Autor según el artículo: Caballol, R. ; Alcover-Fortuny, G. ; Pierloot, K. ; De Graaf, C.

Departamento: Química Física i Inorgànica

Autor/es de la URV: CABALLOL LORENZO, ROSA; Alcover-Fortuny, G. ; Pierloot, K. ; DE GRAAF , CORNELIS

Palabras clave: DFT calculations electronic structure

Resumen: Electronic structure calculations have been performed on four dierent Mn corrole and corrolazine complexes to clarify the role of the imide axial ligand on the relative stability of the dierent spin states and the stabilization of the high valent Mn ion in these complexes. Multicongurational perturbation theory energy calculations on the DFT optimized geometries shows that all complexes have a singlet ground state except the complex with the strongest electron with- drawal axial ligand, which is found to have a triplet ground state. The analysis of the sigma and pi interaction between metal and imide ligand shows that this spin crossover is caused by a subtle interplay of geometrical factors (Mn-N distance and coordination angle) and the electron withdrawal character of the imide. The analysis of the multicongurational wave functions reveals that the formally MnV ion is stabilized by an important electron transfer from both the equatorial cor-role/corrolazine ligand and the axial imide. The macrocycle donates roughly half an electron, being somewhere between the closed-shell trianionic and the dian-ionic radical form. The imide ligand transfers 2.5 electrons to the metal center, resulting in an eective d-electron count close to ve in all complexes.

Grupo de investigación: Química Quàntica

Áreas temáticas: Química Química Chemistry

Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 0020-1669

Identificador del autor: 0000-0003-1946-3497; ; ; 0000-0001-8114-6658

Fecha de alta del registro: 2018-02-28

Página final: 5280

Volumen de revista: 55

Versión del articulo depositado: info:eu-repo/semantics/submittedVersion

Enlace a la fuente original: https://pubs.acs.org/doi/10.1021/acs.inorgchem.6b00194

Programa de financiación: plan; Excelencia; CTQ2014- 51938-P altres; Grupos Consolidados; 2014SGR199 altres; Red de Química Teórica; XRQTC european; COST Ac- tion ECOSTBio; CM1305

DOI del artículo: 10.1021/acs.inorgchem.6b00194

Entidad: Universitat Rovira i Virgili

Año de publicación de la revista: 2016

Página inicial: 5274

Tipo de publicación: Article Artículo Article