Photochromism of phenoxynaphthacenequinones: diabatic or adiabatic phenyl group transfer?

被引：14
作者：
Born, Reto
Fischer, Walter
Heger, Dominik
Tokarczyk, Bogdan
Wirz, Jakob
机构：
[1] Univ Basel, Dept Chem, CH-4056 Basel, Switzerland
[2] Ciba Specialty Chem Inc, CH-4002 Basel, Switzerland
来源：
PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES | 2007年 / 6卷 / 05期
关键词：
D O I：
10.1039/b618661k
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 photochromic reactions of 6-phenyloxy-5,12-naphthacenequinone ( 1) and of the 6,11-diphenyloxy derivative 2 were investigated by subpicosecond pump-probe, photoacoustic, and emission spectroscopies, and by nanosecond laser. ash photolysis ( LFP). The transformation of the trans-quinones 1 and 2 to their ana-isomers proceeds via short-lived triplet states of 1 and 2 ( tau ca. 2 ns) and spiro-bridged biradical intermediates ( ca. 6 ns). The long-lived ( mu s) ana-triplets that are observed by LFP of 1 and 2 are formed ( predominantly) by reexcitation of the biradicals and ana-quinones, which appear during the laser pulse. The reverse reaction, ana -> trans, proceeds exclusively from the lowest pi, pi* singlet state of the ana-quinones.
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页码：552 / 559
页数：8
相关论文
共 40 条
[1]   COMPREHENSIVE ABSORPTION, PHOTOPHYSICAL CHEMICAL, AND THEORETICAL-STUDY OF 2-5-RING AROMATIC HYDROCARBON DIONES [J].
BECKER, RS ;
NATARAJAN, LV .
JOURNAL OF PHYSICAL CHEMISTRY, 1993, 97 (02) :344-349
[2]  
BELAITS IL, 1986, ZH FIZ KHIM+, V60, P640
[3]   SYNTHESIS OF NEW PHOTOCHROMIC POLYMERS BASED ON PHENOXYNAPHTHACENEQUINONE [J].
BUCHHOLTZ, F ;
ZELICHENOK, A ;
KRONGAUZ, V .
MACROMOLECULES, 1993, 26 (05) :906-910
[4]   CONJUGATED RADICALS .3. CALCULATIONS OF ELECTRONIC SPECTRA OF ALTERNANT ODD RADICALS OF ALLYL, BENZYL, AND PHENALENYL TYPES [J].
CARSKY, P ;
ZAHRADNI.R .
JOURNAL OF PHYSICAL CHEMISTRY, 1970, 74 (06) :1249-&
[5]   TRIPLET STATES OF SOME COMMON PHOTOSENSITIZNG DYES [J].
CHAMBERS, RW ;
KEARNS, DR .
PHOTOCHEMISTRY AND PHOTOBIOLOGY, 1969, 10 (03) :215-&
[6]   CLASSIFICATION OF PHOTOCHEMICAL REACTIONS [J].
DAUBEN, WG ;
SALEM, L ;
TURRO, NJ .
ACCOUNTS OF CHEMICAL RESEARCH, 1975, 8 (02) :41-54
[7]   Amperometric transduction and amplification of optical signals recorded by a phenoxynaphthacenequinone monolayer electrode: Photochemical and pH-gated electron transfer [J].
Doron, A ;
Portnoy, M ;
LionDagan, M ;
Katz, E ;
Willner, I .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (37) :8937-8944
[8]  
ELTSOV AV, 1993, J PHOTOCH PHOTOBIO A, V70, P103
[9]   SYNTHESIS AND PHOTOCHROMISM IN SOLUTION OF PHENOXYNAPHTHACENEQUINONE DERIVATIVES [J].
FANG, Z ;
WANG, SZ ;
YANG, ZF ;
CHEN, B ;
LI, FT ;
WANG, JQ ;
XU, SX ;
JIANG, ZJ ;
FANG, TR .
JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY, 1995, 88 (01) :23-30
[10]  
Forster T., 1970, Pure Appl. Chem, V24, P443, DOI [10.1351/pac197024030443, DOI 10.1351/PAC197024030443]
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