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The Supplementary Material contains additional figures of X-ray structures from Photochemistry of framework-supported M(diimine)(CO)3X complexes in three-dimensional lithium-carboxylate metal-organic frameworks: monitoring the effect of framework cations

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posted on 2016-11-17, 11:58 authored by Thomas J. Reade, Thomas S. Murphy, James A. Calladine, Ian P. Clark, Gregory M. Greetham, Michael Towrie, William Lewis, Michael W. George, Neil R. Champness
The structures and photochemical behaviour of two new metal-organic frameworks (MOFs) are reported. Reaction of Re(2,2'-bipy'-5,5'-dicarboxylic acid)(CO)3Cl or Mn(2,2'-bipy'-5,5'-dicarboxylic acid)(CO)3Br with either LiCl or LiBr, respectively, produces single crystals of {Li2(DMF)2 [(2,2'-bipy'-5,5'-dicarboxylate)Re(CO)3Cl]}n (ReLi) or {Li2(DMF)2[(2,2'-bipy'-5,5'-dicarboxylate)Mn(CO)3Br]}n (MnLi). The structures formed by the two MOFs comprise one-dimensional chains of carboxylate-bridged Li(I) cations that are cross-linked by units of Re(2,2'-bipy'-5,5'-dicarboxylate)(CO)3Cl (ReLi) or Mn(2,2'-bipy'-5,5'- dicarboxylate)(CO)3Br (MnLi). The photophysical and photochemical behaviour of both ReLi and MnLi are probed. The rhenium-containing MOF, ReLi, exhibits luminescence and the excited state behaviour, as established by time-resolved infrared measurements, are closer in behaviour to that of unsubstituted [Re(bipy)(CO)3Cl] rather than a related MOF where the Li(I) cations are replaced by Mn(II) cations. These observations are further supported by DFT calculations. Upon excitation MnLi forms a dicarbonyl species which rapidly recombines with the dissociated CO, in a fashion consistent with the majority of the photoejected CO not escaping the MOF channels.

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    Philosophical Transactions of the Royal Society A: Mathematical, Physical & Engineering Sciences

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