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Picosecond time-resolved infrared spectroscopic investigation into electron localisation in the excited states of Re(i) polypyridyl complexes with bridging ligands

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Abstract

Mono- and binuclear complexes of Re(CO)3Cl with dipyrido[2,3-a:3′,2′-c]-6,7-dimethylphenazine (ppbMe2) were synthesised and their photophysical properties probed using picosecond time-resolved infrared spectroscopy (TRIR). Excitation of these complexes in solution at 400 nm produces short-lived excited states. The IR spectrum of the excited state of the mononuclear [Re(CO)3Cl(ppbMe2)] have ν(CO) bands shifted to higher wavenumber relative to those of the ground state. This is consistent with formation of a 3MLCT excited state. The IR spectrum of the excited state of the bimetallic [(Re(CO)3Cl)2(μ-ppbMe2)] shows the formation of two distinct groups of ν(CO) bands. This is interpreted as the formation of two distinct Re sites arising from a localised MLCT state with formally oxidised Re centre and a formally reduced bridging ligand. The ν(CO) bands of the adjacent Re centre are affected by the reduction of the bridging ligand. On the IR timescale the excited state structure is best formulated as [Cl(CO)3ReII(μ-ppbMe2·−)ReI(CO)3Cl].

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Authors and Affiliations

  1. School of Chemistry, University of Nottingham, University Park, Nottingham, UK, NG7 2RD

    Marina K. Kuimova, Xue-Zhong Sun & Michael W. George

  2. Department of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand

    Keith C. Gordon & Sarah L. Howell

  3. CCLRC Rutherford Appleton Laboratory, Central Laser Facility, Chilton, Didcot, Oxfordshire, UK, OX11 0QX

    Pavel Matousek, Anthony W. Parker & Michael Towrie

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  1. Marina K. Kuimova
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  2. Keith C. Gordon
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Kuimova, M.K., Gordon, K.C., Howell, S.L. et al. Picosecond time-resolved infrared spectroscopic investigation into electron localisation in the excited states of Re(i) polypyridyl complexes with bridging ligands. Photochem Photobiol Sci 5, 82–87 (2006). https://doi.org/10.1039/b508335d

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