Synthesis, crystal and electronic structure, physical properties and 121Sb and 151Eu Mössbauer spectroscopy of the Eu14AlPn11 series (Pn = As, Sb),Inorganic Chemistry Frontiers

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Synthesis, crystal and electronic structure, physical properties and 121Sb and 151Eu Mössbauer spectroscopy of the Eu14AlPn11 series (Pn = As, Sb)
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2018-11-16 00:00:00 , DOI: 10.1039/c8qi01099d
Mathis Radzieowski _{1,

2,

3,

4} , Theresa Block _{1,

2,

3,

4} , Steffen Klenner _{1,

2,

3,

4} , Yuemei Zhang _{5,

6,

7} , Boniface P. T. Fokwa _{5,

6,

7} , Oliver Janka _{1,

2,

3,

4}

Affiliation

The pnictides Eu₁₄AlAs₁₁ and Eu₁₄AlSb₁₁ were synthesized from the elements in sealed niobium ampoules. They crystallize in the tetragonal crystal system (Eu₁₄AlAs₁₁: a = 1627.6(2), c = 2180.0(4) pm; Eu₁₄AlSb₁₁: a = 1725.6(2), c = 2289.7(7) pm) with space group I4₁/acd, isostructural to Ca₁₄AlSb₁₁ and can be described as Zintl phases. The Al atoms are surrounded by four pnictogen atoms, forming [AlPn₄]⁹⁻ tetrahedra. Additionally isolated Pn³⁻ anions and linear Pn₃⁷⁻ trimers can be found in the crystal structure. The compounds can be described according to (Eu²⁺)₁₄(AlPn⁹⁻)(Pn³⁻)₄(Pn₃⁷⁻). Eu₁₄AlAs₁₁ and Eu₁₄AlSb₁₁ both exhibit an antiferromagnetic transition at T_N = 10.5(1) K and 12.5(1) K, respectively. For the antimonide, the magnetic transition has been confirmed by additional heat capacity measurements. Resistivity investigations indicate that Eu₁₄AlSb₁₁ is a semiconductor with a band gap of E_g = 0.28(5) eV close to room temperature. According to the Zintl formalism, the Eu atoms are divalent, which has been confirmed by magnetic susceptibility and additional ¹⁵¹Eu Mössbauer spectroscopic studies. The measurements conducted at 6 K, below the magnetic ordering temperature, show a full hyperfine field splitting with complex spectra underlining the recorded magnetic data. Furthermore, ¹²¹Sb Mössbauer spectroscopic studies have been conducted to study the different antimonide entities in the title compounds.

中文翻译：

Eu ₁₄ AlPn ₁₁系列（Pn = As，Sb）的合成，晶体和电子结构，物理性质以及¹²¹ Sb和¹⁵¹ EuMössbauer光谱

由密封的铌安瓿瓶中的元素合成了磷化物Eu ₁₄ AlAs ₁₁和Eu ₁₄ AlSb ₁₁。它们在四方晶体系统中结晶（Eu ₁₄ AlAs ₁₁：a = 1627.6（2），c = 2180.0（4）pm; Eu ₁₄ AlSb ₁₁：a = 1725.6（2），c = 2289.7（7）pm）有空间组我4 ₁ / ACD，同构对于Ca ₁₄的AlSb ₁₁，并且可以被描述为津特耳相。Al原子被四个光子原子包围，形成[AlPn₄ ]^9-四面体。在晶体结构中还可以发现其他隔离的Pn³⁻阴离子和线性Pn₃⁷⁻三聚体。所述化合物可以根据（Eu²⁺）₁₄（AlPn^9-）（Pn^3-）₄（Pn₃^7-）来描述。Eu₁₄ AlAs₁₁和Eu₁₄ AlSb₁₁都在T _N处显示反铁磁跃迁分别为10.5（1）K和12.5（1）K。对于锑化物，已通过其他热容测量确定了磁性跃迁。电阻率研究表明，Eu ₁₄ AlSb ₁₁是一种半导体，其带隙为E _g = 0.28（5）eV，接近室温。根据辛特尔形式论，the原子是二价的，这已通过磁化率和其他¹⁵¹ EuMössbauer光谱研究证实。在低于磁场有序温度的6 K下进行的测量显示出完整的超精细场分裂，其中复杂的频谱突显了所记录的磁性数据。此外，¹²¹进行了SbMössbauer光谱研究，以研究标题化合物中的不同锑化物。

更新日期：2018-11-16

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