Preparation, structure, and electrochemistry of porphyrinato titanium (IV) benzenedithiolates with a trithiole ring, a dithiin ring, and two 2-cyanoethylthio groups

The reaction of tetra(p-tolyl)porphyrinato titanium (IV) oxide (2) with 4,7-diethyl-5,6-dimercaptobenzo[1,2,3] trithiole (3a) produced the corresponding titanium (IV) complex, tetra(p-tolyl)porphyrinato titanium (IV) trithiolobenzenedithiolate (4a), fused with a trithiole ring. Related compounds 4b and 4c were prepared by a similar reaction of 2 with 5,8-diethyl-6,7-dimercaptobenzo[1,4]dithiin (3b) and 3,6-diethyl-4,5-dimercapto-1,2-bis(2-cyanoethylthio)benzene (3c). The structure of 4b was determined by X-ray crystallography. Compound 4c was further treated with cesium hydroxide to produce the corresponding dithiolate anion 4c2S, which was deposited on the gold electrode. The electrochemical property of the gold electrode was determined by cyclic voltammetry. The structure of simplified model compound 4b′ was optimized using the DFT method with the Gaussian 09 program. The optimized structure was utilized to calculate the NMR chemical shifts, the HOMO and LUMO energy levels, and the electronic transition...