Swain Abinash, Sharma Tanu, Rajaraman Gopalan
Department of Chemistry, IIT Bombay, Powai, Mumbai - 400076, India.
Chem Commun (Camb). 2023 Mar 14;59(22):3206-3228. doi: 10.1039/d2cc06041h.
Enhancing blocking temperature () is one of the holy grails in Single Molecule Magnets(SMMs), as any future potential application in this class of molecules is directly correlated to this parameter. Among many factors contributing to a reduction of value, Quantum Tunnelling of Magnetisation (QTM), a phenomenon that is a curse or a blessing based on the application sought after, tops the list. Theoretical tools based on density functional and CASSCF/RASSI-SO methods have played a prominent role in estimating various spin Hamiltonian parameters and establishing the mechanism of magnetization relaxation in this class of molecules. Particularly, various strategies to quench QTM effects go hand-in-hand with experiments, and different methods proposed to quell QTM effects are scattered in the literature. In this perspective, we have explored various approaches that are proposed in the literature to quench QTM effects, and these include the role of (i) local symmetry of lanthanides, (ii) super-exchange interaction in {3d-4f} complexes, (iii) direct-exchange interaction in {radical-4f} and metal-metal bonded complexes to suppress the QTM, (iv) utilizing external stimuli such as an electric field or pressure to modulate the QTM and (v) avoiding QTM effects by stabilising toroidal states in 4f and {3d-4f} clusters. We believe the strategies summarized here will help to design new-generation SMMs.
提高阻塞温度( )是单分子磁体(SMMs)领域的圣杯之一,因为这类分子未来的任何潜在应用都与该参数直接相关。在导致 值降低的众多因素中,磁化量子隧穿(QTM)位居榜首,这一现象根据所追求的应用既可能是祸也可能是福。基于密度泛函以及CASSCF/RASSI - SO方法的理论工具在估算这类分子的各种自旋哈密顿量参数和建立磁化弛豫机制方面发挥了重要作用。特别是,各种抑制QTM效应的策略与实验相辅相成,文献中提出的不同抑制QTM效应的方法也较为分散。从这个角度出发,我们探讨了文献中提出的各种抑制QTM效应的方法,这些方法包括:(i)镧系元素的局部对称性的作用;(ii){3d - 4f}配合物中的超交换相互作用;(iii){自由基 - 4f}和金属 - 金属键合配合物中的直接交换相互作用以抑制QTM;(iv)利用外部刺激如电场或压力来调节QTM;(v)通过稳定4f和{3d - 4f}簇中的环形态来避免QTM效应。我们相信这里总结的策略将有助于设计新一代的SMMs。