TRANS-STILBENE-AMINE EXCIPLEXES - PHOTOCHEMICAL ADDITION OF SECONDARY AND TERTIARY-AMINES TO STILBENE
TRANS-STILBENE-AMINE EXCIPLEXES - PHOTOCHEMICAL ADDITION OF SECONDARY AND TERTIARY-AMINES TO STILBENE
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DOI：
10.1021/ja00466a035
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发表时间：
1977-01-01
影响因子：
15
通讯作者：
HO, TI
中科院分区：
文献类型：
--
作者：
LEWIS, FD;HO, TI
伊朗的荧光。R-芪被几种仲胺和叔胺猝灭。叔胺在非极性溶剂中的猝灭伴随着激基复合物荧光的出现。在极性和非极性溶剂中的二级和叔胺的荧光猝灭的温度依赖性是可逆的激基复合物的形成在所有情况下的指示。只有在极性非质子溶剂中，叔胺的C-H键才能加成到单态二苯乙烯上。从叔胺到二苯乙烯的电子转移显然必须先于质子转移。仲丁胺的NH键与二苯乙烯的加成在所有非质子溶剂中都发生。比较了二苯乙烯与仲胺、叔胺和共轭二烯形成的激基复合物的行为，二苯乙烯和其它二芳基乙烯与富电子的2· 3和贫电子的4烯烃、二烯、5· 6和胺发生了一系列光化学加成反应。7我们最近对Z/YZ/tt-二苯乙烯和碳酸二苯亚乙烯酯与共轭二烯的光化学[T2 S + 25]环加成反应中的激基复合物中间体进行了表征。图6在这些Tr-供体-Ir-受体ex-中的前线轨道相互作用。
The fluorescence of iran. r-stilbene is quenched by several secondary and tertiary amines. Quenching by tertiary amines in nonpolar solvents is accompanied by the appearance of exciplexfluorescence. The temperature dependence of fluo-rescence quenching by secondary and tertiary amines in polar and nonpolar solvents is indicative of reversible exciplex formation in all cases. Addition of the a C--H bond of tertiary amines to singlet stilbene occurs only in polar aprotic solvents. Electron transfer from the tertiary amine to stilbene apparently must precede proton transfer. The addition of the NH bond of secon-dary amines to stilbene occurs in all aprotic solvents. The behavior of exciplexes formed from rranx-stilbene with secondary and tertiary amines and conjugated dienes is compared.Stilbene and other diarylethylenes undergo a number of photochemical addition reactions with electron-rich2· 3 and electron-poor4 alkenes, dienes, 5· 6 and amines. 7We have re-cently characterized the exciplex intermediates in the photo-chemical [T2S+ 25] cycloaddition reactions of Z/YZ/tt-stilbene and diphenylvinylene carbonatewith conjugated dienes. 6 Frontier orbital interactions in these Tr-donor-ir-acceptor ex-