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Titolo:
Stirring effects on the spontaneous formation of chirality in the homoassociation of diprotonated meso-tetraphenylsulfonato porphyrins
Autore:
Rubires, R; Farrera, JA; Ribo, JM;
Indirizzi:
Univ Barcelona, Dept Quim Organ, E-08028 Barcelona, Spain Univ Barcelona Barcelona Spain E-08028 m Organ, E-08028 Barcelona, Spain
Titolo Testata:
CHEMISTRY-A EUROPEAN JOURNAL
fascicolo: 2, volume: 7, anno: 2001,
pagine: 436 - 446
SICI:
0947-6539(20010119)7:2<436:SEOTSF>2.0.ZU;2-J
Fonte:
ISI
Lingua:
ENG
Soggetto:
RESONANCE LIGHT-SCATTERING; ABSOLUTE ASYMMETRIC-SYNTHESIS; SYMMETRY-BREAKING; J-AGGREGATE; CRYSTALLIZATION; COMPLEXES; CRYSTALS; DIMERS;
Keywords:
aggregation; asymmetric amplification; chirality; circular dichroism; exciton coupling; porphyrinoids;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
64
Recensione:
Indirizzi per estratti:
Indirizzo: Rubires, R Univ Barcelona, Dept Quim Organ, Marti I Franques 1, E-08028 Barcelona, Spain Univ Barcelona Marti I Franques 1 Barcelona Spain E-08028 pain
Citazione:
R. Rubires et al., "Stirring effects on the spontaneous formation of chirality in the homoassociation of diprotonated meso-tetraphenylsulfonato porphyrins", CHEM-EUR J, 7(2), 2001, pp. 436-446

Abstract

Homoassociates of the achiral title porphyrins in acid solutions show spontaneous symmetry breaking, which can be detected by circular dichroism (CD). The CD spectra are due to differential scattering and differential absorption contributions, the relative significance of which is related to the shape and size of the homoassociate. When an earlier model, designed for the association of these diprotonated por phyrins (J aggregates with the geometry of stepped sheets of intramolecular-stabilised zwitterions), was appliedto an exciton-coupling point-dipole approximation, the folding of the one dimensional homoassociates explained the CD signals detected. An effect of the vortex direction, caused by stirring or rotary evaporation, upon the exciton chirality sign was detected. In the case of H2TPPS3, the number of experiments performed gave a statistical significance to this effect. This vortex effect can be attributed to enhancement of the chirality fluctuations that originate in the diffusion-limited aggregation to high-molecular-weight homoassociates In this sense, the phenomenon could be general for supramolecular systems that are obtained under kinetic control, and its detection would be possible when inherent chiral chromophores were being generated inthe association process.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 20/09/20 alle ore 09:24:38