Photoprocesses of molecules with 2-nitrobenzyl protecting groups and caged organic acids

被引:41
作者
Bley, Filiz [2 ]
Schaper, Klaus [2 ]
Goerner, Helmut [1 ]
机构
[1] Max Planck Inst Bioanorgan Chem, Mulheim, Germany
[2] Univ Dusseldorf, Inst Organ Chem & Makromol Chem, D-4000 Dusseldorf, Germany
关键词
D O I
10.1111/j.1751-1097.2007.00215.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
The 308 nm photoinduced formation of the nitroso product and the intermediacy of the aci-nitro form(s) were studied for a series of 2-nitrobenzyl alkyl and aryl esters (1a-4e) and bis-(nitrophenyl)methyl acetates (5a-6b) by time-resolved UV-vis spectroscopy. A triplet state appears as major transient, when 2-nitrobenzyl derivatives I are substituted by 4,5-dimethoxy (2) and 4,5-methylenedioxy (3/4) groups. This triplet of charge transfer character is, however, not part of the route via the aci-nitro into the 2-nitroso form. The activation energy and preexponential factor of the longest lifetime component (tau(aci)), i.e. the major part of the aci-nitro decay, were determined. The carboxylic acids as leaving groups have rather small effects on tau(aci). An additional nitrated phenyl ring in alpha-position (5) leads generally to shorter tau(aci) value. Otherwise, the photogeneration of nitroso products is similar. The quantum yield ((Phi(d)) varies only moderately with structure, the yield of the aci-nitro form and Phi(d) are correlated and little affected by solvent properties.
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页码:162 / 171
页数:10
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