Abstract
The macrocycle L, prepared by template condensation of bis-6,6″-(α-methylhidrazino)-4 ′-phenyl-2,2 ′:6″,2 ′-terpyridine with glyoxal, forms a stable crystalline complex of copper(II) [Cu(L)(H 2O) 2][PF 6] 2 which has been used as a starting material to prepare, for electrochemical studies, a series of seven coordinate copper(II) complexes [Cu(L)X 2][PF 6] 2 (X=pyridine, 4-cyanopyridine, 4-aminopyridine, 4-dimethylaminopyridine, pyrazine, imidazole, 1-methylimidazole, 2-methylimidazole, and trimethylphosphite). Cyclic voltammetry of the aquo complex in DMSO show one reversible reduction wave at −0.36 V versus Ag/AgBF 4 reference electrode and controlled potential electrolysis in the presence of trimethylphosphite affords a diamagnetic species which has been assigned as a mononuclear d 10 Cu(I) species. The crystal and molecular structure of [Cu(L)(imidazole) 2][PF 6] 2 shows the metal to be in a pentagonal bipyramidal N 7 environment.
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