New μ4-Oxido-Bridged Copper Benzoate Quasi-Tetrahedron and Bis-μ3-Hydroxido-Bridged Copper Azide and Copper Thiocyanate Stepped Cubanes: Core Conversion, Structural Diversity, and Magnetic Properties
- 24 June 2010
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 49 (14) , 6575-6585
Abstract
[Cu2(μ4-O)Cu2] and [Cu2(μ3-OH)2Cu2] geometrical arrangements are found in a new family of tetranuclear complexes: [Cu4(μ4-O)(μ-bip)2(μ-O2CPh)4]·0.5CH2Cl2 (1·0.5CH2Cl2), [Cu4(μ3-OH)2(μ-bip)2(N3)4] (2), and [Cu4(μ3-OH)2(μ-bip)2(NCS)4(DMF)2] (3·2DMF) [Hbip = 2,6-bis(benzyliminomethyl)-4-methylphenol; DMF = dimethylformamide]. These complexes have been characterized by X-ray crystallography, and their magnetic properties have been studied. Complex 1 reacts with azide and thiocyanate anions, leading to 2 and 3 with a change of the [Cu4(μ4-O)] core into [Cu4(μ3-OH)2] units. These compounds are new examples of [Cu4] complexes where CuII ions are connected by two types of water-derived ligands: oxide and hydroxide. Formation of these [Cu4] complexes can be controlled by changing the bridging ligands, which allows an effective tuning of the self-assembly. The study of the magnetic properties reveals that these complexes exhibit strong intramolecular antiferromagnetic interactions to yield a ST = 0 ground state. For the three complexes, the temperature dependence of the magnetic susceptibility was fitted using a model with two isolated S = 1/2 dimers based on the H = −2J{SCu,1·SCu,2} spin Hamiltonian with J/kB = −289 K for 1; J/kB = −464 and −405 K for 2 and 3, respectively (where J is the exchange constant through the oxido−phenoxido or hydroxido−phenoxido bridges, respectively).Keywords
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