Liu Cai-Ming, Zhang De-Qing, Zhu Dao-Ben
Beijing National Laboratory for Molecular Sciences, Center for Molecular Science, Key Laboratory of Organic Solids, Institute of Chemistry, CAS Research/Education Center for Excellence in Molecular Science, Chinese Academy of Sciences, No. 2 1st North Street, Zhongguancun, Beijing, 100190, China.
Sci Rep. 2017 Nov 14;7(1):15483. doi: 10.1038/s41598-017-15852-1.
Solvents play important roles in our lives, they are also of interest in molecular materials, especially for molecular magnets. The solvatomagnetic effect is generally used for trigger and/or regulation of magnetic properties in molecule-based systems, however, molecular nanomagnets showing solvatomagnetic effects are very difficult to obtain. Here we report four 3d-4f heterometallic cluster complexes containing ROH lattice solvent molecules, [CuTb(HL)(OAc)(hfac)]∙2ROH {HL = 1,3-Bis[tris(hydroxymethyl)methylamino]propane, hfac = hexafluoroacetylacetonate; R = CH, 1; R = CH, 2; R = CH, 3; R = H, 4}. Single-molecule magnet (SMM) properties of these four complexes were observed to be dependent on the ROH lattice solvent molecule. There is an interesting magneto-structural correlation: the larger the R group, the higher the energy barrier. For the first time, the solvatomagnetic effect is used for the continuous fine adjustment of the energy barrier of 0D molecular nanomagnets. Additionally, [CuDy(HL)(OAc)(hfac)]∙2MeOH (5), an analogue of [CuTb(HL)(OAc)(hfac)]∙2MeOH (1), is also reported for comparison.
溶剂在我们的生活中扮演着重要角色，它们在分子材料领域也备受关注，尤其是对于分子磁体。溶剂磁效应通常用于触发和/或调节基于分子的体系中的磁性，然而，具有溶剂磁效应的分子纳米磁体很难获得。在此，我们报道了四种含有ROH晶格溶剂分子的3d-4f异金属簇配合物，[CuTb(HL)(OAc)(hfac)]∙2ROH {HL = 1,3-双[三(羟甲基)甲基氨基]丙烷，hfac = 六氟乙酰丙酮；R = CH，1；R = CH，2；R = CH，3；R = H，4}。观察到这四种配合物的单分子磁体（SMM）性质取决于ROH晶格溶剂分子。存在一种有趣的磁结构相关性：R基团越大，能垒越高。首次将溶剂磁效应用于对0D分子纳米磁体的能垒进行连续精细调节。此外，还报道了[CuDy(HL)(OAc)(hfac)]∙2MeOH（5），它是[CuTb(HL)(OAc)(hfac)]∙2MeOH（1）的类似物，用于比较。
