LnPcCl and Ln(HPc)(OAc)2 (Ln = Tb, Ho, Tm, Lu, H2Pc = phthalocyanine) were synthesized. Their electronic structures were studied by XPS. The experimental results of binding energies for the complexes indicate that the bonds of the complexes have a certain covalent character depending on L ?Ln charge transfer. This L ?Ln charge transfer process of phthalocyanine complexes differs from that of crown ether complexes. Both coordination and substitution are included in the former case, but only coordination in the latter. Phthalocyanine ring is an electrophilic group and its electronegativity is large. So, the O 1s binding energies of coordinating O atoms of acetate in LnPc(OAc)2 are larger than those of Ln(OAc)3. The magnitude of valent charge delocalized from ligand onto metal atom is dependent on electronegativity, coordination no., valence state, etc. Because coordination no. of Ln in Ln(HPc)(OAc)2 is larger than that in LnPcCl and electronegativity of Cl in LnPcCl is larger than that of O in Ln(HPc)(OAc)2, the Ln 4d5/2 binding energies of Ln(HPc)(OAc)2 are less than those of LnPcCl.

Key words: PHTHALOCYANINE P, CHLORIDE, ELEMENTAL ANALYSIS, X-RAY PHOTOELECTRON SPECTROMETRY, CHEMICAL BONDS, RARE EARTH METAL COMPLEX, ELECTRONIC STRUCTURE, TITANIUM COMPLEX, ACETIC ACID P, THULIUM COMPLEX