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Providing theoretical insight into the role of symmetry in the photoisomerization mechanism of a non-symmetric dithienylethene photoswitch

Dithienylethene (DTE) molecular photoswitches have shown to be excellent candidates in the design of efficient optoelectronic devices, due to their high photoisomerization quantum yield (QY), for which symmetry is suggested to play a crucial role. Here, we present a theoretical study on the photoche...

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Detalles Bibliográficos
Autores principales: Salazar, Edison, Reinink, Suzanne, Faraji, Shirin
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9116444/
https://www.ncbi.nlm.nih.gov/pubmed/35531648
http://dx.doi.org/10.1039/d2cp00550f
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author Salazar, Edison
Reinink, Suzanne
Faraji, Shirin
author_facet Salazar, Edison
Reinink, Suzanne
Faraji, Shirin
author_sort Salazar, Edison
collection PubMed
description Dithienylethene (DTE) molecular photoswitches have shown to be excellent candidates in the design of efficient optoelectronic devices, due to their high photoisomerization quantum yield (QY), for which symmetry is suggested to play a crucial role. Here, we present a theoretical study on the photochemistry of a non-symmetric dithienylethene photoswitch, with a special emphasis on the effect of asymmetric substitution on the photocyclization and photoreversion mechanisms. We used the Spin-Flip Time Dependent Density Functional Theory (SF-TDDFT) method to locate and characterize the main structures (conical intersections and minima) of the ground state and the first two excited states, S(1) and S(2), along the ring-opening/closure reaction coordinate of the photocyclization and photoreversion processes, and to identify the important coordinates governing the radiationless decay pathways. Our results suggest that while the main features that characterize the photoisomerization of symmetric DTEs are also present for the photoisomerization of the non-symmetric DTE, the lower energy barrier on S(1) along the cycloreversion reaction speaks in favor of a more efficient and therefore a higher cycloreversion QY for the non-symmetric DTEs, making them a better candidate for molecular optoelectronic devices than their symmetric counterparts.
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spelling pubmed-91164442022-06-13 Providing theoretical insight into the role of symmetry in the photoisomerization mechanism of a non-symmetric dithienylethene photoswitch Salazar, Edison Reinink, Suzanne Faraji, Shirin Phys Chem Chem Phys Chemistry Dithienylethene (DTE) molecular photoswitches have shown to be excellent candidates in the design of efficient optoelectronic devices, due to their high photoisomerization quantum yield (QY), for which symmetry is suggested to play a crucial role. Here, we present a theoretical study on the photochemistry of a non-symmetric dithienylethene photoswitch, with a special emphasis on the effect of asymmetric substitution on the photocyclization and photoreversion mechanisms. We used the Spin-Flip Time Dependent Density Functional Theory (SF-TDDFT) method to locate and characterize the main structures (conical intersections and minima) of the ground state and the first two excited states, S(1) and S(2), along the ring-opening/closure reaction coordinate of the photocyclization and photoreversion processes, and to identify the important coordinates governing the radiationless decay pathways. Our results suggest that while the main features that characterize the photoisomerization of symmetric DTEs are also present for the photoisomerization of the non-symmetric DTE, the lower energy barrier on S(1) along the cycloreversion reaction speaks in favor of a more efficient and therefore a higher cycloreversion QY for the non-symmetric DTEs, making them a better candidate for molecular optoelectronic devices than their symmetric counterparts. The Royal Society of Chemistry 2022-05-02 /pmc/articles/PMC9116444/ /pubmed/35531648 http://dx.doi.org/10.1039/d2cp00550f Text en This journal is © the Owner Societies https://creativecommons.org/licenses/by/3.0/
spellingShingle Chemistry
Salazar, Edison
Reinink, Suzanne
Faraji, Shirin
Providing theoretical insight into the role of symmetry in the photoisomerization mechanism of a non-symmetric dithienylethene photoswitch
title Providing theoretical insight into the role of symmetry in the photoisomerization mechanism of a non-symmetric dithienylethene photoswitch
title_full Providing theoretical insight into the role of symmetry in the photoisomerization mechanism of a non-symmetric dithienylethene photoswitch
title_fullStr Providing theoretical insight into the role of symmetry in the photoisomerization mechanism of a non-symmetric dithienylethene photoswitch
title_full_unstemmed Providing theoretical insight into the role of symmetry in the photoisomerization mechanism of a non-symmetric dithienylethene photoswitch
title_short Providing theoretical insight into the role of symmetry in the photoisomerization mechanism of a non-symmetric dithienylethene photoswitch
title_sort providing theoretical insight into the role of symmetry in the photoisomerization mechanism of a non-symmetric dithienylethene photoswitch
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9116444/
https://www.ncbi.nlm.nih.gov/pubmed/35531648
http://dx.doi.org/10.1039/d2cp00550f
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