Satoru Yoshino

Syntheses of near infrared absorbed phthalocyanines to utilize photosensitizers

Phthalocyanines have become of major interest as functional colorants for various applications. In order to use various applications especially photosensitizers, the absorption maxima called Q-band of phthalocyanines are required to be shifted to the near infrared region. Substituted phthalocyanine analog alkylbenzopiridoporphyrazins, especially zinc bis(1,4-didecylbenzo)-bis(3,4-pyrido)porphyrazine, and toroidal-shaped phthalocyanines having aminoamine dendric side chains such as toroidal zinc poly(aminoamine)phthalocyanine dendrons were synthesized. Phthalocyanines of two types reportedly use photosensitizers for photodynamic therapy of cancer. The respective efficacies of photodynamic therapy of cancer for zinc bis(1,4-didecylbenzo)-bis(3,4-pyrido)porphyrazine and its regioisomers were estimated using laser-flash photolysis. The capability of using photodynamic therapy for toroidal zinc poly(aminoamine)phthalocyanine dendrons was assessed using a cancer cell culture. Both phthalocyanines were suitable for the use as a photosensitizer as photodynamic therapy of cancer. Then, non-peripheral thioaryl substituted phthalocyanines, 1,4,8,11,15,18,22,25-octakis(thioaryl)phthalocyanines, such as 1,4,8,11,15,18,22,25-octakis(thiophenylmethyl)phthalocyanines, 1,4,8,11,15,18,22,25-octakis(thiophenylmethoxy)phthalocyanines, and 1,4,8,11,15,18,22,25-octakis(thiophenyl tert-butyl)phthalocyanines were also synthesized in order to develop next- generation photovoltaic cells and/or dye-sensitized solar cells. Non-peripheral substituted 1,4,8,11,15,18,22,25-octakis(thioaryl)phthalocyanines exhibited a Q-band in the near infrared region. Electrochemical measurements were performed on the above-mentioned 1,4,8,11,15,18,22,25-octakis(thioaryl)phthalocyanines described above to examine their electron transfer abilities and electrochemical mechanisms. The compounds 1,4,8,11,15,18,22,25-octakis(thioaryl)phthalocyanines are anticipated to be appropriate materials for use in the next generation of photovoltaic cells.

Synthesis of arylsulfanyl-subphthalocyanines and their ring expansion reaction

For dye-sensitized solar cells, phthalocyanines require strong absorption of far-red light between 700 and 850 nm because of their high electron transfer efficiency. Nevertheless phthalocyanines lack of affinity to basal plats, they inhibit utilization as dye-sensitized solar cell photosensitizer. Then, subphthalocyanines are used as precursors to prepare asymmetric 3:1 type phthalocyanines using a ring-enlargement technique to give affinity to basal plates. As subphthalocyanines having arylsulfanyl substituents used as a precursor, asymmetric phthalocyanines are expected to have good affinity to basal plates. Spectroscopic properties and electron transfer abilities to synthesize non-peripheral arylsulfanyl-subphthalocyanines were estimated. In addition to prepare as trial, asymmetric 3:1 type phthalocyanine, hexakis[(4-methylphenyl)thio]phthalocyanine, was synthesized from corresponding subphthalocyanine.