RESUMO
Reactions of trinickel complex of tripodal tris-tacn ligand N(CH2 -m-C6 H4 -CH2 tacn)3 (L, tacn=1,4,7-triazacyclononane) in acetonitrile-methanol solution with and without phosphate led to two complexes of distinct nuclearities, [(NiII Cl)3 (CH3 OH)3 (HPO4 )L](PF6 ) (Ni3 , 1) and [(NiII5 (CN)4 (H2 O)8 Cl)6 L8 ]Cl30 (Ni30 , 2). Ligand L takes upward and downward conformation in the structure of 1 and 2, respectively. It is proposed that phosphate directs the upward conformation of Ni3 L to form 1. In the absence of phosphate, Ni3 L assembles with cyanide ions, which are formed by Ni-catalyzed C-CN bond cleavage of acetonitrile, to give a nano-sized Ni30 cage. Complex 2 represents a discrete truncated octahedron cage assembled with [Ni5 (CN)4 ]6+ squares and large and flexible triangular ligands, which is scarcely observed for self-assembled metal-organic cages. The magnetic properties of 1 and 2 were examined, showing intriguing magnetic properties.
