Author, as appears in the article.: Alcover-Fortuny, Gerard; de Graaf, Coen; Caballol, Rosa;
Department: Química Física i Inorgànica
URV's Author/s: Caballol Lorenzo, Rosa / De Graaf, Cornelis
Keywords: Spectra Perturbation Metalloporphyrin Magnetization Iron(ii) Excited-states Complexes Azobenzene Approximation Ano basis-sets
Abstract: 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.
Thematic Areas: 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
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: coen.degraaf@urv.cat
Author identifier: 0000-0001-8114-6658
Record's date: 2024-09-07
Papper version: info:eu-repo/semantics/acceptedVersion
Link to the original source: https://pubs.rsc.org/en/content/articlelanding/2015/CP/C4CP04402A#!divAbstract
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Physical Chemistry Chemical Physics. 17 (1): 217-225
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
Article's DOI: 10.1039/C4CP04402A
Entity: Universitat Rovira i Virgili
Journal publication year: 2015
Publication Type: Journal Publications
Repositori URV