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    Photophysical and photochemical trends in tricarbonyl rhenium(I) N- heterocyclic carbene complexes

    198945_198945.pdf (1.502Mb)
    Access Status
    Open access
    Authors
    Vaughan, J.
    Reid, Brodie
    Wright, Phillip
    Ramchandani, S.
    Skelton, B.
    Raiteri, Paolo
    Muzzioli, S.
    Brown, David
    Stagni, S.
    Massi, Massimiliano
    Date
    2014
    Type
    Journal Article
    
    Metadata
    Show full item record
    Citation
    Vaughan, Jamilia G. and Reid, Brodie L. and Wright, Phillip J. and Ramchandani, Sushil and Skelton, Brian W. and Raiteri, Paolo and Muzzioli, Sara and Brown, David H. and Stagni, Stefano and Massi, Massimiliano. 2014. Photophysical and photochemical trends in tricarbonyl rhenium(I) N- heterocyclic carbene complexes. Inorganic Chemistry. 53 (7): pp. 3629-3641.
    Source Title
    Inorganic Chemistry
    DOI
    10.1021/ic403138a
    ISSN
    0020-1669
    Funding and Sponsorship
    http://purl.org/au-research/grants/arc/FT130100463
    http://purl.org/au-research/grants/arc/FT130100033
    http://purl.org/au-research/grants/arc/LE130100052
    Remarks

    This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://doi.org/10.1021/ic403138a

    URI
    http://hdl.handle.net/20.500.11937/36738
    Collection
    • Curtin Research Publications
    Abstract

    A family of tricarbonyl Re(I) complexes of the formulation fac-[Re(CO)3(NHC)L] has been synthesized and characterized, both spectroscopically and structurally. The NHC ligand represents a bidentate N-heterocyclic carbene species where the central imidazole ring is substituted at the N3 atom by a butyl, a phenyl, or a mesityl group and substituted at the N1 atom by a pyridyl, a pyrimidyl, or a quinoxyl group. On the other hand, the ancillary L ligand alternates between chloro and bromo. For the majority of the complexes, the photophysical properties suggest emission from the lowest triplet metal-to-ligand charge transfer states, which are found partially mixed with triplet ligand-to-ligand charge transfer character. The nature and relative energy of the emitting states appear to be mainly influenced by the identity of the substituent on the N3 atom of the imidazole ring; thus, the pyridyl complexes have blue-shifted emission in comparison to the more electron deficient pyrimidyl complexes. The quinoxyl complexes show an unexpected blue-shifted emission, possibly occurring from ligand-centered excited states.No significant variations were found upon changing the substituent on the imidazole N3 atom and/or the ancillary ligand. The photochemical properties of the complexes have also been investigated, with only the complexes bound to the pyridyl-substituted NHC ligands showing photoinduced CO dissociation upon excitation at 370 nm, as demonstrated by the change in the IR and NMR spectra as well as a red shift in the emission profile after photolysis. Temperature-dependent photochemical experiments show that CO dissociation occurs at temperatures as low as 233 K, suggesting that the Re–C bond cleaves from excited states of metal-to-ligand charge transfer nature rather than thermally activated ligand field excited states. A photochemical mechanism that takes into account the reactivity of the complexes bound to the pyridyl-NHC ligand as well as the stability of those bound to the pyrimidyl- and quinoxyl-NHC ligands is proposed.

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