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科学通报  2013 

光系统Ⅱ水氧化中心Mn4Ca簇中μ4-O5原子的指认

, PP. 2717-2720

Keywords: 光系统Ⅱ,Mn4Ca簇,水氧化,锰配合物,DFT理论计算

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Abstract:

光系统Ⅱ水氧化中心Mn4Ca簇的结构最近取得了重要进展,但其μ4-O5原子由于受周围金属离子的影响以及X射线的破坏作用,对其指认尚缺乏必要的实验和理论依据.本文合成出一个与Mn4Ca簇的电性和配位环境类似的Mn配合物,其中含有2个μ4-O原子,它们与金属离子之间的距离在1.89~2.10?范围内,比光系统Ⅱ晶体结构中Mn4Ca簇的μ4-O5原子与金属锰离子间的距离(2.40~2.61?)短~0.5?.此外,对Mn4Ca簇的DFT理论研究显示,无论是μ4-O还是μ4-OH,O原子均会偏移4个金属离子的中心位置,其与4个金属离子的距离差异达0.7~1.0?,这些均与光系统Ⅱ的晶体结构明显不符.这些结果显示光系统Ⅱ晶体结构中Mn4Ca簇的μ4-原子不可能是μ4-O,μ4-OH或μ4-OH2,我们对它的指认提出了质疑.

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