Author: ["Alexander J. Blake","Neil R. Champness","Timothy L. Easun","David R. Allan","Harriott Nowell","Michael W. George","Junhua Jia","Xue-Zhong Sun"]
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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)3X 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)3Br by single-crystal X-ray diffraction. Metal–organic frameworks (MOFs) are typically built by linking metal centres with organic bridges. By using metal–diimine complexes as linkers, researchers have now immobilized these photoresponsive moieties into a MOF scaffold, which enabled them to observe a different excited state from that occurring in solution, and study a photoreaction crystallographically. Cite this article
Blake, A., Champness, N., Easun, T. et al. Photoreactivity examined through incorporation in metal−organic frameworks. Nature Chem 2, 688–694 (2010). https://doi.org/10.1038/nchem.681 