Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
1] Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA [2] Max-Planck-Institut für Chemische Physik Fester Stoffe, Dresden 01187, Germany.
Nat Commun. 2015 Mar 6;6:6489. doi: 10.1038/ncomms7489.
The Zintl concept is important in solid-state chemistry to explain how some compounds that combine electropositive and main group elements can be stable at formulas that at their simplest level do not make any sense. The electronegative elements in such compounds form a polyatomic electron-accepting molecule inside the solid, a 'polyanion', that fills its available energy states with electrons from the electropositive elements to obey fundamental electron-counting rules. Here we use this concept to discover a large family of filled skutterudites based on the group 9 transition metals Co, Rh, and Ir, the alkali, alkaline-earth, and rare-earth elements, and Sb4 polyanions. Forty-three new filled skutterudites are reported, with 63 compositional variations--results that can be extended to the synthesis of hundreds of additional new compounds. Many interesting electronic and magnetic properties can be expected in future studies of these new compounds.
Zintl 概念在固态化学中很重要，它可以解释为什么一些由正电性和主族元素组成的化合物在最简单的公式下可以稳定存在，而这些公式在最初看起来并没有任何意义。在这样的化合物中，电负性元素在固体内部形成一个多原子的电子受体分子，即“多阴离子”，它通过从正电性元素中获取电子来填充其可用的能态，以遵守基本的电子计数规则。在这里，我们使用这个概念来发现一大类基于第 9 族过渡金属 Co、Rh 和 Ir、碱金属、碱土金属和稀土元素以及 Sb4 多阴离子的填充型 skutterudites。报道了 43 种新的填充型 skutterudites，有 63 种组成变化——这些结果可以扩展到数百种新化合物的合成。在对这些新化合物的未来研究中，可以预期会出现许多有趣的电子和磁性性质。
