PHOTOCHEMISTRY OF 2,5-DIMETHYL-1,3,5-HEXATRIENES IN ARGON MATRICES - FORMATION OF ISOMERS AND ROTAMERS

Citation
Am. Brouwer et Hjc. Jacobs, PHOTOCHEMISTRY OF 2,5-DIMETHYL-1,3,5-HEXATRIENES IN ARGON MATRICES - FORMATION OF ISOMERS AND ROTAMERS, Recueil des travaux chimiques des Pays-Bas, 114(11-12), 1995, pp. 449
Citations number
56
Categorie Soggetti
Chemistry
ISSN journal
01650513
Volume
114
Issue
11-12
Year of publication
1995
Database
ISI
SICI code
0165-0513(1995)114:11-12<449:PO2IAM>2.0.ZU;2-0
Abstract
Irradiation of argon matrix-isolated E-2,5-dimethyl-1,3,5-hexatriene r esults in the formation of thermodynamically less stable rotamers. In contrast, the corresponding Z-triene readily undergoes light-induced d ouble bond isomerization to produce the E isomer. The cZc rotamer of Z -2,5-dimethylhexatriene is obtained by irradiation of 1,4-dimethyl-1,3 -cyclohexadiene. Characteristic features in the UV and IR absorption s pectra of the various rotational and geometric isomers are discussed. Recent theoretical work has indicated that single and double bond isom erizations are both possible starting from the A excited state surface of E and Z-hexatriene. Experimentally, we have found clear preference s for either of the two, depending on the initial geometry.