Red-Light-Driven Photocatalytic Reduction of CO2 using Os(II)鈥揜e(I) Supramolecular Complexes

详细信息    查看全文

• 作者：Yusuke Tamaki ; Kazuhide Koike ; Tatsuki Morimoto ; Yasuomi Yamazaki ; Osamu Ishitani
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：October 21, 2013
• 年：2013
• 卷：52
• 期：20
• 页码：11902-11909
• 全文大小：453K
• 年卷期：v.52,no.20(October 21, 2013)
• ISSN：1520-510X

文摘

The novel supramolecular complexes, which are composed of an [Os(5dmb)₂(BL)]²⁺-type complex (5dmb = 5,5鈥?dimethyl-2,2鈥?bipyridine; BL = 1,2-bis(4鈥?methyl-[2,2鈥?bipyridin]-4-yl)ethane) as a photosensitizer and cis,trans-[Re(BL)(CO)₂{P(p-X-C₆H₄)₃}₂]⁺-type complexes (X = F, Cl) as a catalyst, have been synthesized. They photocatalyzed selective reduction of CO₂ to CO under red-light irradiation (位 > 620 nm). The photocatalytic abilities were affected by the phosphine ligands on the Re unit, and the supramolecule with P(p-Cl-C₆H₄)₃ ligands exhibited better photocatalysis (桅_CO = 0.12, TON_CO = 1138, TOF_CO = 3.3 min^鈥?). The detailed studies clarified the electron balance and material balance; i.e., one molecule of the sacrificial electron donor (1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH)) donated two electrons, one molecule of CO₂ accepted the two electrons, and another CO₂ molecule served as an 鈥淥^{2鈥?/sup>鈥?acceptor to give each molecule of the two-electron oxidized compound of BIH, CO, and HCO₃鈥?/sup>.}