Copper(II) Catecholate Complexes with Polypyridyl Ligands

Copper(II) catecholate complexes based on 3,6-di-tert-butyl-o-benzoquinone with N-donor ligands of the phenanthroline series have been synthesized: (3,6-Cat)Cu(Phen) (I), (3,6-Cat)Cu(DPQ) (II), and (3,6-Cat)Cu(DPPZ) (III), where 3,6-Cat is the 3,6-di-tert-butyl-o-benzoquinone dianion, Phen is phenanthroline, DPQ is dipyrido[3,2-d:2',3'-f]quinoxaline, and DPPZ is dipyrido[3,2-alpha:2',3'-c]phenazine. The synthesized copper(II) complexes demonstrate intramolecular ligand-to-ligand charge transfer responsible for their intense violet color. The electronic structure of the synthesized chromophores was studied by electronic spectroscopy, cyclic voltammetry, and quantum-chemical calculations. The molecular and crystal structures of the synthesized compounds were determined by X-ray diffraction analysis (CIF files CCDC 2250975 (I center dot THF), 2250976 ([(II center dot THF)(II)]center dot 3THF), 2250977 (II)).