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Issue 10, 2014
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A dodecanuclear copper(II) cage self-assembled from six dicopper building units

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Reaction of the dinucleating phenol-based ligand, H3bpmp (2,6-bis-[(3-hydroxy-propylimino)-methyl]-4-methyl-phenol), with Cu2+ ions in the presence of a hybrid base (NEt3 and NaN3) necessary for the in situ generation of required numbers of hydroxido ions, results in the formation of a novel NO3 capped and HO supported {Cu12} coordination complex {Cu63-OH)33-Hbpmp)33-NO3)}2(NO3)2(OH)2·2H2O·2MeOH (1). When the components are combined in right proportions (metal : ligand : NEt3 : NaN3 = 2 : 1 : 3 : 2) in MeOH, twelve Cu2+ ions assemble in a cuboctahedral geometry, containing six square and eight triangular faces around a considerable void space. Six of the eight [Cu3] triangular faces are bound by the six Hbpmp2− ligands with six free pendant propanol arms around the central hexagonal plane. X-ray structure determination indicates new geometrical features for the core formation and reveals the face-capping potential of the H3bpmp ligand for the growth of a cuboctahedral coordination cage with the support of anions like HO and NO3. The experimentally observed (J/kB = −173 K) strong antiferromagnetic coupling within the Cu12 complex has been justified by the DFT calculations.

Graphical abstract: A dodecanuclear copper(ii) cage self-assembled from six dicopper building units

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Publication details

The article was received on 06 Nov 2013, accepted on 24 Dec 2013 and first published on 02 Jan 2014

Article type: Paper
DOI: 10.1039/C3DT53144A
Citation: Dalton Trans., 2014,43, 4076-4085
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    A dodecanuclear copper(II) cage self-assembled from six dicopper building units

    A. K. Ghosh, M. Pait, R. Clérac, C. Mathonière, V. Bertolasi, A. Bauzá, A. Frontera, K. Pramanik and D. Ray, Dalton Trans., 2014, 43, 4076
    DOI: 10.1039/C3DT53144A

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