Synthesis and Characterization of New Mixed Rare Earth Triple-Decker Complexes With Tetra(tert-butyl)phthalocyaninato and Meso-Tetrakis(4-pyridyl)porphyrinato Ligands

Four new mixed 3(4), 12(13), 21(22), 30(31)-tetra(tert-butyl)phthalocyaninato tetrakis(4-pyridyl)porphyrinato rare earth triple-decker complexes M2(TPyP)(TBPc)2 (M˭Ce, Sm, Tb, and Tm) have been prepared by treating M(acac)(TPyP) with corresponding homoleptic substituted bis(phthalocyaninato) rare earth complexes M(TBPc)2 in refluxing 1,2,4-trichlorobenzene (TCB), typical for the light, middle, and heavy rare earths, respectively. Typical IR marker bands of the substituted phthalocyanine dianion Pc(TBPc)2− show strong bands at ca. 1323 cm−1, and are attributed to pyrrole C˭C stretchings. The TPyP2− IR marker band at ca. 1270–1300 cm−1 was not observed for these compounds. A very strong band at 1500 cm−1 with contributions from both pyrrole C˭C and aza C˭N stretchings and also isoindole stretching was the marker Raman band of (TBPc)2−. Their electrochemical properties were investigated by cyclic voltammetry and differential pulse voltammetry. The four complexes were also characterized by EA, MS, and UV-vis ...