The XANES (X-ray absorption near edge structure) spectra of copper(II) ions in solid state and in solution of the square-planar copper(II) complexes with tetraaza macrocycles were measured. The peaks in the measured XANES spectra shifted to lower energy side with increasing the electron density of central copper(II) ions. The molecular orbital calculations for the complexes were carried out by the DV-Xα method, and the theoretical XANES spectra were estimated. The clear chemical shift obtained by this XANES study is evaluated and leads to a new concept of π-back donation between the copper(II) complexes and counter anion in aqueous solution.
