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Pressure-dependent luminescence spectroscopy of molybdenum(IV) oxo complexes.
MedLine Citation:
PMID:  20354622     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
Luminescence spectra are reported for trans-[MoOCl(CN-t-Bu)(4)]BPh(4) and trans-[MoOF(pyridine)(4)]BPh(4). 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)]BPh(4), and a red-shift of -8 cm(-1) kbar(-1) is obtained for [MoOF(pyridine)(4)]BPh(4). At pressures above 25 kbar, the luminescence maximum of [MoOCl(CN-t-Bu)(4)]BPh(4) 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.
Authors:
Etienne Lanthier; Jesper Bendix; Christian Reber
Publication Detail:
Type:  Journal Article     Date:  2010-03-08
Journal Detail:
Title:  Dalton transactions (Cambridge, England : 2003)     Volume:  39     ISSN:  1477-9234     ISO Abbreviation:  Dalton Trans     Publication Date:  2010 Apr 
Date Detail:
Created Date:  2010-03-31     Completed Date:  2010-08-04     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101176026     Medline TA:  Dalton Trans     Country:  England    
Other Details:
Languages:  eng     Pagination:  3695-705     Citation Subset:  -    
Affiliation:
Département de chimie, Université de Montréal, Montréal, QC H3C 3J7, Canada.
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