Holm Aaron P, Park Seon-Mi, Condron Cathie L, Olmstead Marilyn M, Kim Hyungrak, Klavins Peter, Grandjean Fernande, Hermann Raphaël P, Long Gary J, Kanatzidis Mercouri G, Kauzlarich Susan M, Kim Sung-Jin
Department of Chemistry, University of California, One Shields Avenue, Davis, California 95616, USA.
Inorg Chem. 2003 Jul 28;42(15):4660-7. doi: 10.1021/ic034054w.
A new transition-metal-containing Zintl compound, Eu(10)Mn(6)Sb(13), was prepared by a high-temperature Sn-flux synthesis. The structure was determined by single-crystal X-ray diffraction. Eu(10)Mn(6)Sb(13) crystallizes in the monoclinic space group C2/m with a = 15.1791(6) A, b = 19.1919(7) A, c = 12.2679(4) A, beta = 108.078(1)*, Z = 4 (R1 = 0.0410, wR2 = 0.0920), and T = 90(2) K. The structure of Eu(10)Mn(6)Sb(13) is composed of double layers of Mn-centered tetrahedra separated by Eu(2+) cations. The double layers are composed of edge- and corner-sharing Mn-centered tetrahedra which form cavities occupied by Eu(2+) cations and Sb(2) dumbbells. Linear Sb(3) trimers bridging two tetrahedra across the cavity are also present. Bulk susceptibility data indicate paramagnetic behavior with a ferromagnetic component present below 60 K. Temperature-dependent electrical resistivity measurements show semiconducting behavior above 60 K (E(a)() = 0.115(2) eV), a large and unusually sharp maximum in the resistivity at approximately 40 K, and metallic behavior below 40 K. (151)Eu Mössbauer spectra confirm that the europium is divalent with an average isomer shift of -11.2(1) mm/s at 100 K; the spectra obtained below 40 K reveal magnetic ordering of six of the seven europium sublattices and, at 4.2 K, complete ordering of the seven europium sublattices.
通过高温锡熔剂合成法制备了一种新型含过渡金属的津特耳化合物Eu(10)Mn(6)Sb(13)。其结构通过单晶X射线衍射确定。Eu(10)Mn(6)Sb(13)结晶于单斜空间群C2/m，a = 15.1791(6) Å，b = 19.1919(7) Å，c = 12.2679(4) Å，β = 108.078(1)°，Z = 4（R1 = 0.0410，wR2 = 0.0920），温度T = 90(2) K。Eu(10)Mn(6)Sb(13)的结构由以Mn为中心的四面体双层组成，双层被Eu(2+)阳离子分隔。双层由边共享和角共享的以Mn为中心的四面体组成，这些四面体形成了被Eu(2+)阳离子和Sb(2)哑铃状离子占据的空穴。还存在跨越空穴连接两个四面体的线性Sb(3)三聚体。体磁化率数据表明其具有顺磁行为，在60 K以下存在铁磁成分。与温度相关的电阻率测量显示，在60 K以上具有半导体行为（激活能E(a) = 0.115(2) eV），在约40 K时电阻率出现一个大且异常尖锐的最大值，在40 K以下具有金属行为。(151)Eu穆斯堡尔谱证实，铕为二价，在100 K时平均同质异能移为-11.2(1) mm/s；在40 K以下获得的谱表明七个铕亚晶格中的六个存在磁有序，在4.2 K时七个铕亚晶格完全有序。
