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[CrIII8MII6]n+(MII= Cu, Co) face-centred, metallosupramolecular cubes

[CrIII8MII6]n+(MII= Cu, Co) face-centred, metallosupramolecular cubes
[CrIII8MII6]n+(MII= Cu, Co) face-centred, metallosupramolecular cubes
Four [CrIII8MII6]n+ (MII = Cu, Co) coordination cubes of formulae [Cr8Co6L24Cl12] (1), [Cr8Co6L24(SCN)12] (2), [Cr8Cu6L24(H2O)12](SO4)6 (3), and [Cr8Cu6L24Cl12] (4) (where HL is 1-(4-pyridyl)butane-1,3-dione), were synthesised using the [CrIIIL3] metalloligand in combination with a variety of MII salts. The metallic skeleton of each cage describes a cube in which the [CrIIIL3] moieties occupy the eight vertices and the MII ions lie at the centre of the six faces. The axial coordination sites of the MII cations are occupied by either H2O molecules or Cl?/SCN? anions originating from the MII salt used in the synthesis, resulting in neutral 1, 2 and 4 and the cage in 3 being a 12+ cation; the charge-balancing SO42? anions accommodated both inside and outside the cube. Magnetic susceptibility and magnetisation measurements reveal weak exchange between nearest neighbour metal ions, mediated via the L? ligands. The modular assembly of the cubes suggests that any combination of [MIIIL3] metalloligand and MII salt will work, potentially resulting in an enormous family of supramolecular assemblies. The charge of the cubes is controlled by the nature of the ligand occupying the axial sites on the MII ions, suggesting trivial ligand exchange may offer control over, amongst others, solubility, reactivity, post-synthetic modification and substrate specificity. The large internal cavities of the cubes also suggest host–guest chemistry may be a fruiful route to encapsulating magnetic and/or redox active guests which could be employed to control magnetic behaviour, and the construction of multifunctional materials.
1466-8033
4914-4920
O'Connor, H.M.
02f5febc-9c28-4d38-a787-822a78d68071
Sanz, S.
1acc8c92-0a0e-4beb-bc82-3cf553148cb4
Pitak, M.B.
eeb6a00f-2291-4376-830f-d30dfd607ed1
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Nichol, G.S.
3374433a-0953-43a7-bd27-7f1772d1ab3c
Piligkos, S.
b8f89d99-7567-482b-a804-8a7efe86c682
Lusby, P.J.
43407977-b1c9-4824-b99b-dc3075ed2f8e
Brechin, E.K.
439a0a90-77ae-446b-9b16-14522d4463b0
O'Connor, H.M.
02f5febc-9c28-4d38-a787-822a78d68071
Sanz, S.
1acc8c92-0a0e-4beb-bc82-3cf553148cb4
Pitak, M.B.
eeb6a00f-2291-4376-830f-d30dfd607ed1
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Nichol, G.S.
3374433a-0953-43a7-bd27-7f1772d1ab3c
Piligkos, S.
b8f89d99-7567-482b-a804-8a7efe86c682
Lusby, P.J.
43407977-b1c9-4824-b99b-dc3075ed2f8e
Brechin, E.K.
439a0a90-77ae-446b-9b16-14522d4463b0

O'Connor, H.M., Sanz, S., Pitak, M.B., Coles, S.J., Nichol, G.S., Piligkos, S., Lusby, P.J. and Brechin, E.K. (2016) [CrIII8MII6]n+(MII= Cu, Co) face-centred, metallosupramolecular cubes. CrystEngComm, 18 (26), 4914-4920. (doi:10.1039/C6CE00654J).

Record type: Article

Abstract

Four [CrIII8MII6]n+ (MII = Cu, Co) coordination cubes of formulae [Cr8Co6L24Cl12] (1), [Cr8Co6L24(SCN)12] (2), [Cr8Cu6L24(H2O)12](SO4)6 (3), and [Cr8Cu6L24Cl12] (4) (where HL is 1-(4-pyridyl)butane-1,3-dione), were synthesised using the [CrIIIL3] metalloligand in combination with a variety of MII salts. The metallic skeleton of each cage describes a cube in which the [CrIIIL3] moieties occupy the eight vertices and the MII ions lie at the centre of the six faces. The axial coordination sites of the MII cations are occupied by either H2O molecules or Cl?/SCN? anions originating from the MII salt used in the synthesis, resulting in neutral 1, 2 and 4 and the cage in 3 being a 12+ cation; the charge-balancing SO42? anions accommodated both inside and outside the cube. Magnetic susceptibility and magnetisation measurements reveal weak exchange between nearest neighbour metal ions, mediated via the L? ligands. The modular assembly of the cubes suggests that any combination of [MIIIL3] metalloligand and MII salt will work, potentially resulting in an enormous family of supramolecular assemblies. The charge of the cubes is controlled by the nature of the ligand occupying the axial sites on the MII ions, suggesting trivial ligand exchange may offer control over, amongst others, solubility, reactivity, post-synthetic modification and substrate specificity. The large internal cavities of the cubes also suggest host–guest chemistry may be a fruiful route to encapsulating magnetic and/or redox active guests which could be employed to control magnetic behaviour, and the construction of multifunctional materials.

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Accepted/In Press date: 18 April 2016
e-pub ahead of print date: 18 April 2016
Published date: 14 July 2016
Organisations: Faculty of Natural and Environmental Sciences

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Local EPrints ID: 403370
URI: http://eprints.soton.ac.uk/id/eprint/403370
ISSN: 1466-8033
PURE UUID: 906ce5c7-c11d-4165-a58d-03ba4adc6d88
ORCID for M.B. Pitak: ORCID iD orcid.org/0000-0002-3680-7100
ORCID for S.J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 30 Nov 2016 13:56
Last modified: 16 Mar 2024 03:05

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Contributors

Author: H.M. O'Connor
Author: S. Sanz
Author: M.B. Pitak ORCID iD
Author: S.J. Coles ORCID iD
Author: G.S. Nichol
Author: S. Piligkos
Author: P.J. Lusby
Author: E.K. Brechin

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