Issue 45, 2013

Chelation-driven fluorescence deactivation in three alkali earth metal MOFs containing 2,2′-dihydroxybiphenyl-4,4′-dicarboxylate

Abstract

Three new metal–organic frameworks (MOFs) have been synthesised from alkali earth metal ions of increasing ionic radii (Mg, Ca and Sr) and 2,2′-dihydroxybiphenyl-4,4′-dicarboxylic acid (H4diol). The distinct coordination environments, framework topologies and the non-coordinated diol moieties accessed are a result of using differently sized metal ions for MOF synthesis which affects the ability of the diol moieties to chelate the metal. Detailed structural analysis of [Sr3(H2diol)3(DMF)5], [Ca3.5(Hdiol)(H2diol)2(DMF)5]·1.2DMF and [Mg(H2diol)(DMF)2]·DMF show distinctive variations in variable temperature expansion/contraction properties and porosity. In addition, [Sr3(H2diol)3(DMF)5] and [Ca3.5(Hdiol)(H2diol)2(DMF)5]·1.2DMF display a broad fluorescence emission (λmax = ~435 nm) under ultraviolet light due to the presence of non-coordinated biphenyl-diol moieties within the structures, while chelation of Mg by the diol pocket in [Mg(H2diol)(DMF)2]·DMF leads to quenching of the ligand fluorescence.

Graphical abstract: Chelation-driven fluorescence deactivation in three alkali earth metal MOFs containing 2,2′-dihydroxybiphenyl-4,4′-dicarboxylate

Supplementary files

Article information

Article type
Paper
Submitted
28 Jun 2013
Accepted
02 Sep 2013
First published
04 Sep 2013

CrystEngComm, 2013,15, 9722-9728

Chelation-driven fluorescence deactivation in three alkali earth metal MOFs containing 2,2′-dihydroxybiphenyl-4,4′-dicarboxylate

D. Rankine, T. D. Keene, C. J. Sumby and C. J. Doonan, CrystEngComm, 2013, 15, 9722 DOI: 10.1039/C3CE41253A

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