Brammer, L. orcid.org/0000-0001-6435-7197, Lang, F., Singh, D.C.N.G. et al. (5 more authors) (2022) Metal‐ligand lability and ligand mobility enables framework transformation via ligand release in a family of crystalline 2D coordination polymers. Chemistry – A European Journal, 28 (51). e202201408. ISSN 0947-6539
Abstract
A family of seven silver(I)-perfluorocarboxylate-quinoxaline coordination polymers, [Ag 4 (O 2 CR F ) 4 (quin) 4 ] 1 - 5 (R F = (CF 2 ) n-1 CF 3 ) 4 , n = 1 to 5); [Ag 4 (O 2 C(CF 2 ) 2 CO 2 ) 2 (quin) 4 ] 6 ; [Ag 4 (O 2 CC 6 F 5 ) 4 (quin) 4 ] 7 (quin = quinoxaline), denoted by composition as 4:4:4 phases , was synthesised from reaction of the corresponding silver(I) perfluorocarboxylate with excess quinoxaline. Compounds 1 - 7 adopt a common 2D layered structure in which 1D silver-perfluorcarboxylate chains are crosslinked by ditopic quinoxaline ligands. Solid-state reaction upon heating, involving loss of one equivalent of quinoxaline, yielding new crystalline 4:4:3 phases [Ag 4 (O 2 C(CF 2 ) n-1 CF 3 ) 4 (quin) 3 ] n ( 8 - 10 , n = 1 to 3), was followed in situ by PXRD and TGA studies. Crystal structures were confirmed by direct syntheses and structure determination. The solid-state reaction converting 4:4:4 to 4:4:3 phase materials involves cleavage and formation of Ag–N and Ag–O bonds to enable the structural rearrangement. One of the 4:4:3 phase coordination polymers ( 10 ) shows the remarkably high dielectric constant in the low electric field frequency range.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, (http://creativecommons.org/licenses/by/4.0/) which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
Keywords: | coordination polymer solid-state reaction in situ X-ray diffraction crystal engineering dielectric constant |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Funding Information: | Funder Grant number ENGINEERING AND PHYSICAL SCIENCE RESEARCH COUNCIL GR/T26047/01 |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 27 Jun 2022 17:53 |
Last Modified: | 02 Dec 2022 16:59 |
Status: | Published |
Publisher: | Wiley |
Refereed: | Yes |
Identification Number: | 10.1002/chem.202201408 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:188478 |