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Issue 16, 2016
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Unique trapping of paddlewheel copper(ii) carboxylate by ligand-bound {Cu2} fragments for [Cu6] assembly

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Abstract

The bridging nature of in situ generated hydroxide ions and carboxylates (RCOO; R = CH3, C2H5, CH2Ph) has been utilized to design a new family of [Cu6] coordination complexes: [Cu63-OH)2(μ-H2L)21,1,3-O2CCH3)21,3-O2CCH3)2(μ-ClO4)2](ClO4)2·H2O (1), [Cu63-OH)2(μ-H2L)21,1,3-O2CC2H5)4(μ-ClO4)2](ClO4)2·2H2O (2) and [Cu63-OH)2(μ-H2L)21,3-O2CCH2Ph)4(ClO4)2](ClO4)2·2H2O (3). Tetracarboxylate bridged {Cu2} core units are trapped between two ligand-bound {Cu2(μ-H2L)(μ-OH)}2+ subunits forming the [Cu6] complexes. The hexanuclear {Cu63-OH)2(H2L)2(μ-O2CR)4}4+ cores having six interconnected CuII ions assume a hitherto unknown dumbbell-shaped topology. Detailed characterizations have been done using X-ray crystallography and variable temperature magnetic measurements. For complexes 1–3, the dominant coupling constant (J′) values between carboxylate bridged copper centers are −36.2 to −45.2 cm−1 for short Cu⋯Cu separations of 2.540–2.578 Å. In MeCN solutions all three complexes showed catalytic oxidation of 3,5-di-tert-butyl catechol (3,5-DTBCH2) in air.

Graphical abstract: Unique trapping of paddlewheel copper(ii) carboxylate by ligand-bound {Cu2} fragments for [Cu6] assembly

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Supplementary files

Article information


Submitted
09 Jan 2016
Accepted
29 Feb 2016
First published
01 Mar 2016

Dalton Trans., 2016,45, 6928-6938
Article type
Paper

Unique trapping of paddlewheel copper(II) carboxylate by ligand-bound {Cu2} fragments for [Cu6] assembly

K. Chattopadhyay, B. K. Shaw, S. K. Saha and D. Ray, Dalton Trans., 2016, 45, 6928 DOI: 10.1039/C6DT00103C

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