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

来源：

JOURNAL OF PHYSICAL CHEMISTRY | 1991年 / 95卷 / 22期

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

页码：8466 / 8473

页数：8

共 66 条

[61]

Turro, 1991, MODERN MOL PHOTOCHEM

[62] POLARIZATION DIFFUSION EFFECTS ON REACTION-RATES IN POLAR-SOLVENTS [J].