Infrared spectroscopic characteristics of phthalocyanine in mixed [tetrakis(4-chlorophenyl)porphyrinato](phthalocyaninato) rare earth double-deckers

The infra-red (IR) spectroscopic data for a series of 15 mixed [tetrakis(4-chlorophenyl)porphyrinato](phthalocyaninato) rare earth double-decker complexes with tervalent rare earths MIII(TClPP)(Pc) (M = Y, La, …, Lu except Ce and Pm) and intermediate-valent cerium Ce(TClPP)(Pc) have been collected with resolution of 2 cm−1. For MIII(TClPP)(Pc), typical IR marker band of the monoradical anion Pc− shows the most intense absorption band whose frequency linearly varies in the range from 1311 cm−1 for La(TClPP)(Pc) to 1320 cm−1 for Lu(TClPP)(Pc) along with the decrease of rare earth ionic size. The peaks at 1016-1023 cm−1 are assigned to CCl stretchings. For Ce(TClPP)(Pc), a medium band at 1329 cm−1 with contribution from pyrrole stretching was the marker IR band of phthalocyanine dianion Pc2−. The TClPP− IR marker band at ca. 1270-1300 cm−1 was not observed for these compounds. These facts indicate that the hole in these double-deckers is mainly localized at the phthalocyanine ring.