Synthesis, Structure, Property, and Dinuclear Cu(II) Complexation of Tetraoxacalix[2]arene[2]phenanthrolines

A number of novel tetraoxacalix[2]arene[2]phenanthrolines 7-11 containing phenanthroline and diverse aromatic linkages were conveniently synthesized by a one-pot protocol between a series of dihydroxy arenes and 1,10-phenanthroline derivatives. Single-crystal diffraction analysis revealed that the resulting macrocycles possess diverse conformational and cavity structures which are regulated by the different aromatic linkages. In line with the length of the aromatic linkages, the distance between the two phenanthroline moieties ( d_N-N) gradually increases from 6.92 to 13.30 Å, respectively. The physicochemical properties of these macrocyclic compounds were investigated by spectroscopic, CV, and DPV measurements. Owing to the coordination ability of the phenanthroline moieties and the tunable conformational structure, the macrocyclic hosts can form distinct dinuclear complexation with Cu²⁺. Typically, with a short aromatic linkage the 7b-2Cu(II) complex gives an O-bridged dicopper structure, while with long linkage the 11b-2Cu(II) complex possesses two discrete copper centers. The spectroscopic structure and the redox property of the dicopper complexes were investigated by XPS, CV, and DPV techniques. This work hence provides a platform to access biomimetic copper-containing small-molecule models with well-defined structures.