Investigations of the effect of the non-manganese metal in heterometallic-oxido cluster models of the oxygen evolving complex of photosystem II: lanthanides as substitutes for calcium.
Investigations of the effect of the non-manganese metal in heterometallic-oxido cluster models of the oxygen evolving complex of photosystem II: lanthanides as substitutes for calcium.
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DOI：
10.1021/ic5015219
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发表时间：
2015-01-05
影响因子：
4.6
通讯作者：
Agapie T
中科院分区：
文献类型：
--
作者：
Lin PH;Takase MK;Agapie T
报道了以1，3，5-三芳基苯为配位基团的配体(L3-)负载的九个新簇合物[LLnMnIV3O4(OAc)3(DMF)n]+(Ln=La3+，Ce3+，Nd3+，Eu3+，Gd3+，Tb3+，Dy3+，Yb3+和Lu3+，n=2或3)的合成和电化学性质。用Ln(OTf)3处理LMn_3CaO_4(OAc)_3(THF)，再用La~(2+)与Ca~(2+)进行金属取代，得到了所有配合物。结构表征证实，簇合物中含有[LnMn3O_4]立方烷基元。用循环伏安法研究了氧化还原非活性中心对Mn3O4磁芯电子性质的影响。观察到簇合物的氧化还原电势与稀土金属离子的离子半径或pKa呈线性相关。LMnIV3GdO4(OAc)3(DMF)2与十甲基二茂铁化学还原生成LGdMnIV2MnIIIO4(OAc)3(DMF)2，这是一种罕见的混价[MMn3O4]立方烷。稀土配位的配体可以被其他给体取代，包括生物底物水。合成了锰和稀土的混合氧化物立方烷簇合物[LnMnIV3O4]，作为光系统II的析氧络合物(OEC)的模型。这些簇合物的氧化还原电位与稀土的Lewis酸度呈线性关系，以离子半径或金属水络合物的pKa表示。[DyMnIV3O4]立方烷中混价的[GdMnIV2MnIIIO4]团簇和水与稀土配位的罕见例子提供了OEC的各种状态的模型。
We report the syntheses and electrochemical properties of nine new clusters ([LLnMnIV3O4(OAc)3(DMF)n]+ (Ln = La3+, Ce3+, Nd3+, Eu3+, Gd3+, Tb3+, Dy3+, Yb3+, and Lu3+, n = 2 or 3)) supported by a ligand (L3–) based on a 1,3,5-triarylbenzene motif appended with alkoxide and pyridine donors. All complexes were obtained by metal substitution of Ca2+ with lanthanides upon treatment of previously reported LMn3CaO4(OAc)3(THF) with Ln(OTf)3. Structural characterization confirmed that the clusters contain the [LnMn3O4] cubane motif. The effect of the redox-inactive centers on the electronic properties of the Mn3O4 cores was investigated by cyclic voltammetry. A linear correlation between the redox potential of the cluster and the ionic radii or pKa of the lanthanide metal ion was observed. Chemical reduction of the LMnIV3GdO4(OAc)3(DMF)2 cluster with decamethylferrocene, resulted in the formation of LGdMnIV2MnIIIO4(OAc)3(DMF)2, a rare example of mixed-valence [MMn3O4] cubane. The lanthanide-coordinated ligands can be substituted with other donors, including water, the biological substrate. Mixed-oxide cubane clusters of manganese and lanthanides, [LnMnIV3O4], were synthesized as models of the oxygen evolving complex (OEC) of photosystem II. The redox potentials of these clusters show linear dependence with the lanthanide Lewis acidity, measured as radius of the ion or the pKa of the metal aquo complex. Rare examples of mixed-valent [GdMnIV2MnIIIO4] cluster and water coordination to the lanthanide in the [DyMnIV3O4] cubane provide models of the various states of the OEC.
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影响因子：
15
作者：
Kanady, Jacob S.;Lin, Po-Heng;Carsch, Kurtis M.;Nielsen, Robert J.;Takase, Michael K.;Goddard, William A., III;Agapie, Theodor
通讯作者：
Agapie, Theodor
影响因子：
15
作者：
Leeladee, Pannee;Baglia, Regina A.;Goldberg, David P.
通讯作者：
Goldberg, David P.
影响因子：
3.3
作者：
KOK, B;FORBUSH, B;MCGLOIN, M
通讯作者：
MCGLOIN, M
DOI：
10.1016/0005-2728(93)90057-m
发表时间：
1993-03-01
期刊：
BIOCHIMICA ET BIOPHYSICA ACTA
影响因子：
--
作者：
BAKOU, A;GHANOTAKIS, DF
通讯作者：
GHANOTAKIS, DF
影响因子：
2.8
作者：
Horwitz, CP;Ciringh, Y;Weintraub, ST
通讯作者：
Weintraub, ST