Counter-complementarity control of the weak exchange interaction in a bent {Ni(ii)3} complex with a μ-phenoxide-μ-carboxylate double bridge. (3rd October 2019)

• Record Type: Journal Article
• Authors: Fiorini, Guillermo; Carrella, Luca; Rentschler, Eva; Alborés, Pablo
• Is Part Of: New journal of chemistry. Volume 43:Number 41(2019)
• Page Start: 16218
• Page End: 16225
• Publication Date: 2019-10-03
• Subjects: Chemistry -- Periodicals; Chimie -- Périodiques; 540
• DOI: 10.1039/c9nj03574e
• Languages: English
• ISSNs: 1144-0546

Abstract

Abstract : We report a combined computational and experimental study of a weak exchange interaction in a bent {Ni(ii )3 } complex controlled by counter-complementarity. Abstract : 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.