title: Supramolecular Photoinduced Electron Transfer between a Redox-Active Hexanuclear Metal-Organic Cylinder and an Encapsulated Ruthenium(II) Complex.
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.
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116023, P. R. China), Fax.
authors.forename: Lu
authors.initials: L
authors.lastname: Yang
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116023, P. R. China), Fax. hecheng@dlut.edu.cn.
authors.forename: Cheng
authors.initials: C
authors.lastname: He
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116023, P. R. China), Fax.
authors.forename: Xin
authors.initials: X
authors.lastname: Liu
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116023, P. R. China), Fax.
authors.forename: Jing
authors.initials: J
authors.lastname: Zhang
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116023, P. R. China), Fax.
authors.forename: Hui
authors.initials: H
authors.lastname: Sun
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, 116023, P. R. China), Fax. guohm@dlut.edu.cn.
authors.forename: Huimin
authors.initials: H
authors.lastname: Guo
keywords: electron transfer; encapsulation; hydrogen; metal-organic cylinders; ruthenium