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首页> 外文期刊>Chemistry: A European journal >Catalytic Photooxidation of 4-Methoxybenzyl Alcohol with a Flavin-Zinc(II)-Cyclen Complex
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Catalytic Photooxidation of 4-Methoxybenzyl Alcohol with a Flavin-Zinc(II)-Cyclen Complex

机译：黄素锌（II）-环配合物催化4-甲氧基苄醇的光氧化

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摘要

Flavin-zinc(II)-cyclen 10 contains a covalently linked substrate binding site(zinc(II)-cyclen)and a chromophore unit(flavin).Upon irradiation,compound 10 effectively oxidizes 4-methoxybenzyl alcohol(11-OCH_3)to the corresponding benzalde-hyde both in water and in acetonitrile.In the presence of air,the reduced flavin 10-H_2 is reoxidized,and so catalytic amounts of 10 are sufficient for alcohol conversion.The mechanism of oxidation is based on photoinduced electron transfer from the coordinated benzyl alcohol to the flavin chromophore.This intramolecular process provides a much higher photooxidation efficiency,with quantum yields 30 times those of the comparable intermolecular process with a flavin chromophore without a binding site.For the reaction in buffered aqueous solution a quantum yield of PHI = 0.4 is observed.The turnover number in acetonitrile is increased(up to 20)by high benzyl alcohol concentrations.The results show that the covalent combination of a chromophore and a suitable binding site may lead to photomediators more efficient than classical sensitizer molecules.
机译：Flavin-zinc（II）-cycln 10包含一个共价连接的底物结合位点（zinc（II）-cycln）和一个生色团单元（flavin）。在辐照下，化合物10有效地将4-甲氧基苄醇（11-OCH_3）氧化为在空气中，还原的黄素10-H_2被再氧化，因此催化量10足以进行醇转化。氧化的机理是基于光催化电子从分子内过程提供了更高的光氧化效率，其量子产率是无键合黄素生色团的分子间过程的30倍。对于在缓冲水溶液中的反应，PHI的量子产率观察到= 0.4，高苯甲醇浓度使乙腈的周转数增加（最多20），结果表明发色团和西装的共价组合能够结合的位点可能导致光介体比传统的敏化剂分子更有效。

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