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[CrIII8NiII6]n+ heterometallic coordination cubes

[CrIII8NiII6]n+ heterometallic coordination cubes
[CrIII8NiII6]n+ heterometallic coordination cubes
Three new heterometallic [CrIII8NiII6] coordination cubes of formulae  [CrIII8NiII6L24(H2O)12](NO3)12 (1), [CrIII8NiII6L24(MeCN)7(H2O)5](ClO4)12 (2), and [CrIII8NiII6L24Cl12] (3) (where HL = 1-(4-pyridyl)butane-1,3-dione), were synthesised using the paramagnetic metalloligand [CrIIIL3] and the corresponding NiII salt. The magnetic skeleton of each capsule describes a face-centred cube in which the eight CrIII and six NiII ions occupy the eight vertices and six faces of the structure, respectively. Direct current magnetic susceptibility measurements on (1) reveal weak ferromagnetic interactions between the CrIII and NiII ions, with JCr-Ni = + 0.045 cm−1. EPR spectra are consistent with weak exchange, being dominated by the zero-field splitting of the CrIII ions. Excluding wheel-like structures, examples of large heterometallic clusters containing both CrIII and NiII ions are rather rare, and we demonstrate that the use of metalloligands with predictable bonding modes allows for a modular approach to building families of related polymetallic complexes. Compounds (1)–(3) join the previously published, structurally related family of [MIII8MII6] cubes, where MIII = Cr, Fe and MII = Cu, Co, Mn, Pd.
molecular magnetism, supramolecular Chemistry, heterometallic clusters, magnetometry, EPR spectroscopy
1420-3049
O'Connor, Helen M.
d826fdbd-f27d-4b62-b37f-7d4a551ee26b
Sanz, Sergio
d7d88bc7-d8c4-4003-818d-ce6bc965cbe9
Scott, Aaron J.
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Pitak, Mateusz
eeb6a00f-2291-4376-830f-d30dfd607ed1
Klooster, Wim
64dc0111-f415-4226-9189-45764c0933d9
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Chilton, Nicholas F.
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McInnes, Eric J.L.
bba4b839-d79c-4561-b6e7-c002cc251ff4
Lusby, Paul J.
7edd6163-af61-4425-83ef-bf48d9c9b094
Weihe, Høgni
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Piligkos, Stergios
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Brechin, Euan K.
3f928747-2144-43c3-8ac8-9b2013437edc
O'Connor, Helen M.
d826fdbd-f27d-4b62-b37f-7d4a551ee26b
Sanz, Sergio
d7d88bc7-d8c4-4003-818d-ce6bc965cbe9
Scott, Aaron J.
6f3935c9-4a9e-443f-9abe-7e38b61d7a2b
Pitak, Mateusz
eeb6a00f-2291-4376-830f-d30dfd607ed1
Klooster, Wim
64dc0111-f415-4226-9189-45764c0933d9
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Chilton, Nicholas F.
850941d1-c8bf-40fd-abaa-6a5467a0e549
McInnes, Eric J.L.
bba4b839-d79c-4561-b6e7-c002cc251ff4
Lusby, Paul J.
7edd6163-af61-4425-83ef-bf48d9c9b094
Weihe, Høgni
170e792d-b85a-4e12-b8c0-d5afa41f292b
Piligkos, Stergios
50cdf27a-f790-4aab-92e8-80d433567f4e
Brechin, Euan K.
3f928747-2144-43c3-8ac8-9b2013437edc

O'Connor, Helen M., Sanz, Sergio, Scott, Aaron J., Pitak, Mateusz, Klooster, Wim, Coles, Simon J., Chilton, Nicholas F., McInnes, Eric J.L., Lusby, Paul J., Weihe, Høgni, Piligkos, Stergios and Brechin, Euan K. (2021) [CrIII8NiII6]n+ heterometallic coordination cubes. Molecules, 26 (3), [757]. (doi:10.3390/molecules26030757).

Record type: Article

Abstract

Three new heterometallic [CrIII8NiII6] coordination cubes of formulae  [CrIII8NiII6L24(H2O)12](NO3)12 (1), [CrIII8NiII6L24(MeCN)7(H2O)5](ClO4)12 (2), and [CrIII8NiII6L24Cl12] (3) (where HL = 1-(4-pyridyl)butane-1,3-dione), were synthesised using the paramagnetic metalloligand [CrIIIL3] and the corresponding NiII salt. The magnetic skeleton of each capsule describes a face-centred cube in which the eight CrIII and six NiII ions occupy the eight vertices and six faces of the structure, respectively. Direct current magnetic susceptibility measurements on (1) reveal weak ferromagnetic interactions between the CrIII and NiII ions, with JCr-Ni = + 0.045 cm−1. EPR spectra are consistent with weak exchange, being dominated by the zero-field splitting of the CrIII ions. Excluding wheel-like structures, examples of large heterometallic clusters containing both CrIII and NiII ions are rather rare, and we demonstrate that the use of metalloligands with predictable bonding modes allows for a modular approach to building families of related polymetallic complexes. Compounds (1)–(3) join the previously published, structurally related family of [MIII8MII6] cubes, where MIII = Cr, Fe and MII = Cu, Co, Mn, Pd.

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Accepted/In Press date: 30 January 2021
Published date: 2 February 2021
Keywords: molecular magnetism, supramolecular Chemistry, heterometallic clusters, magnetometry, EPR spectroscopy

Identifiers

Local EPrints ID: 447086
URI: http://eprints.soton.ac.uk/id/eprint/447086
ISSN: 1420-3049
PURE UUID: baa66dbe-8503-4cf1-adcb-c571350a3924
ORCID for Mateusz Pitak: ORCID iD orcid.org/0000-0002-3680-7100
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 03 Mar 2021 17:30
Last modified: 04 Mar 2021 02:35

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Contributors

Author: Helen M. O'Connor
Author: Sergio Sanz
Author: Aaron J. Scott
Author: Mateusz Pitak ORCID iD
Author: Wim Klooster
Author: Simon J. Coles ORCID iD
Author: Nicholas F. Chilton
Author: Eric J.L. McInnes
Author: Paul J. Lusby
Author: Høgni Weihe
Author: Stergios Piligkos
Author: Euan K. Brechin

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