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Synthesis, Structure, and Magnetic Properties of Rare-Earth Bis(diazabutadiene) Diradical Complexes
Haihan Yan1, Botao Wu1, Yin-Shan Meng2
1Beijing National Laboratory for Molecular Sciences and Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China.
Abstract:
New kinds of diradical rare-earth metal complexes supported by diazabutadiene (DAD) ligands, [(DAD)2LnN(TMS)2] (1; Ln = Dy, Lu; TMS = SiMe3), were synthesized and studied. They showed a new [radical-Ln-radical] alignment with distorted square-pyramidal geometry. Structural and density functional theory analysis illustrated the radical anionic nature of the ligands. Magnetic studies revealed antiferromagnetic coupling of the two radicals in 1-Lu. 1-Dy showed typical single-molecule-magnet (SMM) behavior with an effective energy barrier of 231 K, which is much higher than those of similar radical-containing SMMs. Magnetostructural analysis suggests that the anionic [N(TMS)2]- group plays a vital role in the SMM property. This study provides a new platform for further improving the performance of radical-Ln SMMs.
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