Discrete and Polymeric, Mono- and Dinuclear Silver Complexes of a Macrocyclic Tetraoxime Ligand with AgI–AgI Interactions

Macrocyclic compounds that can bind cationic species efficiently and selectively with their cyclic cavities have great potential as excellent chemosensors for metal ions. Recently, we have developed a tetraoxime-type tetraazamacrocyclic ligand 1 formed through a facile one-pot cyclization reaction. Aiming to explore and bring out the potential of the tetraoxime macrocycle 1 as a chelating sensor, we report herein the preparation of several kinds of silver complexes of 1 and their unique coordination structures determined by single-crystal X-ray diffraction analyses. As a result, the formation of two kinds of discrete structures, monomeric complexes [Ag(1)X] (X = counter anions) and a dimeric complex [Ag2(1)2]X2, and two kinds of polymeric structures from a mononuclear complex, [Ag(1)]nXn, and from a dinuclear complex, [Ag2(1)X2]n, was demonstrated. In the resulting complexes, the structurally flexible macrocyclic ligand 1 was found to provide several different coordination modes. Notably, in some silver complexes of 1, AgI-AgI interactions were observed with different AgI-AgI distances which depend on the kind of counter anions and the chemical composition.