On the solvatochromic properties of the oxalate-bridged complexes [( tBuCO2)3M2]2(μ-O 2C2O2) where M = Mo or W

Malcolm H. Chisholm, Nathan J. Patmore

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Abstract

The room temperature electronic absorption spectra of the oxalate bridged MM quadruply bonded complexes [(tBuCO2)3M 2]2(μ-O2C2O2), where M = Mo or W have been recorded in H2O, THF:H2O mixtures, THF, CH2Cl2, toluene, DMSO, aniline, toluene saturated with N,N-dimethylaniline and ethanol. The strong absorptions in the visible region of the electronic absorption spectra assignable to the metal-to-ligand (bridge) charge transfer are shown to be highly solvent dependent. Those samples prepared in H2O, CH2Cl2 and toluene are shown to comprise of a suspension of microcrystalline particles ranging in size from 100 nm to 5 μm. Individual particles were found by scanning electron microscopy to have an aspect ratio of ∼10:1, all being needle shaped. The spectra in THF, EtOH, aniline, DMSO and toluene-N,N-dimethylaniline all show similar vibronic progressions and are attributed to discrete solvated molecular species. The spectra recorded in aniline are notably red-shifted which is proposed to arise from a combination of hydrogen bonding and Lewis base stabilization of the photoexcited state.

Original languageEnglish
Pages (from-to)3877-3882
Number of pages6
JournalInorganica Chimica Acta
Volume357
Issue number13
Early online date19 Aug 2004
DOIs
Publication statusPublished - 1 Nov 2004
Externally publishedYes

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