Molecular Wires Comprising π-Extended Ethynyl- and Butadiynyl-2,5-Diphenyl-1,3,4-Oxadiazole Derivatives: Synthesis, Redox, Structural, and Optoelectronic Properties

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
π-conjugated molecules, Donor−(C⋮C)n−OXD (n = 1, 2) and OXD−(C⋮C)n−Donor−(C⋮C)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.