Illumination with Ultraviolet or Visible Light Induces Chemical Changes in the Water-soluble Manganese Complex, [Mn4O6(bpea)4]Br4

被引：16

作者：

Antal, Taras K. ^{[1
]}

Lo, Wayne ^{[2
]}

Armstrong, William H. ^{[2
]}

Tyystjarvi, Esa ^{[1
]}

机构：

[1] Univ Turku, Dept Biol, SF-20500 Turku, Finland

[2] Boston Coll, Dept Chem, Eugene F Merkert Chem Ctr, Chestnut Hill, MA 02167 USA

来源：

PHOTOCHEMISTRY AND PHOTOBIOLOGY | 2009年 / 85卷 / 03期

基金：

芬兰科学院; 美国国家科学基金会;

关键词：

OXYGEN-EVOLVING COMPLEX; PHOTOSYSTEM-II; CRYSTAL-STRUCTURE; PHOTOINHIBITION; OXIDATION; PHOTODAMAGE; MECHANISM; RELEVANCE; ION;

D O I：

10.1111/j.1751-1097.2008.00502.x

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

We measured the photosensitivity of an artificial tetranuclear oxo-Mn(IV) complex, [Mn4O6(bpea)(4)]Br-4, which has an adamantane-shaped {Mn4O6}(4+) core. Illumination caused changes in the absorption spectrum of the compound consistent with a one-electron reduction in the compound. Bromide appears to be the most probable electron donor in the reaction system. Chemical modification of the cluster appears to destabilize it, predisposing it to reductive degradation. UV light was more efficient than visible light in causing the changes. The data support the suggestion that the natural oxygen-evolving Mn complex is photosensitive and can oxidize components of the oxygen-evolving complex in its excited state causing photoinhibition, and that photostability is an important issue in designing Mn complexes for artificial photosynthesis. Furthermore, light-induced oxidation of bromide by [Mn4O6(bpea)(4)](4+) may suggest that oxidation of chloride is involved in natural water splitting or has been involved during the evolution of the water-splitting enzyme.

引用

页码：663 / 668

页数：6

共 30 条

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