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Supramolecular Photoinduced Electron Transfer between a Redox-Active Hexanuclear Metal-Organic Cylinder and an Encapsulated Ruthenium(II) Complex

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Indexed by:期刊论文

Date of Publication:2016-04-04

Journal:CHEMISTRY-A EUROPEAN JOURNAL

Included Journals:SCIE、EI、PubMed

Volume:22

Issue:15

Page Number:5253-5260

ISSN No.:0947-6539

Key Words:electron transfer; encapsulation; hydrogen; metal-organic cylinders; ruthenium

Abstract:By using redox-active nickel(II) ions as the connect nodes, a hexanuclear metal-organic cylinder (Ni-YL) was achieved through self-assembly with a large cavity and an opening windows capable to accommodate guest molecules. The suitable cavity of Ni-YL provides an opportunity to encapsulate the anionic ruthenium bipyridine derivative [Ru(dcbpy)(3)] (dcbpy=2,2-bipyridine-4,4-dicarboxylic acid) as the photosensitizer for light-driven reactions. The host-guest behavior between Ni-YL and [Ru(dcbpy)(3)] was investigated by mass spectrometry, NMR spectroscopy, and computational studies, revealing an effective binding of the guest [Ru(dcbpy)(3)] within the cavity of Ni-YL. Optical experiments suggested a pseudo-intramolecular photoinduced electron transfer (PET) process between the [Ru(dcbpy)(3)] and the host Ni-YL, leading to an efficient light-driven hydrogen production based on this system. Control experiments with a mononuclear Ni complex as a reference photocatalyst and the inactive [Fe(dcbpy)(3)] as an inhibitor for comparison were also performed to confirm such a supramolecular photocatalysis process.

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