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Phase control of ferromagnetic copper(II) carbonate coordination polymers through reagent concentration

Phase control of ferromagnetic copper(II) carbonate coordination polymers through reagent concentration
Phase control of ferromagnetic copper(II) carbonate coordination polymers through reagent concentration

A significant degree of control over the dimensionality and magnetic connectivity of CuII carbonate coordination polymers is achieved through varying the concentration of ammonia in the reactant solution. Higher concentration leads to a two-dimensional ferromagnetic [Cu3(2,4′-bipy)6(CO3)2]n 2n+ kagome structure while lower concentration develops a ferromagnetic [Cu(2,4′-bipy)2(H2O)2][Cu(2,4′-bipy)2(CO3)2] chain (where 2,4′-bipy = 2,4′-bipyridine). The carbonate anion in the structures arises from the fixation of atmospheric CO2 by the basic ammonia solution. Modelling the magnetic susceptibility of 1 and 2 reveals ferromagnetic interactions with J/kB = +28.1 K for 1 and +13.99 K for 2. (H = –J). The use of a monodentate polypyridine ligand results in the suppression of the superexchange pathway between layers in 1, removing the metamagnetic behaviour seen in related compounds where a ditopic ligand presents the ability for the layer to couple antiferromagnetically. Attempts to substitute 2,4′-bipy for 4-(N,N-dimethylamino)pyridine (4-dmap) result in a discrete species [Cu(4-ampy)4](ClO4)2 (3).

Chain structures, Coordination polymers, Kagome structures, Layered compounds, Magnetic properties
1434-1948
5223-5228
Mulrooney, David Z.T.
6288c7c0-0eb0-4e33-acf3-a930f3c40687
Clements, John E.
fabfdce4-e737-4da9-ae2e-3610e2b1de2b
Ericsson, Daniel J.
8dfd3a9e-478f-4701-8228-9a6591d3c1b3
Price, Jason R.
b4b3362d-8a02-4446-8e83-302ae792f6b0
Kühne, Irina A.
a75f6bb9-ee66-49d5-9a75-c8a15232efe8
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Kepert, Cameron J.
189dc2eb-da77-4b14-a6f8-7075b27c50e9
Keene, Tony D.
fb859c26-6a1d-4c43-a15f-f329bc8d34d7
Mulrooney, David Z.T.
6288c7c0-0eb0-4e33-acf3-a930f3c40687
Clements, John E.
fabfdce4-e737-4da9-ae2e-3610e2b1de2b
Ericsson, Daniel J.
8dfd3a9e-478f-4701-8228-9a6591d3c1b3
Price, Jason R.
b4b3362d-8a02-4446-8e83-302ae792f6b0
Kühne, Irina A.
a75f6bb9-ee66-49d5-9a75-c8a15232efe8
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Kepert, Cameron J.
189dc2eb-da77-4b14-a6f8-7075b27c50e9
Keene, Tony D.
fb859c26-6a1d-4c43-a15f-f329bc8d34d7

Mulrooney, David Z.T., Clements, John E., Ericsson, Daniel J., Price, Jason R., Kühne, Irina A., Coles, Simon J., Kepert, Cameron J. and Keene, Tony D. (2018) Phase control of ferromagnetic copper(II) carbonate coordination polymers through reagent concentration. European Journal of Inorganic Chemistry, 2018 (48), 5223-5228. (doi:10.1002/ejic.201801041).

Record type: Article

Abstract

A significant degree of control over the dimensionality and magnetic connectivity of CuII carbonate coordination polymers is achieved through varying the concentration of ammonia in the reactant solution. Higher concentration leads to a two-dimensional ferromagnetic [Cu3(2,4′-bipy)6(CO3)2]n 2n+ kagome structure while lower concentration develops a ferromagnetic [Cu(2,4′-bipy)2(H2O)2][Cu(2,4′-bipy)2(CO3)2] chain (where 2,4′-bipy = 2,4′-bipyridine). The carbonate anion in the structures arises from the fixation of atmospheric CO2 by the basic ammonia solution. Modelling the magnetic susceptibility of 1 and 2 reveals ferromagnetic interactions with J/kB = +28.1 K for 1 and +13.99 K for 2. (H = –J). The use of a monodentate polypyridine ligand results in the suppression of the superexchange pathway between layers in 1, removing the metamagnetic behaviour seen in related compounds where a ditopic ligand presents the ability for the layer to couple antiferromagnetically. Attempts to substitute 2,4′-bipy for 4-(N,N-dimethylamino)pyridine (4-dmap) result in a discrete species [Cu(4-ampy)4](ClO4)2 (3).

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e-pub ahead of print date: 29 November 2018
Published date: 31 December 2018
Keywords: Chain structures, Coordination polymers, Kagome structures, Layered compounds, Magnetic properties

Identifiers

Local EPrints ID: 428316
URI: http://eprints.soton.ac.uk/id/eprint/428316
ISSN: 1434-1948
PURE UUID: c112343d-efdd-410c-b33e-71e3ce93f5b4
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272
ORCID for Tony D. Keene: ORCID iD orcid.org/0000-0003-2297-4327

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Date deposited: 20 Feb 2019 17:30
Last modified: 20 Apr 2021 04:01

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Contributors

Author: David Z.T. Mulrooney
Author: John E. Clements
Author: Daniel J. Ericsson
Author: Jason R. Price
Author: Irina A. Kühne
Author: Simon J. Coles ORCID iD
Author: Cameron J. Kepert
Author: Tony D. Keene ORCID iD

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