Articles producció científica> Química Física i Inorgànica

Why thermal isomerization of the chromic switch spiropyran-merocyanine is enhance in polar protic solvents. A computational study of the reaction mechanism

  • Dades identificatives

    Identificador: imarina:6300692
    Autors:
    Kovalenko, OlhaReguero, Mar
    Resum:
    Spiropyran (SP) is a chromic material that undergoes isomerization to merocyanine (MC) under irradiation. To extend its applicability as a molecular switch, it would be convenient to be able to induce and control its isomerization also in the dark, what seems to be possible in acidic media. We present here a computational study of the mechanism of isomerization of protonated SP. We have found that protonation induces the stabilization of MC, protonated at O, relative to SP, protonated at N. Given the different site of protonation for both species, the ring-opening reaction must take place together with a proton transfer event. We have shown that the barrier of this process decreases if a protic solvent molecule take part in the reaction. In this way, the rate determining step of the process is the isomerization between different rotamers of protonated MC. The detailed knowledge of the reaction mechanism can help in the design of structural or electronic modifications of SP to improve its switchability.
  • Altres:

    Autor segons l'article: Kovalenko, Olha; Reguero, Mar;
    Departament: Química Física i Inorgànica
    Autor/s de la URV: Reguero de la Poza, Maria del Mar
    Paraules clau: Spiropyran Reaction mechanism Photochromic spiropyrans Molecules Molecular switch Merocyanine Exchange Dynamics Dft Conformations Chromic materials Behavior
    Resum: Spiropyran (SP) is a chromic material that undergoes isomerization to merocyanine (MC) under irradiation. To extend its applicability as a molecular switch, it would be convenient to be able to induce and control its isomerization also in the dark, what seems to be possible in acidic media. We present here a computational study of the mechanism of isomerization of protonated SP. We have found that protonation induces the stabilization of MC, protonated at O, relative to SP, protonated at N. Given the different site of protonation for both species, the ring-opening reaction must take place together with a proton transfer event. We have shown that the barrier of this process decreases if a protic solvent molecule take part in the reaction. In this way, the rate determining step of the process is the isomerization between different rotamers of protonated MC. The detailed knowledge of the reaction mechanism can help in the design of structural or electronic modifications of SP to improve its switchability.
    Àrees temàtiques: Química Physics, multidisciplinary Physics and astronomy (miscellaneous) Mathematical physics Materiais Matemática / probabilidade e estatística Interdisciplinar Geociências General physics and astronomy Ensino Engenharias iv Engenharias iii Engenharias ii Condensed matter physics Ciências biológicas ii Biotecnología Atomic and molecular physics, and optics Astronomia / física
    Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
    Adreça de correu electrònic de l'autor: mar.reguero@urv.cat
    Identificador de l'autor: 0000-0001-9668-8265
    Data d'alta del registre: 2023-02-19
    Versió de l'article dipositat: info:eu-repo/semantics/acceptedVersion
    Enllaç font original: https://iopscience.iop.org/article/10.1088/1402-4896/ab5ff2
    Referència a l'article segons font original: Physica Scripta. 95 (5):
    Referència de l'ítem segons les normes APA: Kovalenko, Olha; Reguero, Mar; (2020). Why thermal isomerization of the chromic switch spiropyran-merocyanine is enhance in polar protic solvents. A computational study of the reaction mechanism. Physica Scripta, 95(5), -. DOI: 10.1088/1402-4896/ab5ff2
    URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
    DOI de l'article: 10.1088/1402-4896/ab5ff2
    Entitat: Universitat Rovira i Virgili
    Any de publicació de la revista: 2020
    Tipus de publicació: Journal Publications
  • Paraules clau:

    Atomic and Molecular Physics, and Optics,Condensed Matter Physics,Mathematical Physics,Physics and Astronomy (Miscellaneous),Physics, Multidisciplinary
    Spiropyran
    Reaction mechanism
    Photochromic spiropyrans
    Molecules
    Molecular switch
    Merocyanine
    Exchange
    Dynamics
    Dft
    Conformations
    Chromic materials
    Behavior
    Química
    Physics, multidisciplinary
    Physics and astronomy (miscellaneous)
    Mathematical physics
    Materiais
    Matemática / probabilidade e estatística
    Interdisciplinar
    Geociências
    General physics and astronomy
    Ensino
    Engenharias iv
    Engenharias iii
    Engenharias ii
    Condensed matter physics
    Ciências biológicas ii
    Biotecnología
    Atomic and molecular physics, and optics
    Astronomia / física
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