Articles producció científica> Química Física i Inorgànica

Spin-crossover in phenylazopyridine-functionalized Ni-porphyrin: trans-cis isomerization triggered by pi-pi interactions

  • Dades identificatives

    Identificador: imarina:5128337
    Autors:
    Alcover-Fortuny, Gerardde Graaf, CoenCaballol, Rosa
    Resum:
    Reversible, room-temperature light-induced spin-crossover has been reported in a Ni¿porphyrin functionalized with a phenylazopyridine (PAPy) ligand (Venkataramani et al., Science, 2011, 331, 445). Upon light irradiation (500 nm), the azopyridine moiety induces a change in the Ni(II) coordination sphere from square planar (n = 4) to square pyramid (n = 5), leading to a change in the total spin of the molecule from S = 0 to S = 1. The trans¿cis isomerization in the azopyridine ligand has been proposed to trigger the spin-crossover effect. However, the radiation used to induce the HS state is about 135 nm red-shifted with respect to the radiation used for trans¿cis isomerization of the N[double bond, length as m-dash]N double bond in other compounds. To elucidate the light-induced spin-crossover mechanism of this Ni(II) compound, a combined DFT/CASSCF/CASPT2 study has been performed to determine the most stable cis and trans conformers with n = 4 or n = 5, and to characterize the excitation that triggers the SCO process. π¿π interactions between porphyrin and PAPy are shown to play an essential role in the spin crossover.
  • Altres:

    Autor segons l'article: Alcover-Fortuny, Gerard; de Graaf, Coen; Caballol, Rosa;
    Departament: Química Física i Inorgànica
    Autor/s de la URV: Caballol Lorenzo, Rosa / De Graaf, Cornelis
    Paraules clau: Spectra Perturbation Metalloporphyrin Magnetization Iron(ii) Excited-states Complexes Azobenzene Approximation Ano basis-sets
    Resum: Reversible, room-temperature light-induced spin-crossover has been reported in a Ni¿porphyrin functionalized with a phenylazopyridine (PAPy) ligand (Venkataramani et al., Science, 2011, 331, 445). Upon light irradiation (500 nm), the azopyridine moiety induces a change in the Ni(II) coordination sphere from square planar (n = 4) to square pyramid (n = 5), leading to a change in the total spin of the molecule from S = 0 to S = 1. The trans¿cis isomerization in the azopyridine ligand has been proposed to trigger the spin-crossover effect. However, the radiation used to induce the HS state is about 135 nm red-shifted with respect to the radiation used for trans¿cis isomerization of the N[double bond, length as m-dash]N double bond in other compounds. To elucidate the light-induced spin-crossover mechanism of this Ni(II) compound, a combined DFT/CASSCF/CASPT2 study has been performed to determine the most stable cis and trans conformers with n = 4 or n = 5, and to characterize the excitation that triggers the SCO process. π¿π interactions between porphyrin and PAPy are shown to play an essential role in the spin crossover.
    Àrees temàtiques: Química Physics, atomic, molecular & chemical Physics and astronomy (miscellaneous) Physics and astronomy (all) Physical and theoretical chemistry Odontología Medicina ii Medicina i Materiais Matemática / probabilidade e estatística Interdisciplinar Geociências General physics and astronomy General medicine Farmacia Ensino Engenharias iv Engenharias iii Engenharias ii Ciências biológicas ii Ciências biológicas i Ciências ambientais Ciências agrárias i Ciência de alimentos Ciência da computação Chemistry, physical Biotecnología Biodiversidade Astronomia / física
    Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
    Adreça de correu electrònic de l'autor: coen.degraaf@urv.cat
    Identificador de l'autor: 0000-0001-8114-6658
    Data d'alta del registre: 2024-09-07
    Versió de l'article dipositat: info:eu-repo/semantics/acceptedVersion
    Enllaç font original: https://pubs.rsc.org/en/content/articlelanding/2015/CP/C4CP04402A#!divAbstract
    URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referència a l'article segons font original: Physical Chemistry Chemical Physics. 17 (1): 217-225
    Referència de l'ítem segons les normes APA: Alcover-Fortuny, Gerard; de Graaf, Coen; Caballol, Rosa; (2015). Spin-crossover in phenylazopyridine-functionalized Ni-porphyrin: trans-cis isomerization triggered by pi-pi interactions. Physical Chemistry Chemical Physics, 17(1), 217-225. DOI: 10.1039/C4CP04402A
    DOI de l'article: 10.1039/C4CP04402A
    Entitat: Universitat Rovira i Virgili
    Any de publicació de la revista: 2015
    Tipus de publicació: Journal Publications
  • Paraules clau:

    Chemistry, Physical,Physical and Theoretical Chemistry,Physics and Astronomy (Miscellaneous),Physics, Atomic, Molecular & Chemical
    Spectra
    Perturbation
    Metalloporphyrin
    Magnetization
    Iron(ii)
    Excited-states
    Complexes
    Azobenzene
    Approximation
    Ano basis-sets
    Química
    Physics, atomic, molecular & chemical
    Physics and astronomy (miscellaneous)
    Physics and astronomy (all)
    Physical and theoretical chemistry
    Odontología
    Medicina ii
    Medicina i
    Materiais
    Matemática / probabilidade e estatística
    Interdisciplinar
    Geociências
    General physics and astronomy
    General medicine
    Farmacia
    Ensino
    Engenharias iv
    Engenharias iii
    Engenharias ii
    Ciências biológicas ii
    Ciências biológicas i
    Ciências ambientais
    Ciências agrárias i
    Ciência de alimentos
    Ciência da computação
    Chemistry, physical
    Biotecnología
    Biodiversidade
    Astronomia / física
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