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

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



1466-8033
9722-9728
Rankine, Damien
eb763130-6bec-400b-bdc0-bce3a80aca74
Keene, Tony D.
fb859c26-6a1d-4c43-a15f-f329bc8d34d7
Sumby, Christopher J.
98594b5b-a006-42b6-9c9c-f17aa8a4e8f2
Doonan, Christian J.
d722193c-f47b-45a5-845f-8f82b2d7e2d3
Rankine, Damien
eb763130-6bec-400b-bdc0-bce3a80aca74
Keene, Tony D.
fb859c26-6a1d-4c43-a15f-f329bc8d34d7
Sumby, Christopher J.
98594b5b-a006-42b6-9c9c-f17aa8a4e8f2
Doonan, Christian J.
d722193c-f47b-45a5-845f-8f82b2d7e2d3

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).

Record type: Article

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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Published date: 4 September 2013
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow, Chemistry, Faculty of Natural and Environmental Sciences

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Local EPrints ID: 363472
URI: http://eprints.soton.ac.uk/id/eprint/363472
ISSN: 1466-8033
PURE UUID: eeac64f1-7b83-4d0a-a3be-f4b418c37b4e
ORCID for Tony D. Keene: ORCID iD orcid.org/0000-0003-2297-4327

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Date deposited: 25 Mar 2014 13:36
Last modified: 08 Oct 2019 00:36

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Contributors

Author: Damien Rankine
Author: Tony D. Keene ORCID iD
Author: Christopher J. Sumby
Author: Christian J. Doonan

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