PULSED ULTRAVIOLET-LASER PHOTOLYSIS OF SUBSTITUTED PHENYL AZOSULFONATES - WAVELENGTH DEPENDENT EFFECTS

被引：13

作者：

FRANZKE, D ^{[1
]}

VOIT, B ^{[1
]}

NUYKEN, O ^{[1
]}

WOKAUN, A ^{[1
]}

机构：

[1] UNIV BAYREUTH,W-8580 BAYREUTH,GERMANY

来源：

MOLECULAR PHYSICS | 1992年 / 77卷 / 02期

关键词：

D O I：

10.1080/00268979200102511

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：

Aqueous solutions of several substituted phenyl azosulphonates have been irradiated by excimer laser pulses at 308 nm, and by dye laser pulses in the wavelength range 370-390 nm. For the methoxyphenyl azosulphonates, the pathway of photochemical decomposition is found to be strongly wavelength dependent. On a first route, the azosulphonate functional group (-N=N-SO3-) is split off in a one-step reaction, to produce the corresponding methoxyphenol. The second photolysis pathway proceeds via the methoxydiazonium ion as an intermediate, to yield the same final product. The wavelength dependence is sensitive to the substitution geometry on the aromatic ring, i.e., 2- and 4-methoxyphenyl azosulphonates exhibit a complementary behaviour with respect to one- and two-step decomposition. The results are interpreted in terms of semiempirical calculations, in which the changes in phenyl-nitrogen and nitrogen-sulfur bond orders are compared for n --> pi* and pi --> pi* excitations of the parent molecule.

引用

页码：397 / 409

页数：13