Molecular wires comprising pi-extended ethynyl- and butadiynyl-2,5-diphenyl-1,3,4 oxidiazole derivatives: synthesis, redox, structural and optoelectronic properties

Abstract

2,5-Diphenyl-1,3,4-oxadiazole (OXD) derivatives with terminal ethynyl- (4a,b) and butadiynyl- (8a,b) substituents have been synthesized in high yields. 2-Methyl-3,5-hexadiyn-2-ol has not been exploited previously in the synthesis of terminal butadiynes. Crystals of 8a and 8b are remarkably stable to long-term storage under ambient conditions. The X-ray crystal structure of 8a reveals that the butadiyne moieties are spatially isolated by the aromatic moieties, which explains the high stability. Two series of derived -conjugated molecules, Donor-(CC)n-OXD (n = 1, 2) and OXD-(CC)n-Donor-(CC)n-OXD (n = 1) [Donor = tetrathiafulvalene (TTF), bithiophene, 9-(4,5-dimethyl-1,3-dithiol-2-ylidene)fluorene, and triphenylamine], have been synthesized using Sonogashira reactions and characterized by X-ray crystallography, cyclic voltammetry, and optical absorption/emission spectroscopy. The electron-withdrawing effect of the OXD units is manifested by a positive shift of the donor oxidation waves in these systems: the butadiynylene spacer (n = 2) further shifts the first oxidation waves by 40-80 mV compared to analogues n = 1. The absorption spectra of TTF-OXD hybrids 10d and 11 are blue-shifted by 80 nm compared to the bithienyl-bridged derivative 10f and are similar to the butadiynyl-OXD building-block 8a, demonstrating that conjugation is disrupted by a neutral TTF unit. Solutions of the TTF-OXD and 9-(4,5-dimethyl-1,3-dithiol-2-ylidene)fluorene-OXD hybrids, 10d, 10g, 11, and 13, are only very weakly fluorescent due to quenching from the electron-donor moieties. In contrast, the triphenylamine-OXD hybrids 12a, 12b, 14a, and 14b are fluorescent; the PLQYs of the butadiynylene derivatives 14a and 14b are lower than those of the ethynylene-bridged analogues 12a and 12b.