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Solvent-modified dynamic porosity in chiral 3D kagome frameworks

Solvent-modified dynamic porosity in chiral 3D kagome frameworks
Solvent-modified dynamic porosity in chiral 3D kagome frameworks
Dynamically porous metal-organic frameworks (MOFs) with a chiral quartz-based structure have been synthesized from the multidentate ligand 2,2?-dihydroxybiphenyl-4,4?-dicarboxylate (H2diol). Compounds [Ni(II)(H2diol)(S)2]·xS (where S = DMF or DEF) show marked changes in 77 K N2 uptake between partially desolvated [Ni(II)(H2diol)(S)2] (only the pore solvent is removed) and fully desolvated [Ni(II)(H2diol)] forms. Furthermore, [Ni(II)(H2diol)(DMF)2] displays additional solvent-dependent porosity through the rotation of DMF molecules attached to the axial coordination sites of the Ni(II) centre. A unique feature of the four coordinate Ni(II) centre in [Ni(II)(H2diol)] is the dynamic response to its chemical environment. Exposure of [Ni(II)(H2diol)] to H2O and MeOH vapour leads to coordination of both axial sites of the Ni centres and to the generation of a solvated framework, whereas exposure to EtOH, DMF, acetone, and MeCN does not lead to any change in metal coordination or structure metrics. MeOH vapour adsorption was able to be tracked by time-dependent magnetometry as the solvated and desolvated structures have different magnetic moments. Solvated and desolvated forms of the MOF show remarkable differences in their thermal expansivities; [Ni(II)(H2diol)(DMF)2]·DMF displays marked positive thermal expansion (PTE) in the c-axis, yet near to zero thermal expansion, between 90 and 450 K, is observed for [Ni(II)(H2diol)]. These new MOF architectures demonstrate a dynamic structural and colourimetric response to selected adsorbates via a unique mechanism that involves a reversible change in the coordination environment of the metal centre. These coordination changes are mediated throughout the MOF by rotational mobility about the biaryl bond of the ligand.



0300-9246
Keene, Tony D.
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Rankine, Damien
eb763130-6bec-400b-bdc0-bce3a80aca74
Evans, Jack D.
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Southon, Peter D.
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Kepert, Cameron J.
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Aitken, Jade B.
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Sumby, Christopher J.
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Doonan, Christian J.
d722193c-f47b-45a5-845f-8f82b2d7e2d3
Keene, Tony D.
fb859c26-6a1d-4c43-a15f-f329bc8d34d7
Rankine, Damien
eb763130-6bec-400b-bdc0-bce3a80aca74
Evans, Jack D.
99afe675-a637-4132-ab47-7e3ef9ee6983
Southon, Peter D.
a5252047-3b0f-48d6-b946-7b2acf497253
Kepert, Cameron J.
189dc2eb-da77-4b14-a6f8-7075b27c50e9
Aitken, Jade B.
061320d7-dfe9-45b0-8f4c-50ed3b486f66
Sumby, Christopher J.
98594b5b-a006-42b6-9c9c-f17aa8a4e8f2
Doonan, Christian J.
d722193c-f47b-45a5-845f-8f82b2d7e2d3

Keene, Tony D., Rankine, Damien, Evans, Jack D., Southon, Peter D., Kepert, Cameron J., Aitken, Jade B., Sumby, Christopher J. and Doonan, Christian J. (2013) Solvent-modified dynamic porosity in chiral 3D kagome frameworks. Dalton Transactions. (doi:10.1039/c3dt00096f). (PMID:23423162)

Record type: Article

Abstract

Dynamically porous metal-organic frameworks (MOFs) with a chiral quartz-based structure have been synthesized from the multidentate ligand 2,2?-dihydroxybiphenyl-4,4?-dicarboxylate (H2diol). Compounds [Ni(II)(H2diol)(S)2]·xS (where S = DMF or DEF) show marked changes in 77 K N2 uptake between partially desolvated [Ni(II)(H2diol)(S)2] (only the pore solvent is removed) and fully desolvated [Ni(II)(H2diol)] forms. Furthermore, [Ni(II)(H2diol)(DMF)2] displays additional solvent-dependent porosity through the rotation of DMF molecules attached to the axial coordination sites of the Ni(II) centre. A unique feature of the four coordinate Ni(II) centre in [Ni(II)(H2diol)] is the dynamic response to its chemical environment. Exposure of [Ni(II)(H2diol)] to H2O and MeOH vapour leads to coordination of both axial sites of the Ni centres and to the generation of a solvated framework, whereas exposure to EtOH, DMF, acetone, and MeCN does not lead to any change in metal coordination or structure metrics. MeOH vapour adsorption was able to be tracked by time-dependent magnetometry as the solvated and desolvated structures have different magnetic moments. Solvated and desolvated forms of the MOF show remarkable differences in their thermal expansivities; [Ni(II)(H2diol)(DMF)2]·DMF displays marked positive thermal expansion (PTE) in the c-axis, yet near to zero thermal expansion, between 90 and 450 K, is observed for [Ni(II)(H2diol)]. These new MOF architectures demonstrate a dynamic structural and colourimetric response to selected adsorbates via a unique mechanism that involves a reversible change in the coordination environment of the metal centre. These coordination changes are mediated throughout the MOF by rotational mobility about the biaryl bond of the ligand.



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e-pub ahead of print date: 14 February 2013
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow

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Local EPrints ID: 351872
URI: http://eprints.soton.ac.uk/id/eprint/351872
ISSN: 0300-9246
PURE UUID: 3e14fec1-b188-4838-a0f7-96e97930ad47
ORCID for Tony D. Keene: ORCID iD orcid.org/0000-0003-2297-4327

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Date deposited: 29 Apr 2013 08:43
Last modified: 14 Mar 2024 13:44

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Contributors

Author: Tony D. Keene ORCID iD
Author: Damien Rankine
Author: Jack D. Evans
Author: Peter D. Southon
Author: Cameron J. Kepert
Author: Jade B. Aitken
Author: Christopher J. Sumby
Author: Christian J. Doonan

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