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A dodecanuclear copper(II) cage self-assembled\ud from six dicopper building units

By Aloke Kumar Ghosh, Moumita Pait, Rodolphe Clérac, Corine Mathonière, Valerio Bertolasi, Antonio Bauzá, Antonio Frontera, Kausikisankar Pramanikh and Debashis Ray


Reaction of the dinucleating phenol-based ligand, H3bpmp (2,6-bis-[(3-hydroxy-propylimino)-methyl]-\ud 4-methyl-phenol), with Cu2+ ions in the presence of a hybrid base (NEt3 and NaN3) necessary for the\ud in situ generation of required numbers of hydroxido ions, results in the formation of a novel NO3\ud − capped\ud and HO− supported {Cu12} coordination complex {Cu6(μ3-OH)3(μ3-Hbpmp)3(µ3-NO3)}2(NO3)2(OH)2·\ud 2H2O·2MeOH (1). When the components are combined in right proportions (metal : ligand : NEt3 : NaN3 =\ud 2 : 1 : 3 : 2) in MeOH, twelve Cu2+ ions assemble in a cuboctahedral geometry, containing six square and\ud eight triangular faces around a considerable void space. Six of the eight [Cu3] triangular faces are bound\ud by the six Hbpmp2− ligands with six free pendant propanol arms around the central hexagonal plane.\ud X-ray structure determination indicates new geometrical features for the core formation and reveals the\ud face-capping potential of the H3bpmp ligand for the growth of a cuboctahedral coordination cage with\ud the support of anions like HO− and NO3\ud −. The experimentally observed (J/kB = −173 K) strong antiferro-\ud magnetic coupling within the Cu12 complex has been justified by the DFT calculations

Year: 2014
DOI identifier: 10.1039/c3dt53144a
OAI identifier: oai:iris.unife.it:11392/2307018
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