Sustained water oxidation photocatalysis by a bioinspired manganese cluster
Sustained water oxidation photocatalysis by a bioinspired manganese cluster
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DOI：
10.1002/anie.200801132
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发表时间：
2008-01-01
影响因子：
16.6
通讯作者：
Spiccia, Leone
中科院分区：
文献类型：
--
作者：
Brimblecombe, Robin;Swiegers, Gerhard F.;Spiccia, Leone
创建将水分解为 H2 和 O2 的高效催化剂是致力于生产可再生燃料的化学家面临的最大挑战之一。 [1, 2] 光合生物体内的水氧化中心 (WOC) 是唯一能够利用可见光有效光氧化水的自然系统，因此是催化剂设计的蓝图。来自 X 射线衍射的 WOC 原子结构模型之一涉及一个“立方体”核心，该核心由一个 {CaMn3O4} 单元组成，通过一个或两个桥接氧单元与第四个锰原子相连。 [3]已经制备了该位点的一些非生物四锰络合物模拟物，其中包含不完整或扭曲的立方 {Mn4Ox} 核心 [4-7] 或者是更大的 Mnx-oxo 晶格的一部分。 [4]然而，这些都没有表现出对水氧化的活性。我们之前在“立方烷”络合物[Mn4O4L6]家族中合成了原型分子锰-氧立方体[Mn4O4] n+，其中LÀ是二芳基次膦酸酯配体(p-RC6h4) 2PO2À (R= H，烷基，OMe)。[6, 8] 二苯基次膦酸盐复合物（1，R= H，图 1）由锰 (II) 和高锰酸盐在非水溶剂中以高产率自发组装。 [9] 1 中的 {Mn4O4} 6+ 核心释放 O2 在热力学基础上是可能的，但由于六个二芳基次膦酸酯配体（桥接六个立方体面上的锰原子对）产生的核心刚性而无法发生。 1的组装也是由分子内范德驱动的
The creation of efficient catalysts for splitting water into H2 and O2 is one of the greatest challenges for chemists working on the production of renewable fuel.[1, 2] The water oxidizing center (WOC) within photosynthetic organisms is the only natural system able to efficiently photooxidize water using visible light, and is thus a blueprint for catalyst design. One of the atomic structural models of the WOC derived from X-ray diffraction involves a “cubelike” core comprised of a {CaMn3O4} unit tethered to a fourth manganese atom through one or two bridging oxo units.[3] A few nonbiological tetramanganese complex mimics of this site have been prepared that contain an incomplete or distorted cubic {Mn4Ox} core [4–7] or are part of a larger Mnx–oxo lattice.[4] However, none of these have shown activity towards water oxidation.We have previously synthesized a prototypical molecular manganese–oxo cube [Mn4O4] n+ in a family of “cubane” complexes [Mn4O4L6], where LÀ is a diarylphosphinate ligand (p-RC6h4) 2PO2 À (R= H, alkyl, OMe).[6, 8] The diphenylphosphinate complex (1, R= H, Figure 1) assembles spontaneously from manganese (II) and permanganate salts in high yield in non-aqueous solvents.[9] The release of O2 by the {Mn4O4} 6+ core in 1 was shown to be possible on thermodynamic grounds, but cannot take place because of the rigidity of the core arising from the six diarylphosphinate ligands, which bridge pairs of manganese atoms on the six cube faces. The assembly of 1 is also driven by intramolecular van der