Polarized Crystal Spectra of Tris(diethyldithiophosphato)vanadium(III), -chromium(III), and -cobalt(III)
The electronic structures of tris(diethyldithiophosphato)vanadium(III), -chromlum(III), and -cobalt(III) have been investigated using the polarized ligand field spectra of the chromophores doped into the lattice of the colorless crystal of tris(didiethyldithiophosphato)indium(III). Spectra weee measured at 300, 80, and 5°K. Molecular polarizations (perpendicular and parallel to the C3 axes) have been calculated from the crystal spectra observed with light polarized along extinction directions in the monoclinic crystal. The selection rules allow an independent check of these calculations which confirms the validity of the method. Polarizations indicate close adherence to trigonal (D3) selection rules (with the exception of V(dtp)3 at low temperatures) despite the C1 site symmetry of the metal ions. Trigonal splittings, as indicated by band maxima in the lower energy manifold of each spectrum, are 0.6 kK for Cr(dtp)3 and Co(dtp)3 and considerably less than this for V(dtp)3, with the E component at higher energy in each case. The Cr(dtp)3 spectrum has been fitted to a crystal field model which indicates by its unusually large ratio of C/B the predominance of the σ-delocalization mechanism in this complex. © 1971, American Chemical Society. All rights reserved.
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