Carbo-biphenyls and Carbo-terphenyls: Oligo(phenylene ethynylene) Ring Carbo-mers

Abstract

Ring carbo-mers of oligo(phenylene ethynylene)s (OPEn, n=0-2), made of C₂ -catenated C₁₈ carbo-benzene rings, have been synthesized and characterized by NMR and UV-vis spectroscopy, crystallography and voltammetry. Analyses of crystal and DFT-optimized structures show that the C₁₈ rings preserve their individual aromatic character according to structural and magnetic criteria (NICS indices). Carbo-terphenyls (n=2) are reversibly reduced at ca. -0.42 V/SCE, i.e. 0.41 V more readily than the corresponding carbo-benzene (-0.83 V/SCE), thus revealing efficient inter-ring π-conjugation. An accurate linear fit of E_1/2^red1 vs. the DFT LUMO energy suggests a notably higher value (-0.30 V/SCE) for a carbo-quaterphenyl congener (n=3). Increase with n of the effective π-conjugation is also evidenced by a red shift of two of the three main visible light absorption bands, all being assigned to TDDFT-calculated excited states, one of them restricting to a HOMO→LUMO main one-electron transition.

Keywords: OPEs; alkynes; aromaticity; bi-/terphenyl; carbo-benzenes.