Using p-tert-butylthiacalixarene (H6L) as a clustering ligand, five cluster complexes having CoII5 (2), Ni II4 (3) and MIINiII4 (M = CoII (4), MnII (5), and CuII (6)) cores were synthesized. In all the complexes except for 3, a pinched conic L6- acts as a pentanucleating ligand that involves a similar pyramidally arranged cluster core. Each mixed metal complex 4-6 involves four tetragonally arranged NiII ions occupying the basal plane of the pyramid and a M II ion placed at the apex position. In 3, H2L 4- is in a cone conformation and the four NiII ions are arranged on the donor surface of H2L4- in a zigzag manner. The mixed metal complexes 4-6 are synthesized by reacting 3 and the appropriate M(AcO)2 in a 1:1 ratio with a novel metal-induced core rearrangement occurring. In this reaction, the insertion of a MII ion at the apex position forces the calixarene to take a cone conformation and the NiII4 array rearranges to form a tetragonal cluster.
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