Das, M., Craig, G. A., Escudero, D., Murrie, M. , Frontera, A. and Ray, D. (2018) A family of [Cu2], [Cu4] and [Cu5] aggregates: alteration of reaction conditions, ancillary bridges and capping anions. New Journal of Chemistry, 42(17), pp. 14349-14364. (doi: 10.1039/C8NJ02131G)
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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)2(μ1,3-ClO4)(OH2)2](ClO4)3·2H2O (2) and [Cu5(μ-H4L1)2(μ3-OH)2(μ1,3-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 {Cu5(μ3-OH)2(μ1,3-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.
Item Type: | Articles |
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Additional Information: | M.D. is grateful to IIT Kharagpur for her research fellowship. |
Status: | Published |
Refereed: | Yes |
Glasgow Author(s) Enlighten ID: | Craig, Dr Gavin and Murrie, Professor Mark |
Authors: | Das, M., Craig, G. A., Escudero, D., Murrie, M., Frontera, A., and Ray, D. |
College/School: | College of Science and Engineering > School of Chemistry |
Journal Name: | New Journal of Chemistry |
Publisher: | Royal Society of Chemistry |
ISSN: | 1144-0546 |
ISSN (Online): | 1369-9261 |
Published Online: | 17 July 2018 |
Copyright Holders: | Copyright © 2018 The Authors |
First Published: | First published in New Journal of Chemistry 42(17):14349-14364 |
Publisher Policy: | Reproduced in accordance with the copyright policy of the publisher |
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