Suppression of zero-field quantum tunneling of magnetization by a fluorido bridge for a "very hard" 3d-4f single-molecule magnet

Tuning Quantum Tunneling in Isomorphic {MII2DyIII2} “Butterfly” System via 3d-4f Magnetic Interaction

“…11−15 Up to now, various high performance SMMs based on Dy III ions have been reported, 16−20 and the record breaking energy barriers have exceeded 1000 K. 20−22 Nevertheless, it must be stressed that the pitfall of Dy III complexes is the significant quantum tunneling of the magnetization (QTM) related with the rhombic anisotropy, which will result in lower energy barriers and seriously reduce the memory effect of the magnetization. 23 Therefore, suppressing the QTM effect is still a current challenge for chemists that needs to be explored. The previous experimental and theoretical studies have confirmed that introducing strong spin−spin exchange coupling between metal ions and defining high-crystal field symmetry around individual lanthanide ions are two main strategies to suppress the QTM effect.…”

“…Single-molecule magnets (SMMs) are discrete molecules that process slow magnetic relaxation and memory effects, standing as attractive candidates for molecular spintronics devices and high-density information storage. − Important groundwork has been laid to the deep understanding of the mechanism of magnetism through designing SMMs with various structures. − SMMs based on lanthanide Dy III ion are well suited to achieving high-temperature magnetic biostability thanks to their remarkable magnetic anisotropy and Kramers doublet ground state of 6 H 15/2 . − Up to now, various high performance SMMs based on Dy III ions have been reported, − and the record breaking energy barriers have exceeded 1000 K. − Nevertheless, it must be stressed that the pitfall of Dy III complexes is the significant quantum tunneling of the magnetization (QTM) related with the rhombic anisotropy, which will result in lower energy barriers and seriously reduce the memory effect of the magnetization . Therefore, suppressing the QTM effect is still a current challenge for chemists that needs to be explored.…”

Manipulating Solvothermal Coordination-Catalyzed In Situ Tandem Reactions to Construct Dysprosium-Based Complexes with Different Shapes and Zero-Field SMM Behaviors

“…So far, solvothermal black-box reactions are among the most widely used methods for the synthesis of lanthanide multinuclear clusters; however, in this process, organic ligands participate only in coordination to form complexes. − The selection of suitable organic ligands with active functional groups is the premise of coordination-driven in situ tandem reactions. ,, The study of lanthanide complexes has been favored by chemists due to their applications in luminescence, magnetism, catalysis, and separation. − Dy­(III) ions possess Ising-type magnetic anisotropy originating from the Kramer double ground state and are preferred components for building single-molecule magnets (SMMs), which have important significance and potential applications in the fields of density data storage, molecular spintronics, and quantum computing. − After years of exploration, many mononuclear Dy-based SMMs with excellent blocking temperatures and energy barriers have emerged. − For example, in 2018, Tong’s group realized the key parameters for regulating the mononuclear dysprosium complexes through the design of ligands and obtained the axial crystal field, and finally achieved the first breakthrough with a T B temperature of 80 K and U eff as high as 2217 K . In 2016, Zheng’s group reported that a Dy-based SMM was obtained by adjusting the coordination environment, with a U eff = 1815 K and a T B of 14 K .…”

Alkali metal-linked triangular building blocks assemble a high-nucleation lanthanoid cluster based on single-molecule magnets

“…In 2022, Zheng et al. introduced a central fluorine bridge in a 3 d ays-4 f SMM, which strongly suppressed its quantum tunneling phenomenon at zero field; this work provides a basis for understanding the quantum tunneling process and designing a high remanence magnetism Ratio’s SMMs offer a new powerful solution ( Ling et al., 2022 ).…”

“…To design SMMs based on mononuclear complexes with superior performance and special magnetic behavior, the ligand field strength and topology of these complexes are controlled despite the metal center coordination configuration ( Woodru et al., 2013 ; Guo et al., 2018a ; Goodwin et al., 2017 ; Ding et al., 2016 ; Jin et al., 2022 ; Ma et al., 2022 ; Huang et al., 2020 ; Zhang et al., 2020 ; Zhu et al., 2021 ; Ling et al., 2022 ; Liu et al., 2018 ; Guo et al., 2018a , 2018a ; Yu et al., 2022 ). However, developing effective strategies to break through the tremendous progress achieved in SMMs based on mononuclear complexes remains difficult ( Zhang et al., 2020 ; Zhu et al., 2021 ; Ling et al., 2022 ; Liu et al., 2018 ; Lu et al, 2022 ). SMMs containing only one lanthanoid metal center may represent the lower size limit of molecular-based magnetic information storage materials ( Guo et al., 2018b ).…”