A dodecanuclear copper(II) cage self-assembled from six dicopper building units.
Reaction of the dinucleating phenol-based ligand, H3bpmp (2,6-bis-[(3-hydroxy-propylimino)-methyl]-4-methyl-phenol), with Cu(2+) 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 {Cu6(μ3-OH)3(μ3-Hbpmp)3(μ3-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 Cu(2+) 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 Hbpmp(2-) 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.
Department of Chemistry, Indian Institute of Technology, Kharagpur 721 302, India. dray@chem.iitkgp.ernet.in.
Aloke Kumar
AK
Ghosh
Moumita
M
Pait
Rodolphe
R
Clérac
Corine
C
Mathonière
Valerio
V
Bertolasi
Antonio
A
Bauzá
Antonio
A
Frontera
Kausikisankar
K
Pramanik
Debashis
D
Ray
D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D008024:Ligands; D060328:Magnetic Phenomena; D010636:Phenols / Q000737:chemistry; D013696:Temperature
D056831:Coordination Complexes; D008024:Ligands; D010636:Phenols; D003300:Copper