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    The photochemistry of rhenium(I) tricarbonyl N-heterocyclic carbene complexes

    192851_192851.pdf (1.420Mb)
    Access Status
    Open access
    Authors
    Vaughan, J.
    Reid, Brodie
    Ramchandani, S.
    Wright, Phillip
    Muzzioli, S.
    Skelton, B.
    Raiteri, Paolo
    Brown, David
    Stagni, S.
    Massi, Massimiliano
    Date
    2013
    Type
    Journal Article
    
    Metadata
    Show full item record
    Citation
    Vaughan, Jamila G. and Reid, Brodie L. and Ramchandani, Sushil and Wright, Phillip J. and Muzzioli, Sara and Skelton, Brian W. and Raiteri, Paolo and Brown, David H. and Stagni, Stefano and Massi, Massimiliano. 2013. The photochemistry of rhenium(I) tricarbonyl N-heterocyclic carbene complexes. Dalton Transactions. 42 (39): 14100.
    Source Title
    Dalton Tranactions
    DOI
    10.1039/C3DT51614H
    ISSN
    1477-9234
    Remarks

    Copyright © 2013 Royal Society of Chemistry

    URI
    http://hdl.handle.net/20.500.11937/28848
    Collection
    • Curtin Research Publications
    Abstract

    The photophysical and photochemical properties of the new tricarbonyl rhenium(I) complexes bound to N-heterocyclic carbene ligands (NHC), fac-[Re(CO)3(N^C)X] (N^C = 1-phenyl-3-(2-pyridyl)imidazole or 1-quinolinyl-3-(2-pyridyl)imidazole; X = Cl or Br), are reported. The photophysics of these complexes highlight phosphorescent emission from triplet metal-to-ligand (3MLCT) excited states, typical of tricarbonyl rhenium(I) complexes, with the pyridyl-bound species displaying a ten-fold shorter excited state lifetime. On the other hand, these pyridyl-bound species display solvent-dependent photochemical CO dissociation following what appear to be two different mechanisms, with a key step being the formation of cationic tricarbonyl solvato-complexes, being themselves photochemically active. The photochemical mechanisms are illustrated with a combination of NMR, IR, UV-Vis, emission and X-ray structural characterization techniques, clearly demonstrating that the presence of the NHC ligand is responsible for the previously unobserved photochemical behavior in other photoactive tricarbonyl rhenium(I) species. The complexes bound to the quinolinyl-NHC ligand (which possess a lower-energy 3MLCT) are photostable, suggesting that the photoreactive excited state is not any longer thermally accessible. The photochemistry of the pyridyl complexes was investigated in acetonitrile solutions and also in the presence of triethylphosphite, showing a competing and bifurcated photoreactivity promoted by the trans effect of both the NHC and phosphite ligands.

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