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Issue 23, 2016
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Structural, electrochemical and photophysical properties of an exocyclic di-ruthenium complex and its application as a photosensitizer

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Abstract

The reaction of cis-bis(2,2′-bipyridine)dichlororuthenium(II) hydrate with a conformationally mobile bipyridyl macrocycle afforded [(bpy)2Ru(μ-L)Ru(bpy)2]Cl4·6H2O, a bridged di-Ru complex. Single crystal X-ray diffraction showed the macrocyclic ligand adopting a bowl-like structure with the exo-coordinated Ru(II) centers separated by 7.29 Å. Photophysical characterization showed that the complex absorbs in the visible region (λmax = 451 nm) with an emission maximum at 610 nm (τ = 706 ns, ΦPL = 0.021). Electrochemical studies indicate the di-Ru complex undergoes three one-electron reversible reductions and a reversible one-electron oxidation process. This electrochemical reversibility is a key characteristic for its use as an electron transfer agents. The complex was evaluated as a photocatalyst for the electronically mismatched Diels–Alder reaction of isoprene and trans-anethole using visible light. It afforded the expected product in good conversion (69%) and selectivity (dr > 10 : 1) at low loadings (0.5–5.0 mol%) and the sensitizer/catalyst was readily recycled. These results suggest that the bipyridyl macrocycle could be widely applied as a bridging ligand for the generation of chromophore-catalyst assemblies.

Graphical abstract: Structural, electrochemical and photophysical properties of an exocyclic di-ruthenium complex and its application as a photosensitizer

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Publication details

The article was received on 09 Apr 2016, accepted on 16 May 2016 and first published on 17 May 2016


Article type: Paper
DOI: 10.1039/C6DT01377E
Citation: Dalton Trans., 2016,45, 9601-9607
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    Structural, electrochemical and photophysical properties of an exocyclic di-ruthenium complex and its application as a photosensitizer

    S. R. Salpage, A. Paul, B. Som, T. Banerjee, K. Hanson, M. D. Smith, A. K. Vannucci and L. S. Shimizu, Dalton Trans., 2016, 45, 9601
    DOI: 10.1039/C6DT01377E

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