Engineering a high-barrier d-f single-molecule magnet centered with hexagonal bipyramidal Dy(Ⅲ)unit  

作　　者：Wei Deng Chan-Ying Yao Yan-Cong Chen Ying-Qian Zhou Shan-Nan Du Jun-Liang Liu Ming-Liang Tong 

机构地区：[1]Key Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education,School of Chemistry,Institute of Green Chemistry and Molecular Engineering,Guangdong Basic Research Center of Excellence for Functional Molecular Engineering,Sun Yat-sen University,Guangzhou 510006,China

出　　处：《Science China Chemistry》2024年第10期3291-3298,共8页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China(22073115,22131011,21821003);the Fundamental Research Funds for the Central Universities,Sun Yat-sen University(24xkjc003)。

摘　　要：In the pursuit of high-performance single-molecule magnets(SMMs),incorporating intramolecular magnetic coupling emerges as a pivotal strategy.Among these,d-f SMMs have garnered significant attention due to their remarkable versatility,which lies in their ability to tune coordination environments and facilely substitute metal centers.However,achieving performance-centric d-f SMMs through the synergistic interplay between highly anisotropic f ions and d-f magnetic interactions remains a formidable challenge.While mononuclear hexagonal bipyramidal(D_(6h))Dy^(Ⅲ)SMMs have been successfully isolated,the exploration of d-f SMMs featuring D_(6h)-lanthanide metal centers remains uncharted territory.In this study,we employed planar bipodal ligands in conjunction with“staple-like”axial phenoxide ligands to synthesize the first hexagonal bipyramidal d-f SMM.Remarkably,this compound exhibits alternating-current magnetic susceptibilities peaking up to 68 K with an energy barrier surpassing 1,200 K,thus establishing a new benchmark within the heterometallic d-f SMM landscape inclusive of complexes with diamagnetic d metals and paramagnetic f ions.Notably,the ferromagnetic interaction at the d-f sites engenders oscillating relaxation times contingent on the magnetic field—a characteristic distinct from mononuclear SMMs.These findings shed light on a deliberate design approach for d-f SMMs,emphasizing the cooperative utilization of high-barrier lanthanide modules alongside d ions through magnetic interactions.This synergy significantly enhances and diversifies the magnetic dynamics of these intriguing molecular systems.

关 键 词：single-molecule magnets magnetic coupling crystal engineering hexagonal bipyramid energy barrier 

分 类 号：TM27[一般工业技术—材料科学与工程]