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    Syntheses, Spectroscopic, Electrochemical, and Third-Order Nonlinear Optical Studies of a Hybrid Tris{ruthenium(alkynyl)/(2-phenylpyridine)}iridium Complex

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    Authors
    Zhao, H.
    Simpson, Peter
    Barlow, A.
    Moxey, G.
    Morshedi, M.
    Roy, N.
    Philip, R.
    Zhang, C.
    Cifuentes, M.
    Humphrey, M.
    Date
    2015
    Type
    Journal Article
    
    Metadata
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    Citation
    Zhao, H. and Simpson, P. and Barlow, A. and Moxey, G. and Morshedi, M. and Roy, N. and Philip, R. et al. 2015. Syntheses, Spectroscopic, Electrochemical, and Third-Order Nonlinear Optical Studies of a Hybrid Tris{ruthenium(alkynyl)/(2-phenylpyridine)}iridium Complex. Chemistry: A European Journal. 21 (33): pp. 11843-11854.
    Source Title
    Chemistry - A European Journal
    DOI
    10.1002/chem.201500951
    ISSN
    0947-6539
    School
    Nanochemistry Research Institute
    URI
    http://hdl.handle.net/20.500.11937/33156
    Collection
    • Curtin Research Publications
    Abstract

    The synthesis of fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C C-1-C6H2-3,5-Et2-4-C CC6H4-4-C CH)}3] (10), which bears pendant ethynyl groups, and its reaction with [RuCl(dppe)2]PF6 to afford the heterobimetallic complex fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C C-1-C6H2-3,5-Et2-4-C CC6H4-4-C C-trans-[RuCl(dppe)2])}3] (11) is described. Complex 10 is available from the two-step formation of iodo-functionalized fac-tris[2-(4-iodophenyl)pyridine]iridium(III) (6), followed by ligand-centered palladium-catalyzed coupling and desilylation reactions. Structural studies of tetrakis[2-(4-iodophenyl)pyridine-N,C1′](μ-dichloro)diiridium 5, 6, fac-[Ir{N,C1′-(2,2′-NC5H4C6H3-5′-C C-1-C6H2-3,5-Et2-4-C CH)}3] (8), and 10 confirm ligand-centered derivatization of the tris(2-phenylpyridine)iridium unit.Electrochemical studies reveal two (5) or one (6–10) Ir-centered oxidations for which the potential is sensitive to functionalization at the phenylpyridine groups but relatively insensitive to more remote derivatization. Compound 11 undergoes sequential Ru-centered and Ir-centered oxidation, with the potential of the latter significantly more positive than that of Ir(N,C′-NC5H4-2-C6H4-2)3. Ligand-centered π–π* transitions characteristic of the Ir(N,C′-NC5H4-2-C6H4-2)3 unit red-shift and gain in intensity following the iodo and alkynyl incorporation. Spectroelectrochemical studies of 6, 7, 9, and 11 reveal the appearance in each case of new low-energy LMCT bands following formal IrIII/IV oxidation preceded, in the case of 11, by the appearance of a low-energy LMCT band associated with the formal RuII/III oxidation process. Emission maxima of 6–10 reveal a red-shift upon alkynyl group introduction and arylalkynyl π-system lengthening; this process is quenched upon incorporation of the ligated ruthenium moiety on proceeding to 11. Third-order nonlinear optical studies of 11 were undertaken at the benchmark wavelengths of 800 nm (fs pulses) and 532 nm (ns pulses), the results from the former suggesting a dominant contribution from two-photon absorption, and results from the latter being consistent with primarily excited-state absorption.

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