Department of Inorganic Chemistry, Faculty of Science , Palacký University Olomouc , 17. listopadu 12 , 771 46 Olomouc , Czech Republic.
Inorg Chem. 2019 Oct 21;58(20):14046-14057. doi: 10.1021/acs.inorgchem.9b02039. Epub 2019 Oct 9.
Computational studies of sandwich dysprosium double-decker complexes [Dy(L)] as candidates for single-ion magnets with several inorganic aromatic ring systems (P, N, BNH, BPH, BSH) have been performed. The molecular structures were optimized with the TPSSh functional, and the ground state properties were investigated with the complete active space SCF method (CASSCF) complemented by the dynamic correlation dressed correction (DCD-CAS(2)) or NEVPT2. Besides the evaluation of the magnetic moment blocking barrier, the impact of the molecular vibration on the relaxation of magnetization was also inspected. We were able to make predictions about the performance of those molecules as single-molecule magnets, where estimated effective energy barrier, , values are as high as 1475 K in the case of [Dy(N)], which is the most anisotropic complex from our choice of studied compounds, making them a potentially very effective carbon-free alternative to organometallic double-decker dysprosocenium high-temperature single-molecule magnets.
已对夹心型双镝双层配合物[Dy(L)]作为具有多个无机芳香环体系(P、N、BNH、BPH、BSH)的单离子磁体候选物进行了计算研究。采用 TPSSh 函数优化了分子结构，并采用完全活性空间 SCF 方法(CASSCF)辅以动态相关修饰校正(DCD-CAS(2))或 NEVPT2 研究了基态性质。除了评估磁矩阻断势垒外，还检查了分子振动对磁化弛豫的影响。我们能够对这些分子作为单分子磁体的性能进行预测，其中估计的有效能量势垒，在我们选择的研究化合物中，[Dy(N)]的值高达 1475 K，这使其成为最各向异性的配合物，使其成为一种潜在的非常有效的无碳有机金属双镝过氧高温单分子磁体替代品。
