Electronic and resonance-Raman spectra of the linear-chain mixed-valence platinum complexes {[Pt(en)2][Pt(en)2X2]}3[CuX4]4[X = Cl (1) or Br (2)] and [Pt(pn)2][Pt(pn) Br2][Cu3Br5]2(3)(en = ethane-1,2-diamine and pn = propane-1,2-diamine)

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Abstract
Electronic, infrared, and resonance-Raman (r.r.) spectra of the title complexes have been recorded, as well as single-crystal polarised specular-reflectance spectra of complex (2) in the region 5 000–25 000 cm–1. The r.r. spectra have been obtained with exciting lines whose wavenumbers fall within contours of the intense, axially polarised, intervalence bands observed in the 15 000–20 000 cm–1 region of the transmission and specular-reflectance spectra of each complex. The r.r. spectra are characterised by the appearance of an intense progression, v1ν1(reaching at most v1=17) where ν1 is the symmetric (X–PtIV–X) stretching mode. Weak subsidiary progressions, νn+v1ν1, also appear in the spectra, where νn is another Raman-active mode. The spectroscopic constants ω1 and x11 are calculated. The excitation profiles of the Stokes ν1 band and additionally, in the case of the two bromo-complexes, of the Stokes 2ν1, 3ν1, and anti-Stokes ν1 bands, have been measured, and all found to reach maxima on the low-energy side of the electronic band maximum. The present results are compared with previous ones on related linear-chain complexes.

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