SOLUTION PHOTOPHYSICS OF 1-AMINOFLUORENONE AND 3-AMINOFLUORENONE - THE ROLE OF INTERMOLECULAR AND INTRAMOLECULAR HYDROGEN-BONDING IN RADIATIONLESS DEACTIVATION

被引:60
作者
MOOG, RS [1 ]
BUROZSKI, NA [1 ]
DESAI, MM [1 ]
GOOD, WR [1 ]
SILVERS, CD [1 ]
THOMPSON, PA [1 ]
SIMON, JD [1 ]
机构
[1] UNIV CALIF SAN DIEGO,DEPT CHEM,LA JOLLA,CA 92093
关键词
D O I
10.1021/j100175a014
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
Solvent effects on excited-state photophysics of 1-aminofluoren-9-one (1-AF) and 3-aminofluoren-9-one (3-AF) are examined. Solvent-dependent Stokes shifts indicate that the lowest energy electronic transition for both species has substantial charge-transfer character. In addition, the influence of solvent on nonradiative rate constants is investigated. Increased radiationless deactivation of 3-AF in protic solvents relative to that in aprotics is observed and is attributed to intermolecular hydrogen bonding. In contrast, an unusual solvent dependence for k(nr) of 1-AF is observed. The nonradiative rate constant decreases with increasing solvent polarity and is lower in protic solvents than in aprotics. A 1:1 hydrogen-bonded complex of 1-AF with 2,2,2-trifluoroethanol (TFE) is observed in heptane solutions, and k(nr) for this complex is approximately a factor of 4 lower than for 1-AF in pure heptane. These results suggest that the intramolecular hydrogen bond in 1-AF provides a more efficient deactivation pathway than an intermolecular hydrogen bond to the solvent.
引用
收藏
页码:8466 / 8473
页数:8
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