Through triethylphosphite-mediated cross-coupling reaction, 4,5-bis(pyridin-2-ylthio)-1,3-dithiole-2-thione(1) reacted with 2-thiophenecarboxaldehyde(2a) or 3-thiophenecarboxaldehyde(2b) to give 2,2'-[(2-(thiophen-2-ylmethylene)-1,3-dithiole-4,5-diyl)bis(sulfanediyl)]dipyridine(3a) and 2,2'-[(2-(thiophen-3-ylmethylene)-1,3-dithiole-4,5-diyl)bis(sulfanediyl)]dipyridine(3b) with the yields of 64% and 59%, respectively. The dithiafulvalene compounds possessing thienyl and pyridyl groups 3a and 3b were subjected to an iodine-induced oxidative dimerization reactions and then a brief reductive aqueous workup with Na2S2O3 to gain tetrathiafulvalene vinylogues 1,2-bis(4,5-bis(pyridin-2-ylthio)-1,3-dithiol-2-ylidene)-1,2-di(thiophen-2-yl)ethane(4a) and 1,2-bis(4,5-bis(pyridin-2-ylthio)-1,3-dithiol-2-ylidene)-1,2-di(thiophen-3-yl)ethane(4b) with the yields of 24% and 22%, respectively. All novel compounds were identified by the nuclear magnetic resonance spectroscopy(NMR), fourier transform infrared spectroscopy(FTIR) and mass spectroscopy(MS) methods. Meanwhile, the structures of compounds 3a, 3b, 4a and 4b were characterized by X-ray diffraction analysis. The cyclic voltammograms showed that the tetrathiafulvalene vinylogues 4a and 4b displayed quasi-reversible one two-electron redox processes. Combined with quantum chemical calculations, effects of the different thienyl and pyridyl groups substituted tetrathiafulvalene vinylogues 4a and 4b on electrochemical potentials were analysised.
