Photoreactivity examined through incorporation in metal-organic frameworks.
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.
Blake
Alexander J
AJ
School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, UK.
Champness
Neil R
NR
Easun
Timothy L
TL
Allan
David R
DR
Nowell
Harriott
H
George
Michael W
MW
Jia
Junhua
J
Sun
Xue-Zhong
XZ
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
D056831:Coordination Complexes; D007097:Imines; D008024:Ligands; D008345:Manganese; D012211:Rhenium