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

Rankine, Damien, Keene, Tony D., Sumby, Christopher J. and Doonan, Christian J. (2013) Chelation-driven fluorescence deactivation in three alkali earth metal MOFs containing 2,2?-dihydroxybiphenyl-4,4?-dicarboxylate. CrystEngComm, 15 (45), 9722-9728. (doi:10.1039/C3CE41253A).

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 (?max = ~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.

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Contributors

Author: Tony D. Keene

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