Dinuclear Rare-Earth β-Diketiminates with Bridging 3,5-Di tert-butyl-catecholates: Synthesis, Structure, and Single-Molecule Magnet Properties

Svetlana V Klementyeva; Michael T Gamer; Michael Schulze; Nithin Suryadevara; Artem S Bogomyakov; Pavel A Abramov; Sergey N Konchenko; Mario Ruben; Wolfgang Wernsdorfer; Eufemio Moreno-Pineda

doi:10.1021/acs.inorgchem.4c03278

Dinuclear Rare-Earth β-Diketiminates with Bridging 3,5-Di tert-butyl-catecholates: Synthesis, Structure, and Single-Molecule Magnet Properties

Inorg Chem. 2024 Dec 21. doi: 10.1021/acs.inorgchem.4c03278. Online ahead of print.

Authors

Affiliations

¹ Institute of Nanotechnology, Karlsruhe Institute of Technology (KIT) Campus North, P.O. Box 3640, Karlsruhe 76021, Germany.
² Institute of Inorganic Chemistry, Karlsruhe Institute of Technology (KIT) Campus South, Engesserstr. 15, Karlsruhe 76131, Germany.
³ Physical Institute, Karlsruhe Institut of Technology (KIT) Campus South, Wolfgang-Gaede-Str. 1, Karlsruhe 76131, Germany.
⁴ International Tomography Center SB RAS, Institutskaya str. 3a, Novosibirsk 630090, Russia.
⁵ Nikolaev Institute of Inorganic Chemistry SB RAS, Prosp. Lavrentieva 3, Novosibirsk 630090, Russia.
⁶ Novosibirsk State University, Pirogova Str. 2, Novosibirsk 630090, Russia.
⁷ Departamento de Química-Física, Escuela de Química, Facultad de Ciencias Naturales, Exactas y Tecnología, Universidad de Panamá, Panama 0824, Panama.
⁸ Facultad de Ciencias Naturales, Exactas y Tecnología, Grupo de Investigación de Materiales, Universidad de Panamá, Panama 0824, Panama.

PMID: 39707994
DOI: 10.1021/acs.inorgchem.4c03278

Abstract

The dinuclear β-diketiminato complex [L¹ClDy(μ-Cl)₃DyL¹(THF)] (1) (L¹ = {2,6-ⁱPr₂C₆H₃-NC(Me)CHC(Me)N-2,6-ⁱPr₂C₆H₃}^-) was obtained by reaction of DyCl₃ with KL¹ in a molar ratio of 1:1 and used for the preparation of the mixed-ligand complex [L¹Dy(μ-3,5-Cat)]₂ (2) by salt metathesis reaction with 3,5-CatK₂ (3,5-Cat -3,5-di-tert-butyl-catecholate). Reactions of 3,5-CatNa₂ with [L²LnCl₂(THF)₂] (Ln³⁺ = Dy, Y) ligated with the less bulky ligand L² = {2,4,6-Me₃C₆H₂-NC(Me)CHC(Me)N-2,4,6-Me₃C₆H₂}^- afforded the mixed-ligand THF-containing complexes [L²Ln(μ-3,5-Cat)(THF)]₂ (Ln³⁺ = Dy (3a), Y (3b)). All new complexes were fully characterized, and the solid-state structures were determined by single-crystal X-ray diffraction. Magnetic measurements revealed single-molecule magnet behavior for the dysprosium complexes. Sub-Kelvin μSQUID studies confirm the SMM character of the systems, while CASSCF calculation along with simulation of the experimental data yields an antiferromagnetic interaction operating between the Dy³⁺ ions.