New mixed rare earth double-decker complexes with octyloxynaphthyl-porphyrinato and phenylthio-naphthalocyaninato ligands – preparation and spectroscopic characterization

Eight new (porphyrinato)(naphthalocyaninato) rare earth(III) double-decker complexes M^III(TONPP)[Nc(PhS)₈] [M = La, Pr, Nd, Sm, Eu, Gd, Tb, and Dy; TONPP = 5,10,15,20-tetrakis(4-octyloxynaphthyl) porphyrin; Nc(PhS)₈ = 3,4,12,13,21,22,30,31-octa(phenylthio)-2,3-naphthalocyanine] have been prepared and characterized by spectroscopic methods. The UV–vis absorption spectra depend on the central rare earth ionic size, suggesting that all the transitions involve molecular orbitals with contribution from both porphyrin and naphthalocyanine ligands. The IR and Raman spectra of these double-decker compounds were systemically investigated, showing that the electron hole in these mixed double-deckers is mainly localized at the naphthalocyanine ring. Their sandwich nature was also characterized by MS, EA, and ¹H NMR techniques.