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Titolo:
NONVERTICAL TRIPLET EXCITATION TRANSFER TO ARYLALKENE ACCEPTERS - FURTHER EVIDENCE THAT DOUBLE-BOND TORSION IS UNIMPORTANT
Autore:
BRENNAN CM; CALDWELL RA; ELBERT JE; UNETT DJ;
Indirizzi:
UNIV TEXAS,DEPT CHEM RICHARDSON TX 75083 UNIV TEXAS,DEPT CHEM RICHARDSON TX 75083
Titolo Testata:
Journal of the American Chemical Society
fascicolo: 8, volume: 116, anno: 1994,
pagine: 3460 - 3464
SICI:
0002-7863(1994)116:8<3460:NTETTA>2.0.ZU;2-G
Fonte:
ISI
Lingua:
ENG
Soggetto:
ENERGY-TRANSFER; PHOTOACOUSTIC CALORIMETRY; PULSE-RADIOLYSIS; CIS-STILBENE; STATE; DERIVATIVES; RELAXATION; ENERGETICS; LIFETIMES; DESIGN;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Science Citation Index Expanded
Citazioni:
35
Recensione:
Indirizzi per estratti:
Citazione:
C.M. Brennan et al., "NONVERTICAL TRIPLET EXCITATION TRANSFER TO ARYLALKENE ACCEPTERS - FURTHER EVIDENCE THAT DOUBLE-BOND TORSION IS UNIMPORTANT", Journal of the American Chemical Society, 116(8), 1994, pp. 3460-3464

Abstract

Time-resolved kinetic absorption spectrophotometry and photoacoustic calorimetry have been employed in a study of the kinetics and energetics of triplet excitation transfer to a series of arylalkene accepters. Both the cis and trans isomers of beta-methylstyrene are able to achieve significant relaxation in the triplet state. Nonvertical behavior is observed only for the cis isomer, for which single-bond torsions are expected to contribute to the measured relaxation. A comparison of the behavior of tetraphenylallene and its model, 1,1-diphenylethylene, is also revealing. Relaxation through double bond torsion in the allene triplet state leads to an ''allyl-vinyl'' biradical of particularly low energy. Measured energy transfer rate constants for the two molecules display a close correspondence. These results provide further compelling evidence for a recently proposed model for the nonvertical excitation transfer process dominated by single bond torsional modes.

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Documento generato il 30/11/20 alle ore 07:22:41