Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstrasse 30, D-48149 Münster, Germany.
Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, 70569 Stuttgart, Germany.
Dalton Trans. 2023 Jul 4;52(26):8893-8903. doi: 10.1039/d3dt01511d.
Polycrystalline samples of the magnesium-rich intermetallic compounds RECuMg (RE = Dy, Ho, Er, Tm) were synthesized by reaction of the elements in sealed tantalum ampoules heated in a high-frequency induction furnace. Phase purity of the RECuMg phases was ascertained by powder X-ray diffraction patterns. Well-shaped single crystals of HoCuMg could be grown in a NaCl/KCl salt flux and the crystal structure was refined from single crystal X-ray diffraction data: TbCuMg structure-type, space group , = 1361.4(2), = 2039.3(4), = 384.62(6) pm. The crystal structure of the RECuMg phases can be understood as a complex intergrowth variant of CsCl and AlB related slabs. The remarkable crystal chemical motif concerns the orthorhombically distorted bcc-like magnesium cubes with Mg-Mg distances ranging from 306 to 334 pm. At high temperatures DyCuMg and ErCuMg are Curie-Weiss paramagnets with paramagnetic Curie-Weiss temperatures of -15 K and -2 K for RE = Dy and Er, respectively. The effective magnetic moments, 10.66 for RE = Dy and 9.65 for RE = Er prove stable trivalent ground states for the rare earth cations. Magnetic susceptibility and heat capacity measurements reveal long-range antiferromagnetic ordering at low temperatures (<21 K). Whereas DyCuMg exhibits two subsequent antiferromagnetic transitions at = 21 and 7.9 K which successively remove half of the entropy of a doublet crystal field ground state of Dy, ErCuMg shows a single, possibly broadened, antiferromagnetic transition at 8.6 K. The successive antiferromagnetic transitions are discussed with respect to magnetic frustration in the tetrameric units present in the crystal structure.
富镁稀土铜镁金属间化合物 RECuMg(RE = Dy、Ho、Er、Tm)的多晶样品通过在高频感应炉中密封钽管中元素的反应合成。通过粉末 X 射线衍射图谱确定 RECuMg 相的物相纯度。可以在 NaCl/KCl 盐通量中生长 HoCuMg 的单晶,并从单晶 X 射线衍射数据中精修晶体结构:TbCuMg 结构类型,空间群 , = 1361.4(2), = 2039.3(4), = 384.62(6) pm。RECuMg 相的晶体结构可以理解为 CsCl 和 AlB 相关片层的复杂交织变体。显著的晶体化学特征涉及正交畸变的类似 bcc 的镁立方,Mg-Mg 距离范围为 306 至 334 pm。在高温下,DyCuMg 和 ErCuMg 是居里-外斯顺磁体,RE = Dy 和 Er 的顺磁居里-外斯温度分别为-15 K 和-2 K。有效磁矩为 10.66 (RE = Dy)和 9.65 (RE = Er),证明稀土阳离子的稳定三价基态。磁化率和热容测量表明在低温下(<21 K)存在长程反铁磁有序。虽然 DyCuMg 在 = 21 和 7.9 K 处表现出两个连续的反铁磁转变,这些转变相继消除了 Dy 双峰晶场基态的一半熵,但 ErCuMg 在 8.6 K 处表现出单个、可能变宽的反铁磁转变。连续的反铁磁转变与晶体结构中存在的四聚体单元中的磁阻挫有关。