Darstellung und Eigenschaften von Bis(phthalocyaninato)lanthanaten und -ceraten / Preparation and Properties of Bis(phthalocyaninato)lanthanates and -cerates

High yields of bisphthalocyaninates of lanthanum and cerium have been obtained in the strongly exothermic reaction of the dehydrated lanthanoid acetates with molten 1,2-dicyanobenzene in the presence of potassium hydroxide or methylate. Salts of the type (cat)[M(Pc(2—)),] (M = La, Ce) with different cations (cat = K, Bu N, PNP, TDOA) have been isolated. The corresponding “Hydrogen salts” are obtained by thermal decomposition of (Bu N)[M(Pc(2—)) ] at T > 350 C. The dimeric structure is confirmed by negative fast atom bombardement mass spectra. The redox properties have been investigated by cyclovoltammetry and UV, VIS, MIR, FIR and resonance Raman (RR) spectra are reported. Electronic transitions between 2000 and 3000 cm are observed in the low temperature RR spectra of (Bu N)[Ce(Pc(2—)) ] being RR enhanced at 470 nm. From the assignment to the higher transitions within the symmetry split manifolds of the f ground state of Ce the crystal field parameters ζ = 610.5, B = 242.2 and B = 4.1 cm have been determined.