6533b829fe1ef96bd1289b2c

RESEARCH PRODUCT

Counter-complementarity control of the weak exchange interaction in a bent {Ni(ii)3 complex with a μ-phenoxide-μ-carboxylate double bridge

Eva RentschlerLuca M. CarrellaPablo AlborésGuillermo Fiorini

subject

Bent molecular geometryExchange interactionAb initioCiencias Químicas02 engineering and technologyGeneral ChemistryComputer Science::Computational Geometry010402 general chemistry021001 nanoscience & nanotechnologyQuímica Inorgánica y Nuclear01 natural sciencesCatalysisSymmetry (physics)0104 chemical sciencesIonCrystallographychemistry.chemical_compoundchemistryMaterials ChemistryAntiferromagnetismCarboxylateSymmetry breaking0210 nano-technologyno correspondeCIENCIAS NATURALES Y EXACTAS

description

We have prepared and structurally characterized a novel {Ni3} bent complex bearing a double μ-phenoxide-μ-carboxylate bridge. Both terminal Ni(ii) sites are symmetry related, offering a simplified exchange interaction scheme. DC magnetic data is consistent with a weak antiferromagnetic interaction between the central and terminal Ni(ii) ions. As expected for a Ni(ii) system, local zero-field splitting is observed, which can be experimentally established. Broken symmetry quantum chemical calculations, as well as ab initio CASSCF-SA-SOC computations that support the magnetic experimental data, were also performed. From the analysis of other reported closely related Ni(ii) systems, a counter-complementarity effect exerted by the carboxylate bridge is proposed, which might explain the weaker exchange interactions compared to those observed in double μ-phenoxide bridged Ni(ii) compounds. Fil: Fiorini, Guillermo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina Fil: Carrella, Luca. Johannes Gutenberg Universitat Mainz; Alemania Fil: Rentschler, Eva. Johannes Gutenberg Universitat Mainz; Alemania Fil: Alborés, Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Química Inorgánica, Analítica y Química Física; Argentina

yearjournalcountryeditionlanguage
2019-10-01
10.1039/c9nj03574ehttps://pubs.rsc.org/en/content/articlelanding/2019/NJ/C9NJ03574E#!divAbstract