TY - JOUR

T1 - [CrIII8MII6]n+ (MII = Cu, Co) face-centred, metallosupramolecular cubes

AU - O'Connor, H. M.

AU - Sanz, S.

AU - Pitak, M. B.

AU - Coles, S. J.

AU - Nichol, G. S.

AU - Piligkos, Stergios

AU - Lusby, P. J.

AU - Brechin, E. K.

PY - 2016

Y1 - 2016

N2 - 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.

AB - 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.

U2 - 10.1039/c6ce00654j

DO - 10.1039/c6ce00654j

M3 - Journal article

AN - SCOPUS:84976526813

VL - 18

SP - 4914

EP - 4920

JO - CrystEngComm

JF - CrystEngComm

SN - 1466-8033

IS - 26

ER -