Kowacs Tanja, O'Reilly Laura, Pan Qing, Huijser Annemarie, Lang Philipp, Rau Sven, Browne Wesley R, Pryce Mary T, Vos Johannes G
Institut für Anorganische Chemie I, Universität Ulm , Albert-Einstein-Allee 11, 89081 Ulm, Germany.
SRC for Solar Energy Conversion, School of Chemical Sciences, Dublin City University , Dublin 9, Ireland.
Inorg Chem. 2016 Mar 21;55(6):2685-90. doi: 10.1021/acs.inorgchem.5b01752. Epub 2016 Feb 29.
The photocatalytic generation of hydrogen (H2) from protons by two cyclometalated ruthenium-platinum polypyridyl complexes, Ru(bpy)2(2,5-bpp)PtIS (1) and Ru(dceb)2(2,5-bpp)PtIS (2) [where bpy = 2,2'-bipyridine, 2,5-bpp = 2,2',5',2″-terpyridine, dceb = 4,4'-di(carboxyethyl)bipyridine, and S = solvent], is reported. Turnover numbers (TONs) for H2 generation were increased by nearly an order of magnitude by the introduction of carboxyethyl ester units, i.e., from 80 for 1P to 650 for 2P after 6 h of irradiation, with an early turnover frequency (TOF) increasing from 15 to 200 h(-1). The TON and TOF values for 2P are among the highest reported to date for supramolecular photocatalysts. The increase correlates with stabilization of the excited states localized on the peripheral ligands of the light-harvesting Ru(II) center.
报道了两种环金属化钌 - 铂多吡啶配合物Ru(bpy)2(2,5 - bpp)PtIS（1）和Ru(dceb)2(2,5 - bpp)PtIS（2）[其中bpy = 2,2'-联吡啶，2,5 - bpp = 2,2',5',2″-三联吡啶，dceb = 4,4'-二（羧乙基）联吡啶，S = 溶剂]通过质子光催化产氢（H2）的过程。通过引入羧乙酯单元，产氢的周转数（TONs）增加了近一个数量级，即在光照6小时后，从1P的80增加到2P的650，早期周转频率（TOF）从15 h(-1)增加到了200 h(-1)。2P的TON和TOF值是迄今为止报道的超分子光催化剂中最高的之一。这种增加与位于光捕获Ru(II)中心外围配体上的激发态的稳定化相关。
