New light-harvesting molecular systems constructed with a Ru(II) complex and a linear-shaped Re(I) oligomer.
New light-harvesting molecular systems constructed with a Ru(II) complex and a linear-shaped Re(I) oligomer.
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DOI：
10.1021/ja104601b
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发表时间：
2010-07
影响因子：
15
通讯作者：
Youhei Yamamoto;Yusuke Tamaki;Tatsuto Yui;K. Koike;O. Ishitani
中科院分区：
文献类型：
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作者：
Youhei Yamamoto;Yusuke Tamaki;Tatsuto Yui;K. Koike;O. Ishitani
以线性Re(I)低聚物作为光子吸收剂和Ru(II)聚吡啶络合物作为能量受体合成了一种新型的光捕获络合物。 Re(I)低聚物和Ru(II)络合物通过双二亚胺配体彼此连接，即1,2-双[4-(4'-甲基-2,2'-联吡啶基)]乙烷(C2dmb)。这些 Ru(II)-Re(I) 多核配合物，[Ru(dmb)(2)(C2dmb)Re(CO)(2){-PP-Re(dmb)(CO)(2)-PP-Re(dmb)(CO)(3)}(2)](PF(6))(7)， [Ru(dmb)(2)(C2dmb)Re(CO)(2){-PP-Re(dmb)(CO)(3)}(2)](PF(6))(5)，和[Ru(dmb)(2)(C2dmb)Re(CO)(3)-PP-Re(dmb)(CO)(2)-PP-Re(dmb)(CO)(3)](PF(6))(5) (dmb = 4,4'-二甲基-2,2'-联吡啶；PP = 双(二苯基膦)乙炔)，可以强烈吸收多种紫外-可见光，并且在室温下溶液中大部分从 Ru(II) 单元的 (3)MLCT 激发态发射，即使 Re 链吸收光。将它们的光物理性质与相应模型配合物的光物理性质进行比较表明，发生了从Re链到Ru(II)单元的高效能量转移，并且确定了每个Re(I)单元的能量转移速率常数。
A novel type of light-harvesting complexes was synthesized with a linear-shaped Re(I) oligomer as a photon absorber and a Ru(II) polypyridyl complex as an energy acceptor. The Re(I) oligomer and the Ru(II) complex are connected to each other with a bisdiimine ligand, that is, 1,2-bis[4-(4'-methyl-2,2'-bipyridinyl)]ethane (C2dmb). These Ru(II)-Re(I) multinuclear complexes, [Ru(dmb)(2)(C2dmb)Re(CO)(2){-PP-Re(dmb)(CO)(2)-PP-Re(dmb)(CO)(3)}(2)](PF(6))(7), [Ru(dmb)(2)(C2dmb)Re(CO)(2){-PP-Re(dmb)(CO)(3)}(2)](PF(6))(5), and [Ru(dmb)(2)(C2dmb)Re(CO)(3)-PP-Re(dmb)(CO)(2)-PP-Re(dmb)(CO)(3)](PF(6))(5) (dmb = 4,4'-dimethyl-2,2'-bipyridine; PP = bis(diphenylphosphino)acetylene), can strongly absorb a wide range of UV-vis light and emit mostly from the (3)MLCT excited state of the Ru(II) unit at room temperature in solution even when the Re chain absorbs the light. Comparison of their photophysical properties with those of the corresponding model complexes shows that a highly efficient energy transfer from the Re chain to the Ru(II) unit occurs, and the energy transfer rate constants from each Re(I) unit were determined.