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设计、合成了一个新的光合作用给体部分的模型化合物:[Mn2(III,III)L(μ-OAc)2].PF6(化合物1),其中L为2,6-二{[(2-羟基-5-叔丁基苄基)(吡啶-2-亚甲基)-氨基]-亚甲基}-4-甲基苯酚.与以往的模型体系[Mn2(II,II)(bpmp)(μ-OAc)2].ClO4(化合物8)相比,新模型增加了2个酚配体及2个叔丁基.此化合物中2个以伪八面体形状配位的Mn离子通过1个酚基和2个二齿羧基相连.这些基团的引入提高了中心金属Mn的价态,并增加了配体的电子云密度,从而降低了Mn的氧化还原电位.该模型进一步缩小了人工模型体系与天然光合作用释氧中心(OEC)四核锰簇的差异.通过IR、ESI-MS、NMR(gCOSY、gHMBC、gHSQC)及电化学对新配体及络合物进行了表征和测试.
A new model compound for the photosynthetic donor moiety was designed and synthesized: [Mn2 (III, III) L (μ-OAc) 2] .PF6 (Pyridin-2-ylmethylene) -amino] -methylene} -4-methylphenol was synthesized in the same manner as the model system [Mn2 (II, II) (μ-OAc) 2] .ClO4 (Compound 8), two new phenolic ligands and two t-butyl groups were added in the new model.In this compound, two pseudo-octahedrally coordinated Mn ions passed through one Phenol group and two bidentate carboxyl groups.The introduction of these groups increased the valence of the central metal Mn and increased the electron cloud density of the ligand and thus reduced the redox potential of Mn.The model further narrowed the artificial model (OEC) system and the tetranuclear manganese clusters of natural photosynthesis oxygenation center (OEC). The new ligands and complexes were characterized and tested by IR, ESI-MS, NMR (gCOSY, gHMBC, gHSQC)