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    Synthesis, photophysical and electrochemical investigation of dinuclear tetrazolato-bridged rhenium complexes

    189272_189272.pdf (864.9Kb)
    Access Status
    Open access
    Authors
    Wright, Phillip
    Muzzioli, S.
    Werrett, Melissa
    Raiteri, Paolo
    Skelton, B.
    Silvester, Debbie
    Stagni, S.
    Massi, Massimiliano
    Date
    2012
    Type
    Journal Article
    
    Metadata
    Show full item record
    Citation
    Wright, Phillip J. and Muzzioli, Sara and Werrett, Melissa V. and Raiteri, Paolo and Skelton, Brian and Skelton, Brian W. and Silvester, Debbie S. and Stagni, Stefano and Massi, Massimiliano. 2012. Synthesis, photophysical and electrochemical investigation of dinuclear tetrazolato-bridged rhenium complexes. Organometallics. 31 (21): pp. 7566-7578.
    Source Title
    Organometallics
    DOI
    10.1021/om300870a
    ISSN
    02767333
    Remarks

    NOTICE: This is the author’s version of a work in which changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication.

    URI
    http://hdl.handle.net/20.500.11937/8275
    Collection
    • Curtin Research Publications
    Abstract

    Starting from anionic tetrazole-based ligands, namely 5-(4’-cyanophenyl)tetrazolate and 5-(4’-pyridyl)tetrazolate, mononuclear and dinuclear complexes of fac-[Re(CO)3(phen)]+ (phen = 1,10-phenanthroline) were prepared and characterized. For the mononuclear complexes, regioselective coordination of the metal fragments on the negatively charged tetrazolato ring is exclusively obtained. Coordination to the benzonitrile and pyridine groups was achieved by previous alkylation of the tetrazole ring. Dinuclear complexes were obtained by treatment of the corresponding mononuclear tetrazole-bound complexes with fac-[Re(CO)3(phen)(THF)]+. The second rhenium fragment coordinated either to the pyridine ring or, in the case of the benzonitrile ligand, to the tetrazole ring. The electrochemical properties were probed in an imidazolium ionic liquid, highlighting reduction processes centered on the phen ligand and oxidation processes localized on the metal. The photophysical properties of the complexes are characterized by phosphorescent emission from triplet metal-to-ligand charge transfer excited states, with trends in the lifetime and quantum yield in qualitative agreement with the energy gap law. The two dinuclear complexes show almost superimposable emission profiles: in the 5-(4’-cyanophenyl) tetrazolate-bridged complex, the two metal fragments coordinated to the tetrazole are equivalent and share a positive charge of +1. On the other hand, the photophysical properties of the 5-(4’pyridyl)tetrazolate-bridged dinuclear complex suggest energy transfer between the two metal centers.

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