Department of Chemistry, 136 Fleming Building, University of Houston, Houston, Texas 77204-5003, USA.
J Am Chem Soc. 2012 Jul 4;134(26):10721-4. doi: 10.1021/ja300797g. Epub 2012 Jun 20.
Two mononuclear Ru(II) complexes, [Ru(ttbt)(pynap)(I)]I and [Ru(tpy)(Mepy)(2)(I)]I (tpy = 2,2';6,2"-terpyridine; ttbt = 4,4',4"-tri-tert-butyltpy; pynap = 2-(pyrid-2'-yl)-1,8-naphthyridine; and Mepy = 4-methylpyridine), are effective catalysts for the oxidation of water. This oxidation can be driven by a blue (λ(max) = 472 nm) LED light source using [Ru(bpy)(3)]Cl(2) (bpy = 2,2'-bipyridine) as the photosensitizer. Sodium persulfate acts as a sacrificial electron acceptor to oxidize the photosensitizer that in turn drives the catalysis. The presence of all four components, light, photosensitizer, sodium persulfate, and catalyst, are required for water oxidation. A dyad assembly has been prepared using a pyrazine-based linker to join a photosensitizer and catalyst moiety. Irradiation of this intramolecular system with blue light produces oxygen with a higher turnover number than the analogous intermolecular component system under the same conditions.
两个单核 Ru(II) 配合物，[Ru(ttbt)(pynap)(I)]I 和 [Ru(tpy)(Mepy)(2)(I)]I（tpy = 2,2';6,2"-三联吡啶；ttbt = 4,4',4"-三-叔丁基-2,2':6',2"-三联吡啶；pynap = 2-(吡啶-2'-基)-1,8-萘啶；和 Mepy = 4-甲基吡啶），是水氧化的有效催化剂。这种氧化可以使用 [Ru(bpy)(3)]Cl(2)（bpy = 2,2'-联吡啶）作为光敏剂，由蓝色（λ(max) = 472nm）LED 光源驱动。过硫酸钠作为牺牲电子受体，将光敏剂氧化，从而推动催化反应。水氧化需要四种成分，即光、光敏剂、过硫酸钠和催化剂。已经制备了一种使用基于吡嗪的连接体将光敏剂和催化剂部分连接的二聚体组装体。在相同条件下，用蓝光照射这个分子内体系会产生氧气，其周转率比类似的分子间体系更高。
