Development of highly efficient and highly selective photocatalytic oxidation systems based on ruthenium complexes and porphyrins

2015 Fiscal Year Final Research Report

• Project/Area Number: 24245011
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: University of Tsukuba
• Principal Investigator: Kojima Takahiko 筑波大学, 数理物質系, 教授 (20264012)
• Co-Investigator(Renkei-kenkyūsha): ISHIZUKA Tomoya 筑波大学, 数理物質系, 講師 (20435522) ; KOTANI Hiroaki 筑波大学, 数理物質系, 助教 (10610743) ; FUKUZUMI Shunichi 名城大学, 理工学部, 特任教授 (40144430)
• Project Period (FY): 2012-04-01 – 2016-03-31
• Keywords: 触媒・化学プロセス / 再生可能エネルギー / ルテニウム錯体 / ポルフィリン / 光誘起電子移動

Outline of Final Research Achievements

We prepared and characterized Ru(IV)-oxo complexes to reveal their characteristics and reactivity in oxidation reactions of organic substrates. The reactions were revealed to proceed in a unique entropy-controlled mechanism involving adduct formation between Ru(IV)-oxo complexes and substrates. Based on the reactivity, we established highly efficient and highly selective photocatalytic oxidation systems of organic substrates in acidic water. On the other hand, a unique photocatalytic hydrogen evolution system has been developed using a Ru(II) complex having a π-expanded heteroaromatic ligand that acts as a reactive site. On the other hand, a Sc(III)-bound Pd(II)-porphyrin-flavin dyad was synthesized to achieve formation of a charge-separated state surviving for 0.11 s. In addition, photoinduced electron transfer was achieved from metal complexes to a diprotonated from of a new water-soluble saddle-distorted porphyrin.

Free Research Field

錯体化学