Artículo
Abstract:
Three novel diarylethenes derived from benzothiophene were synthesized and their photochemical optical properties studied in four solvents (n-hexane, toluene, acetonitrile and methanol). It was determined that these compounds dramatically increase the light absorption in the visible region upon exposure to UV light, showing two absorption maxima at 420nm and 520nm, respectively. The observed change is completely reverted upon exposure to visible light. The three compounds demonstrate negligible fatigue, excellent stability in the four solvents, and absence of photodegradation and thermal back reactions. This paper also describes a complete study of solvent effects on the kinetics of the ring opening and cycloreversion. While, the UV spectra are little sensitive both to the substitution pattern and to the solvent influence, the kinetics of ring opening/cycloreversion reactions exhibit a more interesting behavior that differs from other diarylethenes reported in the literature. The cyclization kinetics shows a complex order, well fitted by an exponential equation, while the cycloreversion presents first-order kinetics. The whole complex reaction scheme can be explained by the unusual presence of two conformers of the open form, a parallel and an antiparallel conformation. Though other alternative mechanism could explain the kinetics, additional evidence is consistent with the conformational equilibrium proposed: i.e. the solvent influence on the kinetics of the nitrosubstituted substrate, and the double signals for the methyl protons and for the methoxy protons (when present) observed in the nuclear magnetic resonance spectra. These observations are relevant in relation to the application of these novel diarylethenes as potential optical materials. Copyright © 2012 John Wiley & Sons, Ltd.
Registro:
| Documento: | Artículo |
| Título: | Ring opening/closure reactions of novel diheteroarylethenes derivatives. Solvent effects |
| Autor: | Vazquez, A.J.; Nudelman, N.S. |
| Filiación: | Depto. Quimica Organica, Facultad de Ciencias Exactas y Naturales, Ciudad Universitaria, 1428 Buenos Aires, Argentina |
| Palabras clave: | Diarylethenes; Kinetics; Solvent effects; UV spectra; Antiparallel conformations; Conformational equilibrium; Diarylethenes; Exponential equations; First order kinetics; Solvent effects; Substitution patterns; UV spectrum; Conformations; Enzyme kinetics; Kinetics; Magnetic resonance spectroscopy; Olefins; Organic solvents; Ultraviolet spectroscopy; Solvents |
| Año: | 2012 |
| Volumen: | 25 |
| Número: | 11 |
| Página de inicio: | 925 |
| Página de fin: | 932 |
| DOI: | http://dx.doi.org/10.1002/poc.2963 |
| Título revista: | Journal of Physical Organic Chemistry |
| Título revista abreviado: | J Phys Org Chem |
| ISSN: | 08943230 |
| CODEN: | JPOCE |
| Registro: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08943230_v25_n11_p925_Vazquez |
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Citas:
---------- APA ----------
Vazquez, A.J. & Nudelman, N.S. (2012) . Ring opening/closure reactions of novel diheteroarylethenes derivatives. Solvent effects. Journal of Physical Organic Chemistry, 25(11), 925-932.http://dx.doi.org/10.1002/poc.2963
---------- CHICAGO ----------
Vazquez, A.J., Nudelman, N.S. "Ring opening/closure reactions of novel diheteroarylethenes derivatives. Solvent effects" . Journal of Physical Organic Chemistry 25, no. 11 (2012) : 925-932.http://dx.doi.org/10.1002/poc.2963
---------- MLA ----------
Vazquez, A.J., Nudelman, N.S. "Ring opening/closure reactions of novel diheteroarylethenes derivatives. Solvent effects" . Journal of Physical Organic Chemistry, vol. 25, no. 11, 2012, pp. 925-932.http://dx.doi.org/10.1002/poc.2963
---------- VANCOUVER ----------
Vazquez, A.J., Nudelman, N.S. Ring opening/closure reactions of novel diheteroarylethenes derivatives. Solvent effects. J Phys Org Chem. 2012;25(11):925-932.http://dx.doi.org/10.1002/poc.2963
