sub.23NO.sub.2 (M+H).sup.+: 429.1450, found: 429.1409.

4-(4-(2,7-dimethyl-1,3-dioxoisoindolin-4-yl)naphthalen-1-yl)-2-ethyl-7-methylisoindoline-1,3-dione (9)

##STR00035##

[0299] In a vial, finely powdered anhydrous CsF (30 mg, 0.192 mmol) was added to a solution of 2-(Trimethylsilyl)phenyl trifluoromethanesulfonate 1 (0.011 mL, 0.053 mol) and 4-(5-(2,7-dimethyl-1,3-dioxoisoindolin-4-yl)furan-2-yl)-2-ethyl-7-methylisoindoline-1,3-dione (0.02 g, 0.048 mmol) in acetonitrile (0.5 mL) and ethyl acetate (0.5 mL), and the mixture was stirred at r.t. for 12 h. After completion of the reaction, mixture was filtered and solvent was removed under reduced pressure. The residue was dried under high vacuo, affording cyclo-adduct as a white solid (15 mg, 64% yield), HRMS (FD): m/z calcd for C.sub.31H.sub.24N.sub.2O.sub.5(M+Na).sup.+: 527.1583, found: 527.1572 Further, the solution of crude cyclo adduct (15 mg, 0.03 mmol) and anhydrous sodium iodide (0.01 g, 0.066 mmol) in dry acetonitrile (2 mL) and dry dichloromethane (1 mL) was treated with trimethylsilyl chloride (8 L, 0.06 mmol) at 0 C. under argon and stirred for 6 h. The reaction was quenched with the addition of 2 mL of 5% aqueous Na.sub.2S.sub.2O.sub.3. The resulting mixture was then extracted with diethyl ether (10 mL). The organic layer was washed with 5% aqueous Na.sub.2S.sub.2O.sub.3 (2 mL) and brine (5 mL) and dried over anhydrous MgSO.sub.4 and the solvent was evaporated under reduced pressure. The residue thus obtained was purified by flash column chromatography on silica gel (8:2 hexanes/EtOAc) to give deoxygenated product 9 (7 mg, 48% yield) as a white solid.

7,7-(furan-2,5-diyl)bis(2,4-dimethylisoindoline-1,3-dione)

##STR00036##

[0300] DM-3F (44 mg, 0.192 mmol), N-methyl maleimide 5 (43 mg, 0.384 mmol) and p-toluene sulfonyl anhydride (73 mg, 0.384 mmol) were added to ethyl acetate (1 ml) and stirred for 8 h at 60 C. After cooled to room temperature, the reaction was quenched by adding sat. aq. NaHCO.sub.3 (1 mL). The products were extracted with EtOAc (15 mL), and the combined organic extracts were washed with brine, dried over Na.sub.2SO.sub.4, and concentrated in vacuo. The residue was purified by silica-gel flash column chromatography (5:5 hexane/ethyl acetate) to give 7,7-(furan-2,5-diyl)bis(2,4-dimethylisoindoline-1,3-dione) (50 mg, 61% yield) as yellow solid.

[0301] .sup.1H NMR (400 MHz, Chloroform-d) 8.14 (dd, J=8.3, 0.5 Hz, 2H), 7.98 (s, 2H), 7.50 (d, J=0.7 Hz, 1H), 7.48 (d, J=0.7 Hz, 1H), 3.18 (s, 6H), 2.72 (s, 6H); .sup.13C NMR (101 MHz, Chloroform-d) 168.6, 167.8, 149.3, 136.9, 136.6, 131.3, 130.0, 126.3, 125.4, 116.5, 23.8, 17.8; HRMS (ESI): m/z calcd for C.sub.24H.sub.18N.sub.2O.sub.5 (M+Na).sup.+: 414.1113, found: 437.1100.

7,7-(naphthalene-1,4-diyl)bis(2,4-dimethylisoindoline-1,3-dione) (7)

##STR00037##

[0302] In a vial, finely powdered anhydrous CsF (30 mg, 0.192 mmol) was added to a solution of 2-(Trimethylsilyl)phenyl trifluoromethanesulfonate 1 (0.011 mL, 0.053 mmol) and 7,7-(furan-2,5-diyl)bis(2,4-dimethylisoindoline-1,3-dione) (0.02 g, 0.048 mmol) in acetonitrile (0.5 mL) and ethyl acetate (0.5 mL), and the mixture was stirred at r.t. for 12 h. After completion of the reaction, mixture was filtered and solvent was removed under reduced pressure. The residue was dried under high vacuo, affording cyclo-adduct as a white solid (15 mg, 64% yield), HRMS (FD): m/z calcd for C.sub.30H.sub.22N.sub.2O.sub.5: 490.1607, found: 490.1624.

[0303] Further, the solution of crude cyclo adduct (15 mg, 0.03 mmol) and anhydrous sodium iodide (0.01 g, 0.066 mmol) in dry acetonitrile (1 mL) and dry dichloromethane (2 mL) was treated with trimethylsilyl chloride (8 L, 0.06 mmol) at 0 C. under argon and stirred for 6 h. The reaction was quenched with the addition of 2 mL of 5% aqueous Na.sub.2S.sub.2O.sub.3. The resulting mixture was then extracted with diethyl ether (10 mL). The organic layer was washed with 5% aqueous Na.sub.2S.sub.2O.sub.3 (2 mL) and brine (5 mL) and dried over anhydrous MgSO.sub.4 and the solvent was evaporated under reduced pressure. The residue thus obtained was purified by flash column chromatography on silica gel (8:2 hexanes/EtOAc) to give deoxygenated product 7 (7 mg, 48% yield) as a white solid.

[0304] .sup.1H NMR (400 MHz, Chloroform-d) 7.65 (d, J=7.8 Hz, 2H; HC(8)), 7.59-7.54 (m, 4H), 7.48 (s, 2H), 7.37 (dd, J=6.5, 3.3 Hz, 2H), 3.07 (s, 6H), 2.82 (s, 6H); .sup.13C NMR (126 MHz, Chloroform-d) 169.05, 167.71, 137.32, 136.78, 136.31, 136.15, 136.06, 135.88, 135.24, 131.83, 129.84, 129.41, 126.27, 126.18, 126.14, 126.08, 125.78, 125.71, 29.71, 23.64, 17.68.

[0305] HRMS (ESI): m/z calcd for C.sub.30H.sub.22N.sub.2O.sub.4 (M+Na).sup.+: 497.1477, found: 497.1484.

[0306] The physical properties of linear oligomers are influenced by undesired chain-end effects. In this respect, corresponding fully -conjugated macrocycles represent model systems that combine the infinite defect-free -conjugated chain of an idealized polymer with the advantage of a structurally well-defined oligomer, while excluding perturbing end-effects. This renders them suitable candidates for various applications in organic and molecular electronics and for the study of host-guest interactions, aggregation, and self-assembly on surfaces. While macrocyclic oligothiophenes were extensively explored, macrocyclic oligofurans remain unknown. Computational studies demonstrate that these materials exhibit highly attractive properties, namely: [0307] (i) Planarity: For oligothiophenes, relatively small macrocyclic systems were calculated to be non-planar, mainly due to strain. In furan-based systems, however, the exo angle is 8 larger than in thiophene (133 and 125 respectively, FIG. 20) and, as a result, smaller planar macrocyclic systems were calculated to a minimal structure. For example, the 8-membered cyclic oligofuran system is calculated to be completely planar, in contrast to its cyclic oligothiophene analogue. In addition, alkyl groups can be integrated into the polymer to increase solubility and form different types of assemblies, without any significant perturbation of planarity. Such planarity is crucial for -conjugation, making macrocyclic oligofurans attractive candidates for organic electronic materials. [0308] (ii) Quinoid character: Oligofurans display a significantly stronger quinoid character compared with oligothiophenes, as evident from both DFT calculations and X-ray structure. The results demonstrate that this trend is even more pronounced for macrocyclic oligofurans. For example, 8CF shows a strong quinoid character, with the inter-ring CC bond distance being 1.431 compared with 1.455 for 8CT (FIG. 20B). [0309] (iii) HOMO-LUMO gap (HLG): In general, the HLG of linear oligofurans is ca. 0.3 eV higher than that of the corresponding oligothiophenes, with the HLG decreasing with oligomer length to eventually converge to a value of 2.5 eV. Macrocyclic oligofurans differ markedly from this trend, with the HLG decreasing to a value of 2.24 eV for 8CF, which is significantly lower than that of either linear 8F (2.8 eV), polyfuran (2.41 eV) or macrocylic oligothiophenes (FIG. 20A).

[0310] Overall, the computational results reveal that macrocyclic oligofurans, in particular 6CF-8CF, are suitable electronic materials, owing to their planarity, low strain energy, low HOMO-LUMO gap, and strong quinoid character.