Articles producció científica> Química Física i Inorgànica

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

  • Dades identificatives

    Identificador: PC:1175
    Handle: https://hdl.handle.net/20.500.11797/PC1175
    Autors:
    Coen de GraafGerard Alcover-FortunyRosa Caballol
    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 NQN 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: Coen de Graaf Gerard Alcover-Fortuny Rosa Caballol
    Departament: Química Física i Inorgànica
    Autor/s de la URV: Rosa Caballol Gerard Alcover-Fortuny DE GRAAF, CORNELIS
    Paraules clau: spin crossover
    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 NQN 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.
    Grup de recerca: Química Quàntica
    Àrees temàtiques: Química Química Chemistry
    Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 1463-9076
    Identificador de l'autor: 0000-0001-8114-6658 n/a n/a
    Data d'alta del registre: 2015-05-18
    Pàgina final: 225
    Volum de revista: 17
    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/
    DOI de l'article: 10.1039/C4CP04402A
    Entitat: Universitat Rovira i Virgili
    Any de publicació de la revista: 2015
    Pàgina inicial: 217
    Tipus de publicació: Article Artículo Article

  • Paraules clau:

    Fisicoquímica
    Spin (Física nuclear)
    Química quàntica
    spin crossover
    Química
    Química
    Chemistry
    1463-9076

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