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Structural, Electrochemical and Photophysical Properties of an Exocyclic Di-Ruthenium Complex and Its Application as a Photosensitizer

Structural, Electrochemical and Photophysical Properties of an Exocyclic Di-Ruthenium Complex and Its Application as a Photosensitizer

Sahan R Salpage, Avishek Paul, Bozumeh Som, Tanmay Banerjee, Kenneth Hanson, Mark D Smith, Aaron K Vannucci, Linda S Shimizu

Dalton Trans. 2016 Jun 21;45(23):9601-7.

PMID: 27216541

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.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP98014143	cis-Bis(2,2′-bipyridine)dichlororuthenium(II) hydrate		98014-14-3	Price

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