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.
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The authors gratefully acknowledge the support of the Engineering and Physical Sciences Research Council (EP/D058147/1) for funding. We are grateful to the Science and Technology Facilities Council (STFC) for access to the Diamond light source for single-crystal structure analysis. M.W.G. gratefully acknowledges receipt of a Royal Society Wolfson Merit Award. We also thank S. Argent for useful discussions and D. Blackmore for experimental assistance.
The authors declare no competing financial interests.
Supplementary information (PDF 607 kb)
Crystallographic information for the metal−organic framework (ReMn), 1 (CIF 12 kb)
Crystallographic information for the metal−organic framework MnMn), fac-isomer, 2a (CIF 17 kb)
Crystallographic information for the metal−organic framework MnMn), mer-isomer, 2b (CIF 13 kb)
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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
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