Benndorf Christopher, Eckert Hellmut, Janka Oliver
Institut für Anorganische und Analytische Chemie, Universität Münster, Corrensstrasse 28/30, 48149 Münster, Germany.
Institut für Physikalische Chemie, Universität Münster, Corrensstrasse 28/30, 48149 Münster, Germany and Instituto de Física de São Carlos, Universidade de São Paulo, São Carlos, SP 13566-590, Brazil.
Dalton Trans. 2017 Jan 24;46(4):1083-1092. doi: 10.1039/c6dt04314c.
Twenty new rare-earth metal rich intermetallic aluminium compounds, RETAl (RE = Y, Ho, Tm, Lu; T = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt), were synthesized by arc melting the elements. The compounds crystallize, in analogy to e.g. the respective Cd representatives, with a ternary ordered structure as anti-type to the hexagonal CoAl type, with the space group P6/mmc. The three crystallographically independent rare-earth metal sites occupy the aluminium positions of the aristotype, while the transition metal and aluminium atoms are ordered on the two cobalt sites. Like other rare-earth rich compounds the RETX members also exhibit transition-metal-centred T@RE trigonal prisms as striking structural building units. The prepared compounds have been investigated by susceptibility measurements and Al solid-state MAS-NMR measurements conducted on the Pauli-paramagnetic Y and Lu compounds. Some compounds show a certain amount of disorder as seen from the single crystal structure analysis and from signal broadening in the NMR investigations. By separating Knight shifts from second-order quadrupolar shifts via field dependent measurements, monotonic trends can be discerned regarding the effect of the T atom valence electron concentration and period number, as well as the effect of the closed 4f shell contributed in the Lu compounds. The results confirm that a comparison of Knight shifts within a series of isotypic compounds can reveal important electronic structure information in intermetallic systems.
通过电弧熔炼各元素合成了20种新型富稀土金属的金属间铝化合物RETAl(RE = Y、Ho、Tm、Lu;T = Fe、Co、Ni、Ru、Rh、Pd、Os、Ir、Pt)。这些化合物结晶时,类似于各自的镉代表物,具有三元有序结构,为六方CoAl型的反型结构,空间群为P6/mmc。三个晶体学独立的稀土金属位点占据了原型结构中的铝位置,而过渡金属和铝原子在两个钴位点上有序排列。与其他富稀土化合物一样,RETX成员也呈现出以过渡金属为中心的T@RE三角棱柱作为显著的结构构建单元。通过对泡利顺磁性的Y和Lu化合物进行磁化率测量和Al固态MAS-NMR测量,对制备的化合物进行了研究。从单晶结构分析和NMR研究中的信号展宽可以看出,一些化合物表现出一定程度的无序。通过场依赖测量将奈特位移与二阶四极位移分离,可以看出关于T原子价电子浓度和周期数的影响,以及Lu化合物中封闭4f壳层贡献的影响的单调趋势。结果证实,在一系列同型化合物中比较奈特位移可以揭示金属间体系中重要的电子结构信息。