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Issue 17, 2018
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A family of [Cu2], [Cu4] and [Cu5] aggregates: alteration of reaction conditions, ancillary bridges and capping anions

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Abstract

The phenoxido-bridged [Cu2] complex [Cu2(μ-H4L1)(μ-OH)(μ1,3-NO3)(NO3)(OH2)]·H2O (1) and its hierarchical [Cu4] and [Cu5] assemblies [Cu4(μ-H4L1)2(μ-OH)21,3-ClO4)(OH2)2](ClO4)3·2H2O (2) and [Cu5(μ-H4L1)23-OH)21,3-O2CCF3)2(O2CCF3)2](CF3COO)2 (3) were obtained from the reactions of H5L1 (2,6-bis-{(1,3-dihydroxy-2-methylpropan-2-ylimino)methyl}-4-methylphenol) with three copper(II) salts. The available NO3, ClO4 and CF3COO ions have been trapped for ‘spontaneous’ anion-directed ‘self-assembly’ reactions. All the synthesized complexes contain the [Cu2(μ-H4L1)(μ-OH)]2+ fragment, prone to assemble and crystallize [Cu4] and [Cu5] complexes under varying reaction conditions. They were characterized by UV-vis and IR spectroscopy, X-ray diffraction analysis and magnetic studies. A change from NO3 to ClO4 and CF3COO results in different courses of reactions based on Cu2(μ-H4L1) fragments. Binding of NO3 provided 1 as an isolated [Cu2] complex by trapping the reactive fragment. In 2 a perchlorate ligand, in the μ1,3-binding mode, has been realized as a solitary support for the condensation of two Cu2(μ-H4L1) fragments. The {Cu53-OH)21,3-O2CCF3)2}6+ constellation in 3 contains five CuII centers with a unique Z-in distorted octahedral one at the central position. Binding of different anions to the copper(II) centers controls the nuclearity of the reaction products and tuning of the self-aggregation process within the same ligand environment (μ-H4L1). The magnetic properties of the compounds have been studied both experimentally and using DFT calculations, revealing moderate to strong antiferromagnetic coupling in all aggregates.

Graphical abstract: A family of [Cu2], [Cu4] and [Cu5] aggregates: alteration of reaction conditions, ancillary bridges and capping anions

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Publication details

The article was received on 01 May 2018, accepted on 16 Jul 2018 and first published on 17 Jul 2018


Article type: Paper
DOI: 10.1039/C8NJ02131G
New J. Chem., 2018,42, 14349-14364

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    A family of [Cu2], [Cu4] and [Cu5] aggregates: alteration of reaction conditions, ancillary bridges and capping anions

    M. Das, G. A. Craig, D. Escudero, M. Murrie, A. Frontera and D. Ray, New J. Chem., 2018, 42, 14349
    DOI: 10.1039/C8NJ02131G

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