Radical species derived from phenalenone: characterization and role of upper excited states

被引：18

作者：

Flors, C ^{[1
]}

Nonell, S ^{[1
]}

机构：

[1] Univ Ramon Llull, Grp Engn Mol, Inst Quim Sarria, Barcelona 08017, Spain

来源：

JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY | 2004年 / 163卷 / 1-2期

关键词：

aromatic ketone; hydrogen abstraction; ketyl radical; phenalenone; photoinduced electron transfer; radical anion;

D O I：

10.1016/j.jphotochem.2004.01.001

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：

The reactivity of triplet phenalenone (PN) towards typical H- and electron-donors is characterized by means of nanosecond laser flash-photolysis. H-abstraction from tributylstannane occurs with a rate constant of ca. 5 x 10(5) M-1 s(-1). From the activation energy for this reaction, an upper limit for the T-2-T-1 energy gap is calculated as 9 +/- 1 kJ mol(-1) in nonpolar solvents, consistent with the solvent-insensitive high Phi(T) value in phenalenone. Triplet phenalenone also reacts via photoinduced electron transfer with 1,4-diazabicyclo[2.2.2] octane (DABCO) with rate constant close to the diffusional control limit. The spectrum of the solvated free radical anion of phenalenone has a maximum at 440 nm in acetonitrile. (C) 2004 Elsevier B.V. All rights reserved.

引用

页码：9 / 12

页数：4

共 31 条

[1] Type II guanine oxidation photoinduced by the antibacterial fluoroquinolone rufloxacin in isolated DNA and in 2′-deoxyguanosine [J].