Synthesis and Characterization of a RuPt-based Photo-Hydrogen-Evolving Molecular Device Tethered to a Single Viologen Acceptor
Synthesis and Characterization of a RuPt-based Photo-Hydrogen-Evolving Molecular Device Tethered to a Single Viologen Acceptor
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束缚于单一紫罗碱受体的 RuPt 光析氢分子器件的合成和表征
DOI：
10.1002/ejic.201601346
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发表时间：
2017
影响因子：
2.3
通讯作者：
and K. Sakai
中科院分区：
文献类型：
--
作者：
M. Miyaji;K. Kitamoto;H. Ozawa;and K. Sakai
合成了一个以甲基紫精（MV 2+）为配体的双核RuIIPtII配合物{RuPt-MV 2 +; [RuII（bpy）2{phen-bpy（MV 2+）} PtIICl 2]4+，bpy = 2，2 ′-联吡啶，phen = 5-氨基-1，10-邻菲咯啉}，研究了单个MV 2+侧链受体对其光放氢活性的影响.在存在EDTA作为牺牲电子供体的情况下，在RuPt-MV 2+的光照射下，RuPt-MV 2+的单电子还原物质（即，[RuII（bpy）2{phen-bpy（MV+·）} PtIICl 2]3+}是通过分子内电子转移（IET）从[RuII（bpy）2（phen）]2+单元的3 MLCT激发态到MV 2+单元，随后通过EDTA还原[RuIII（bpy）2（phen）]3+单元而产生的主要光产物。尽管RuPt-MV 2+在EDTA存在下显示出PHE活性，但估计的转换数（0.4）小于没有MV 2+系链的母体RuIIPtII系统。从[RuII（bpy）2（phen）]2+单元的3 MLCT激发态到PtIICl 2（bpy）单元的IET的相对小的驱动力（0.08 eV）导致H2的形成，已被判断为本系统观察到的异常低的PHE活性的主要原因。
A dinuclear RuIIPtIIcomplex tethered to a methyl viologen (MV2+) unit {RuPt‐MV2+; [RuII(bpy)2{phen‐bpy(MV2+)}PtIICl2]4+, bpy = 2,2′‐bipyridine, phen = 5‐amino‐1,10‐phenanthroline} has been synthesized to investigate the effect of tethering a single pendant MV2+acceptor on its photo‐hydrogen‐evolving (PHE) activity. Upon photoirradiation of RuPt‐MV2+in the presence of EDTA as a sacrificial electron donor, the one‐electron‐reduced species of RuPt‐MV2+{i.e., [RuII(bpy)2{phen‐bpy(MV+·)}PtIICl2]3+} is generated as a major photoproduct by intramolecular electron transfer (IET) from the3MLCT excited state of the [RuII(bpy)2(phen)]2+unit to the MV2+unit, followed by subsequent reduction of the [RuIII(bpy)2(phen)]3+unit by EDTA. Although RuPt‐MV2+shows PHE activity in the presence of EDTA, the estimated turnover number (0.4) is smaller than that for the parent RuIIPtIIsystem, which has no MV2+tether. The relatively small driving force (0.08 eV) for the IET from the3MLCT excited state of the [RuII(bpy)2(phen)]2+unit to the PtIICl2(bpy) unit, which leads to the H2formation, has been judged to be the major cause of the exceptionally low PHE activity observed for the present system.