Department of Chemistry, Virginia Polytechnic Institute and State University, 107 Davidson Hall, Blacksburg, VA 24061-0212, USA.
ChemSusChem. 2011 Feb 18;4(2):252-61. doi: 10.1002/cssc.201000173. Epub 2010 Nov 24.
Coupling a reactive metal to light absorbers affords molecular devices for photoinitiated electron collection and photocatalytic conversion of substrates to fuels. A new Ru(II),Pt(II) tetrametallic supramolecule, {(phen)(2)Ru(dpp)}(2)Ru(dpq)PtCl(2)(6), and the trimetallic precursors, {(phen)(2)Ru(dpp)}(2)RuCl(2)(4) and {(phen)(2)Ru(dpp)}(2)Ru(dpq)(6), have been synthesized, and their redox, spectroscopic, spectroelectrochemical, photophysical and photocatalytic properties studied. They efficiently absorb UV and visible light. The electrochemistry of {(phen)(2)Ru(dpp)}(2)Ru(dpq)PtCl(2)(6) suggests a lowest-lying terminal Ru→dpq charge-separated state that quenches the emission of the parent complex with non-unity population of the emissive (3)MLCT excited state. Photolysis of {(phen)(2)Ru(dpp)}(2)Ru(dpq)PtCl(2) at 470 nm with DMA gives multielectron reduction, storing electrons in a new manner on the central (dpp)(2)Ru(II)(dpq) moiety. Addition of H(2)O to the photolysis system produces 21 μmol of H(2) in 5 h, with 115 turnovers of the tetrametallic photocatalyst.
将活性金属与光吸收剂偶联，为光引发的电子收集和光催化底物转化为燃料提供了分子器件。一种新的 Ru(II)、Pt(II) 四金属超分子，{(phen)(2)Ru(dpp)}(2)Ru(dpq)PtCl(2)(6)，以及三金属前体，{(phen)(2)Ru(dpp)}(2)RuCl(2)(4) 和 {(phen)(2)Ru(dpp)}(2)Ru(dpq)(6)，已经被合成，并研究了它们的氧化还原、光谱、光谱电化学、光物理和光催化性质。它们能够有效地吸收紫外和可见光。{(phen)(2)Ru(dpp)}(2)Ru(dpq)PtCl(2)(6) 的电化学表明，最低的末端 Ru→dpq 电荷分离态猝灭了母体配合物的发射，其发射态的非单重态(3)MLCT 激发态的人口。{(phen)(2)Ru(dpp)}(2)Ru(dpq)PtCl(2) 在 470nm 下用 DMA 光解产生多电子还原，以一种新的方式将电子存储在中心(dpp)(2)Ru(II)(dpq) 部分上。向光解体系中添加 H(2)O 可在 5 小时内产生 21μmol 的 H(2)，四金属光催化剂的周转率为 115 次。
