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Molecular enneanuclear CuII phosphates containing planar hexanuclear and trinuclear sub-units: syntheses, structures, and magnetism

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Abstract

Highly symmetric enneanuclear copper(II) phosphates [Cu9(Pz)6(μ-OH)33-OH)(ArOPO3)4(DMF)3] (PzH = pyrazole, Ar = 2,6-(CHPh2)2-4-R-C6H2; R = Me, 2MeAr; Et, 2EtAr; iPr, 2iPrAr; and Ar = 2,6-iPr2C6H3, 2Dip) comprising nine copper(II) centers and pyrazole, hydroxide and DMF as ancillary ligands were synthesized by a reaction involving the arylphosphate monoester, 1, copper(I)chloride, pyrazole, and triethylamine in a 4 : 9 : 6 : 14 ratio. All four complexes were characterized by single crystal structural analysis. The complexes contain two distinct structural motifs within the multinuclear copper scaffold: a hexanuclear unit and a trinuclear unit. In the latter, the three Cu(II) centres are bridged by a μ3-OH. Each pair of Cu(II) centers in the trinuclear unit are bridged by a pyrazole ligand. The hexanuclear unit is made up of three dinuclear Cu(II) motifs where the two Cu(II) centres are bridged by an –OH and a pyrazole ligand. The three dinuclear units are connected to each other by phosphate ligands. The latter also aid the fusion of the trinuclear and the hexanuclear motifs. Magnetic studies reveal a strong antiferromagnetic exchange between the Cu(II) centres of the dinuclear units in the hexanuclear part and a strong spin frustration in the trinuclear part leading to a degenerate ground state.

Graphical abstract: Molecular enneanuclear CuII phosphates containing planar hexanuclear and trinuclear sub-units: syntheses, structures, and magnetism

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Article information


Submitted
29 Nov 2019
Accepted
17 Jan 2020
First published
17 Jan 2020

Dalton Trans., 2020, Advance Article
Article type
Paper

Molecular enneanuclear CuII phosphates containing planar hexanuclear and trinuclear sub-units: syntheses, structures, and magnetism

B. Santra, P. Kalita, S. Chandra, D. Mandal, V. Kumar, R. S. Narayanan, A. Dey, N. Chrysochos, V. Huch, S. Biswas, D. Ghoshal, E. C. Sañudo, B. Sarkar, C. Schulzke, V. Chandrasekhar and A. Jana, Dalton Trans., 2020, Advance Article , DOI: 10.1039/C9DT04584H

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