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Photoreactivity examined through incorporation in metal-organic frameworks

Blake, Alexander J., Champness, Neil R., Easun, Timothy, Allan, David R., Nowell, Harriott, George, Michael W., Jia, Junhua and Sun, Xue-Zhong 2010. Photoreactivity examined through incorporation in metal-organic frameworks. Nature Chemistry 2 (8) , pp. 688-694. 10.1038/nchem.681

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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.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Subjects: Q Science > QD Chemistry
Publisher: Nature Publishing Group
ISSN: 1755-4330
Last Modified: 04 Jun 2017 07:58

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