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Issue 15, 2010
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Pressure-dependent luminescence spectroscopy of molybdenum(IV) oxo complexes

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Abstract

Luminescence spectra are reported for trans-[MoOCl(CN-t-Bu)4]BPh4 and trans-[MoOF(pyridine)4]BPh4. The maxima of the broad luminescence bands are at energies of 12000 and 13000 cm−1, respectively. Resolved vibronic structure involves the metal-oxo stretching mode with a vibrational frequency of approximately 950 cm−1 (Raman) in both compounds. The pressure behavior of the luminescence bands shows a distinct difference: a blue shift of +12 cm−1 kbar−1 is observed for [MoOCl(CN-t-Bu)4]BPh4, and a red-shift of -8 cm−1 kbar−1 is obtained for [MoOF(pyridine)4]BPh4. At pressures above 25 kbar, the luminescence maximum of [MoOCl(CN-t-Bu)4]BPh4 shows a change from a blue-shift to a red-shift and the Raman peak corresponding to the metal-oxo stretching mode at 954 cm−1 becomes broad and its maximum decreases with increasing pressure, leading to a strong deviation from the linear increase of +0.24 cm−1 kbar−1 observed at pressures below 25 kbar. These unusual pressure effects are rationalized in terms of the influence of pressure on the metal–ligand bonds and oxo-metal–ligand angles using DFT calculations.

Graphical abstract: Pressure-dependent luminescence spectroscopy of molybdenum(iv) oxo complexes

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Publication details

The article was received on 18 Nov 2009, accepted on 04 Feb 2010 and first published on 08 Mar 2010


Article type: Paper
DOI: 10.1039/B924242B
Citation: Dalton Trans., 2010,39, 3695-3705
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    Pressure-dependent luminescence spectroscopy of molybdenum(IV) oxo complexes

    E. Lanthier, J. Bendix and C. Reber, Dalton Trans., 2010, 39, 3695
    DOI: 10.1039/B924242B

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