Infrared, Raman and resonance Raman spectra of the solid nickel(II) thiophosphate compound (PPh4)3 [(NiPS4)3] and force constants in the trinickel [Ni3P3S12]3− cyclic anion

摘要: The UV–visible (350–900 nm), infrared and Raman (30–800 cm−1) spectra of a new transition metal thiophosphate solid compound, (PPh4)3 [(NiPS4)3], were analyzed using powder samples. Electronic transitions the 1F2 1A1 type originating in (PS4)3− groups detected from visible absorbance measurements 440–520 nm range most expected vibrational modes trimetallic ring anion [Ni3P3S12]3− observed 600–30 cm−1 region. Also, resonance recorded exciting radiation several wavelengths 680–450 excitation profiles fundamentals established: they all peak near 488 exhibit strongest enhancements for totally symmetric non-totally stretching bending (NiS4) groups. It is therefore concluded that ligand to charge-transfer electronic are overlapped involved vibronic coupling mechanisms. Furthermore, assignments checked by valence force field calculation an isolated C3v symmetry. potential energy distributions mean squared amplitudes revealed strong ν(Ni–S) δ(S–P–S) couplings relatively high at 310 cm−1. Compared with results one-dimensional KNiPS4 compound containing infinite anionic chains [NiPS4]−, one notes constant increase on P—S exocyclic (µ1) bonds, no change bridged (µ2 µ3) bonds slight Ni–S constants varying 75 85 N m−1 accordance localized mechanism. Hence comparison induced scattering processes [(NiPS4)3] compounds shows charge transfers crystal effects have influence properties these compounds. Copyright © 1999 John Wiley & Sons, Ltd.