Abstract

The pendant-armed ligands L1 and L2 were synthesized by N-alkylation of the four secondary amine groups of the macrocyclic precursor L using o-nitrobenzylbromide (L1) and p-nitrobenzylbromide (L2). Nitrates and perchlorates of CuII, NiII and CoII were used to synthesize the metal complexes of both ligands and the complexes were characterized by microanalysis, MS-FAB, conductivity measurements, IR and UV-Vis spectroscopy and magnetic studies. The crystal structures of L1, [CuL1](ClO4)2·CH3CN·H2O, [CuL2](ClO4)2·6CH3CN, [CuL2][Cu(NO3)4]·5CH3CN·0.5CH3OH and [NiL2](ClO4)2·3CH3CN·H2O were determined by single crystal X-ray crystallography. These structural analysis reveal the free ligand L1, three mononuclear endomacrocyclic complexes {[CuL1](ClO4)2·CH3CN·H2O, [CuL2](ClO4)2·6CH3CN and [NiL2](ClO4)2·3CH3CN·H2O} and one binuclear complex {[CuL2][Cu(NO3)4]·5CH3CN·0.5CH3OH} in which one of the metals is in the macrocyclic framework and the other metal is outside the ligand cavity and coordinated to four nitrate ions.

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