Chen Zilu, Yu Shui, Wang Rongdong, Li Bo, Yin Bing, Liu Dongcheng, Liang Yuning, Yao Di, Liang Fupei
State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, Guilin 541004, P. R. China.
Dalton Trans. 2019 May 15;48(19):6627-6637. doi: 10.1039/c9dt00364a.
The reactions of dysprosium nitrate with the main ligand of tropolone (HL) in the presence of ancillary ligands of phenanthroline (phen) or 1,3,5-benzenetricarboxylic acid (H3BTC) gave three mononuclear complexes, [Dy(phen)2(L)(NO3)2] (1), [Dy(phen)(L)3]·H2O (2) and [Dy(H3BTC)(H2O)(L)3]2·3H2O (3). They present different sets of mixed ligands. The Dy(iii) ions are ten-coordinated to build a bicapped square anti-prismatic geometry for complex 1 and eight-coordinated in dodecahedral geometries for complexes 2 and 3. Their magnetic properties were investigated in detail. Complexes 1 and 2 are single ion magnets under an external field, and complex 3 is a single ion magnet under zero field. This revealed a tuning effect on the performances of single ion magnets from ancillary ligands. These experimental magnetic behaviours are supported by the results from ab initio calculations, including g-tensors, averaged transition magnetic moments, magnetic easy axes, and crystal field parameters.
硝酸镝与托酚酮主配体（HL）在邻菲罗啉（phen）或1,3,5-苯三甲酸（H₃BTC）辅助配体存在下反应，得到三种单核配合物，即[Dy(phen)₂(L)(NO₃)₂]（1）、[Dy(phen)(L)₃]·H₂O（2）和[Dy(H₃BTC)(H₂O)(L)₃]₂·3H₂O（3）。它们呈现出不同的混合配体组合。Dy(iii)离子在配合物1中为十配位形成双帽方反棱柱几何构型，在配合物2和3中为八配位形成十二面体几何构型。对它们的磁性质进行了详细研究。配合物1和2在外场下为单离子磁体，配合物3在零场下为单离子磁体。这揭示了辅助配体对单离子磁体性能的调控作用。这些实验磁行为得到了从头算计算结果的支持，包括g张量、平均跃迁磁矩、磁易轴和晶体场参数。
