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Triple-decker sandwich complexes, which consist of two cerium ions and three strip-like diarylporphyrins, have been synthesized and their spectroscopic and electrochemical properties and mesomorphism are reported and compared with those of the corresponding double deckers and the parent monomers. The Soret band of the triple-deckers lies at longer and shorter wavelengths than those of the double-deckers and monomers, respectively, while a sequence of small absorptions is observed in the Q band region. These are interpreted on the basis of knowledge of triple-deckers made from tetraphenylporphyrin and octaethylporphyrin. Magnetic circular dichroism (MCD) spectroscopy suggests that the Soret bands of the triple-deckers are a superimposition of at least two transitions to orbitally degenerate states. In the MCD spectra, Faraday A-terms are observed corresponding to each absorption band, suggesting that these triple-deckers take D4h or more plausibly D4d structures. Triple-deckers containing dialkoxyphenyl groups at the 5,15-positions of their parent porphyrin show a mesophase possessing both lamellar and columnar structures at lower temperatures and a columnar mesophase at higher temperatures, which differ in stacking distances. On the other hand, those containing tetraalkoxylated terphenyl groups at the 5,15-positions of their parent porphyrin show only a columnar mesophase with a single stacking distance. These differences in the mesomorphism are explained by differences of the magnitude of the steric hindrance of the side chains for rotation along the axis connecting the center of the three porphyrins.

Comparative study of optical properties of alkylthio-group-substituted phthalocyanine rare-earth metal sandwich complexes (͓(C n S͒ 8 Pc͔ 2 M,MϭEu,Lu,Tb) is presented. Photoluminescence and photoconductivity of ͓(C n S͒ 8 Pc͔ 2 M complex is very weak. Two photoluminescence bands were observed at around 400-650 and 720-800 nm in chloroform solution corresponding to the Soret and Q bands in the absorption spectra, respectively. However, the emission from Eu 3ϩ ion ͑as well as Tb 3ϩ ) was not found compared with other Eu complexes because the 5d levels of the Eu 3ϩ ion lie higher than the triplet level of the ligand. The significant enhancement of the photoconductivity of ͓(C 16 S͒ 8 Pc͔ 2 M after C 60 doping is reported. The photoconductivity is positive at the low electric field in the ohmic regime while it becomes negative at the high electric field upon photoexcitation with strongly absorbed light. The negative photoconductivity is attributed to space-charge effects. The mechanism of photoluminescence and photoconductivity are discussed by taking the electronic energy schemes of phthalocyanine ligands and lanthanide ion and C 60 into consideration.