Photochemistry of framework-supported m(diimine)(CO)3x complexes in three-dimensional lithium carboxylate metal-organic frameworks: Monitoring the efect of framework cations

Thomas J. Reade, Thomas S. Murphy, James A. Calladine, Raphael Horvath, Ian P. Clark, Gregory M. Greetham, Michael Towrie, William Lewis, Michael W. George, Neil R. Champness

Research output: Journal PublicationArticlepeer-review

6 Citations (Scopus)

Abstract

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)3 Cl or Mn(2,2'-bipy-5,5'-dicarboxylic acid)(CO)3Br with LiCl or LiBr, respectively, produces single crystals of {Li2(DMF)2 [(2,2'-bipy-5,5'-dicarboxylate) Re(CO)3Cl]}, (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, is 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 density functional theory 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. This article is part of the themed issue 'Coordination polymers and metal-organic frameworks: materials by design'.

Original languageEnglish
Article number33
JournalPhilosophical transactions. Series A, Mathematical, physical, and engineering sciences
Volume375
Issue number2084
DOIs
Publication statusPublished - 13 Jan 2017

Keywords

  • Metal-organic frameworks
  • Photochemistry
  • Supramolecular chemistry

ASJC Scopus subject areas

  • Mathematics (all)
  • Engineering (all)
  • Physics and Astronomy (all)

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