Modulated self-assembly of hcp topology MOFs of Zr/Hf and the rxtended 4,4′-(Ethyne–1,2–diyl)dibenzoate linker

Boyadjieva, S. S., Firth, F. C. N., Alizadeh Kiapi, M. R., Fairen-Jimenez, D., Ling, S., Cliffe, M. J. and Forgan, R. S. (2023) Modulated self-assembly of hcp topology MOFs of Zr/Hf and the rxtended 4,4′-(Ethyne–1,2–diyl)dibenzoate linker. CrystEngComm, 25(14), pp. 2119-2124. (doi: 10.1039/D2CE01529C)

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Abstract

Careful control of synthetic conditions can enhance the structural diversity of metal-organic frameworks (MOFs) within individual metal-linker combinations. Herein, we show that hcp topology MOFs of both Zr(IV) and Hf(IV), linked by the extended (ethyne–1,2–diyl)dibenzoate linker, can be prepared by modulated self-assembly. The controlled addition of acetic acid and water to solvothermal syntheses is essential to generate these phase pure hcp topology materials, which are characterised experimentally and computationally. The central alkyne unit of the linker can be quantitatively brominated, but this results in partial degradation of the hcp phase, in contrast to the more stable fcu topology analogues. Nevertheless, the MOFs represent new members of the hcp topology isoreticular series showing high crystallinity and porosity, and demonstrate that new materials can be discovered in existing MOF phase spaces through judicious adjustment of key synthetic parameters.

Item Type:Articles
Additional Information:R.S.F. thanks the Royal Society for receipt of a URF and the University of Glasgow for funding. The work has been supported by the European Research Council (ERC) under the European Union's Horizon 2020 Programme for Research and Innovation (R.S.F.: grant agreement no. 677289, SCoTMOF, ERC-2015-STG; D.F.J.: grant agreement no. 726380, NanoMOFdeli, ERC-2016-COG). M.J.C. thanks School of Chemistry at the University of Nottingham for receipt of a Hobday Fellowship. M.R.A.K. acknowledges support from the Cambridge Trust Scholarship and the Trinity-Henry Barlow Scholarship. We acknowledge the use of the ARCHER2 supercomputer through membership of the UK’s HPC Materials Chemistry Consortium, which is funded by EPSRC grant no. EP/R029431.
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Boyadjieva, Sophia and Forgan, Professor Ross
Authors: Boyadjieva, S. S., Firth, F. C. N., Alizadeh Kiapi, M. R., Fairen-Jimenez, D., Ling, S., Cliffe, M. J., and Forgan, R. S.
College/School:College of Science and Engineering > School of Chemistry
Journal Name:CrystEngComm
Publisher:Royal Society of Chemistry
ISSN:1466-8033
ISSN (Online):1466-8033
Published Online:07 March 2023
Copyright Holders:Copyright © 2023 The Royal Society of Chemistry
First Published:First published in CrystEngComm 25(14): 2119-2124
Publisher Policy:Reproduced under a Creative Commons License

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Project CodeAward NoProject NamePrincipal InvestigatorFunder's NameFunder RefLead Dept
172845SCoTMOFRoss ForganEuropean Research Council (ERC)677289Chemistry