Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontatio K1N 6N5, Canada.
Department of Chemistry and Biochemistry, University of California, Los Angeles , Los Angeles, California 90095, United States.
J Am Chem Soc. 2017 Feb 1;139(4):1420-1423. doi: 10.1021/jacs.6b12374. Epub 2017 Jan 17.
Dy single-ion magnets (SIMs) with strong axial donors and weak equatorial ligands are attractive model systems with which to harness the maximum magnetic anisotropy of Dy ions. Utilizing a rigid ferrocene diamide ligand (NN), a Dy SIM, (NN)DyI(THF), 1-Dy (NN = fc(NHSitBuMe), fc = 1,1'-ferrocenediyl), composed of a near linear arrangement of donor atoms, exhibits a large energy barrier to spin reversal (770.8 K) and magnetic blocking (14 K). The effects of the transverse ligands on the magnetic and electronic structure of 1-Dy were investigated through ab initio methods, eliciting significant magnetic axiality, even in the fourth Kramers doublet, thus demonstrating the potential of rigid diamide ligands in the design of new SIMs with defined magnetic axiality.
具有强轴向给体和弱赤道配体的单离子磁体 (SIMs) 是一种极具吸引力的模型系统，可以利用镝离子的最大磁各向异性。利用刚性二茂铁二酰胺配体 (NN)，即单离子磁体 (NN)DyI(THF)，1-Dy（NN = fc(NHSitBuMe)，fc = 1,1'-二茂铁二亚基），由接近线性排列的给体原子组成，表现出较大的自旋反转能垒（770.8 K）和磁阻塞（14 K）。通过从头计算方法研究了横向配体对 1-Dy 磁和电子结构的影响，即使在第四凯末尔简并态中也表现出显著的磁轴向性，从而证明了刚性二酰胺配体在设计具有确定磁轴向性的新型 SIMs 方面的潜力。
