title: Photoreactivity examined through incorporation in metal-organic frameworks.
abstract: Metal-organic frameworks, typically built by bridging metal centres with organic linkers, have recently shown great promise for a wide variety of applications, including gas separation and drug delivery. Here, we have used them as a scaffold to probe the photophysical and photochemical properties of metal-diimine complexes. We have immobilized a M(diimine)(CO)(3)X moiety (where M is Re or Mn, and X can be Cl or Br) by using it as the linker of a metal-organic framework, with Mn(II) cations acting as nodes. Time-resolved infrared measurements showed that the initial excited state formed on ultraviolet irradiation of the rhenium-based metal-organic framework was characteristic of an intra-ligand state, rather than the metal-ligand charge transfer state typically observed in solution, and revealed that the metal-diimine complexes rearranged from the fac- to mer-isomer in the crystalline solid state. This approach also enabled characterization of the photoactivity of Mn(diimine)(CO)(3)Br by single-crystal X-ray diffraction.
authors.affiliation: School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
authors.forename: Alexander J
authors.initials: AJ
authors.lastname: Blake
authors.forename: Neil R
authors.initials: NR
authors.lastname: Champness
authors.forename: Timothy L
authors.initials: TL
authors.lastname: Easun
authors.forename: David R
authors.initials: DR
authors.lastname: Allan
authors.forename: Harriott
authors.initials: H
authors.lastname: Nowell
authors.forename: Michael W
authors.initials: MW
authors.lastname: George
authors.forename: Junhua
authors.initials: J
authors.lastname: Jia
authors.forename: Xue-Zhong
authors.initials: XZ
authors.lastname: Sun
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007097:Imines / Q000737:chemistry*; D007536:Isomerism; D008024:Ligands; D008345:Manganese / Q000737:chemistry; D008968:Molecular Conformation; D055668:Photochemical Processes; D012211:Rhenium / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared
chemical_list: D056831:Coordination Complexes; D007097:Imines; D008024:Ligands; D008345:Manganese; D012211:Rhenium