Photochemistry of framework-supported M(diimine)(CO)3X complexes in three-dimensional lithium carboxylate metal-organic frameworks: monitoring the effect 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: Contribution to journalArticlepeer-review

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)3Cl 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]}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, 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
JournalPhilosophical transactions. Series A, Mathematical, physical, and engineering sciences
Volume375
Issue number2084
Publication statusPublished - 13 Jan 2017

Bibliographical note

Publisher Copyright:
© 2016 The Author(s).

Keywords

  • metal–organic frameworks
  • photochemistry
  • supramolecular chemistry

ASJC Scopus subject areas

  • General Mathematics
  • General Engineering
  • General Physics and Astronomy

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