Reversible energy transfer in metalloporphyrin complexes. A mechanism for photocatalysis.
Reversible energy transfer in metalloporphyrin complexes. A mechanism for photocatalysis.
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金属卟啉配合物中的可逆能量转移。
DOI：
10.1021/ja00729a029
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发表时间：
1970
影响因子：
15
通讯作者：
Whitten Dg
中科院分区：
文献类型：
--
作者：
Wildes Pd;Whitten Dg
之前，我们报道了二苯乙烯类烯烃（如 1-(1-萘基)-2-(4-吡啶基)乙烯 (NPE) 和 4-芪唑）异常有效的顺反光异构化，它们作为配体连接到锌和镁硫卟啉 I 上。 1 2例如，照射脱气苯溶液 5 X 10-6 M 的锌硫卟啉 I 和 5 X 10“3 4M 在 m-NPE 中，在 25-30 时仅被金属卟啉的近紫外或可见光带吸收的光引起 NPE 的顺式到反式异构化，< pc_* t= 7。异构化仅在热力学有利的顺式到反式过程中有效；静止状态包含约 96% 反式。闪光实验表明除了卟啉之外没有瞬变三重态；添加 NPE 后卟啉三重态寿命和吸收光谱没有变化，结果与式 1 和 2 描述的光催化作用一致，其中 MP= 金属卟啉，L= c/j-烯烃，并且
Previously we reported the unusually efficient cis-trans photoisomerization of stilbene-like olefins such as l-(l-naphthyl)-2-(4-pyridyl) ethylene (NPE) and 4-stilbazole attached as ligands to zinc and magnesium etioporphyrin I. 1 2For example, irradiation of degassed benzene solutions 5 X 10-6 M in zinc etioporphyrin I and 5 X 10 “3 4M in m-NPE at 25-30 with light absorbed only by the near-ultraviolet or visible bands of the metalloporphyrin caused cis-to-trans isomerization of NPE with< pc_* t= 7. The isomer-ization was efficient only in the thermodynamically favored cis-to-trans process; stationary states con-tained ca. 96% trans. Flash experiments revealed no transients other than the porphyrin triplet; the por-phyrin triplet lifetime and absorption spectrum were unchanged by addition of NPE. Theresults were consistent with a photocatalysis described by eq 1 and 2, where MP= metalloporphyrin, L= c/j-olefin, and