Abstract
Abstract The intermolecular interactions of thiolate anions and disulfide molecules as disulfide/thiolate ( T 2 / T − , S 2 / S − ) redox couples with a Ru bipyridyl complex (Z907) are investigated using density functional theory. T and S are 1-methyl- 1H -tetrazole-5-thiolate and 2-methyl-5-trifluoromethyl- 2H -1,2,4-triazole-3-thiolate, respectively. Similar to the typical reductant I − , the S atoms of thiolate anions interact with the oxidized Z907 (Z907 + ) via the terminal S atoms of the isothiocyanate (NCS) ligands. However, nearly 40% of the atomic charge and spin still remain after complexation. If a second thiolate anion, as well as I − , is considered, the atomic charge and spin are transferred completely. The distances of the formed S S bonds for the Z907 + –two anions species correspond to isolated dithiolate radicals. These results suggest that Z907 + can be completely regenerated by two thiolate anions via a two-step mechanism rather than by only one thiolate anion through a one-step mechanism as previously suggested. Unlike the I 2 molecule, the unfound Z907–disulfide complex structure supports the slower recombination process with the disulfide/thiolate electrolyte compared with the I 3 − /I − system in dye-sensitized solar cells.
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