Crystal polarised spectra of pentachloromanganese(III) ion

Abstract
Crystal polarised spectra of MnIII ions doped in [Et4N]2InCl5 and of [bipH2]MnCl5(bipH2= bipyridinium ion) have been recorded. From band polarisations and energy shifts it is concluded that the dd transitions occur at < 20 kk (1 kk = 1000 cm–1) and that the absorption present at ca. 24 kk is due to a charge transfer transition. For the doped species an assignment in C4v symmetry, with 5B1 < 5A1 < 5B2 < 5E, is possible, whilst for [bipH2]-MnCl5 an assignment in C2v symmetry seems to explain the polarisations better with 5A2 < 5A1(dz2) < 5B1 < 5B2 < 5A1(dx2y2), i.e. with x- and y-axes lying between the equatorial ligands and not along them. Simple point-charge crystal field calculations, with radial parameter ratios of 1–2, give satisfactory agreement with the observed spectra, while angular overlap calculations give much poorer agreement.

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