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

Research output: Contribution to journalArticle

11 Citations (Scopus)

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.

LanguageEnglish
Pages3877-3882
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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Oxalates
Toluene
oxalates
toluene
Aniline
aniline
Dimethyl Sulfoxide
electronic spectra
Absorption spectra
Lewis Bases
absorption spectra
Lewis base
progressions
needles
Needles
Charge transfer
aspect ratio
Aspect ratio
Suspensions
Hydrogen bonds

Cite this

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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.",
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On the solvatochromic properties of the oxalate-bridged complexes [( tBuCO2)3M2]2(μ-O 2C2O2) where M = Mo or W. / Chisholm, Malcolm H.; Patmore, Nathan J.

In: Inorganica Chimica Acta, Vol. 357, No. 13, 01.11.2004, p. 3877-3882.

Research output: Contribution to journalArticle

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AB - 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.

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