Author, as appears in the article.: Coen de Graaf Gerard Alcover-Fortuny Rosa Caballol
Department: Química Física i Inorgànica
URV's Author/s: Rosa Caballol Gerard Alcover-Fortuny DE GRAAF, CORNELIS
Keywords: spin crossover
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 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.
Research group: Química Quàntica
Thematic Areas: Química Química Chemistry
licence for use: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 1463-9076
Author identifier: 0000-0001-8114-6658 n/a n/a
Record's date: 2015-05-18
Last page: 225
Journal volume: 17
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/
Article's DOI: 10.1039/C4CP04402A
Entity: Universitat Rovira i Virgili
Journal publication year: 2015
First page: 217
Publication Type: Article Artículo Article
Repositori URV