EXCITED-STATE TAUTOMERIZATION OF 7-AZAINDOLE IN WATER

被引:138
作者
CHAPMAN, CF [1 ]
MARONCELLI, M [1 ]
机构
[1] PENN STATE UNIV,DEPT CHEM,152 DAVEY LAB,UNIV PK,PA 16802
关键词
D O I
10.1021/j100200a042
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We have studied the solvent dependence of the steady-state absorption, emission, and time-resolved emission of 7-azaindole (7AI) and two nonreactive analogues, N-methyl-7-azaindole (NMAI) and 7-methyl-7H-pyrrolo[2,3-b]pyridine (7MPP), in an effort to understand the apparently anomalous behavior of 7AI in water. We find that 7AI undergoes the same tautomerization reaction via solvent-catalyzed double proton transfer in water as it does in alcohol solvent. Kinetic modeling shows that the unusual features of the 7AI emission in water arise mainly from quantitative changes in two key rate parameters. In water the rate constant for tautomerization (H2O 1.2 x 10(9) s-1 and D2O 0.35 X 10(9) s-1 at 24-degrees-C) is much slower and simultaneously the nonradiative decay rate of the product is much faster (5 x 10(9) s-1 in both H2O and D2O) than in most alcohols, making observation of the reaction difficult. The reason the reaction rate in water is unusually slow appears to result from differences in the hydrogen bonding structure and dynamics of water compared to monoalcohols.
引用
收藏
页码:8430 / 8441
页数:12
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