Author, as appears in the article.: Caballol, R. ; Alcover-Fortuny, G. ; Pierloot, K. ; De Graaf, C.

Department: Química Física i Inorgànica

URV's Author/s: CABALLOL LORENZO, ROSA; Alcover-Fortuny, G. ; Pierloot, K. ; DE GRAAF , CORNELIS

Keywords: DFT calculations electronic structure

Abstract: 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.

Research group: Química Quàntica

Thematic Areas: Química Química Chemistry

licence for use: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 0020-1669

Author identifier: 0000-0003-1946-3497; ; ; 0000-0001-8114-6658

Record's date: 2018-02-28

Last page: 5280

Journal volume: 55

Papper version: info:eu-repo/semantics/submittedVersion

Link to the original source: https://pubs.acs.org/doi/10.1021/acs.inorgchem.6b00194

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

Article's DOI: 10.1021/acs.inorgchem.6b00194

Entity: Universitat Rovira i Virgili

Journal publication year: 2016

First page: 5274

Publication Type: Article Artículo Article