Previously undescribed complexes of tungstenophosphatometallates with copper ions Cu and hexamethylenetetramine of the composition RbPWOCu(HO) · 9HO (I), RbPWOCu(CHN) · 10HO (II), RbPWOZnCu(HO) · 9HO (III) and RbPWOZnCu(CHN) · 10HO (IV) have been synthesized. The results of chemical analysis, IR and electronic spectroscopy allow us to attribute the obtained compounds to tungstenophosphatometallates with a lacunary structure of the Keggin anion, in which one of the tungsten atoms is replaced by a 3d-element ion (copper or zinc). There is a shift of the absorption maximum of copper ions to the long-wavelength region of the spectrum when transitioning from Cu(HO) to PWOCu(HO), PWOZnCu(HO), PWOCu(HMTA) and PWOZnCu(HMTA), which is a result of the change in the ligand field strength in the inner coordination sphere of the complexes. Temperature dependences of EPR spectra show redistribution of line intensities due to the multi-minimum potential of the crystal field at the location of Cu ions. The height of the crystal field potential barrier for compounds III and IV is 27 and 13 cm, respectively, and depends on the ligand field strength of the immediate environment of Cu ions in the anion structure.
YA. A. MOROZ (Wed,) studied this question.