Abstract：The powder solid state FT-Raman spectra of four unsymmetric dithiolate complexes with formulas (Me4N)2[M(Ln)(SPh)2] (M=Cd and Zn, L1=dmit=1,3-dithiole-2-thione-4,5-dithiolate, L2=dmid=1,3-dithiole-2-one-4,5-dithiolate, SPh= thiophenolate) (2-5) and [Bu4N]2[Zn(dmit)2] (1) were studied and characterized by changing the structures of ligands or the metals of the complexes. The blue shift of the CC peak around 1 420 cm-1 is about 38 cm-1 when the dmit2- is replaced by dmid2-. When Zn2+ is replaced by Cd2+, or dmit2- is replaced by dmid2-, the 990 cm-1 peaks of the pentacyclic ring shift to red by about 11 and 7 cm-1 respectively. Two peaks at 463 and 300 cm-1 were assigned to stretching vibration and bending vibration respectively for the S—C—S bond of S2CCS2 in dmit2-or dmid2-. Red shifts of those two peaks are found when dmit2- is replaced by SPh-, or Zn2+ is replaced by Cd2+; but they will shift to blue when dmit2- is replaced by dmid2-. There are two peaks of Cd—S vibrations with the sulfur atom from thiophenolate and from the ligands dmit2- or dmid2-, which are at about 180 and 140 cm-1 respectively. Just like Cd—S, the vibration of Zn—S has two peaks as well, which are at about 193 and 155 cm-1, respectively.
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