NaGe _3P _3: A new ternary germanium phosphide featuring an unusual [Ge _3P _7] ring

Feng K.; Yin W.; He R.; Lin Z.; Jin S.; Yao J.; Fu P.; Wu Y.

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NaGe _3P _3: A new ternary germanium phosphide featuring an unusual [Ge _3P _7] ring

机译：NaGe _3P _3：一种新的三元磷化磷化物，具有不寻常的[Ge _3P _7]环

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A new ternary germanium phosphide, NaGe _3P _3, was obtained for the first time with the use of NaP as the reactive flux. It crystallizes in the orthorhombic space group Pmc2 _1. The basic structural unit is an unprecedented [Ge _3P _7] ring built from one Ge(P) _4 tetrahedron, one Ge(Ge)(P) _3 tetrahedron and one Ge(Ge)(P) _2 trigonal pyramid with Ge in mixed valences of 4+, 3+ and 1+. The bonding between a tetrahedrally coordinated Ge atom and a trigonal pyramidally coordinated Ge atom (with 4s ~2 lone pair of electrons) is observed for the first time in inorganic compounds. These [Ge _3P _7] rings are connected with each other to form two-dimensional 2∞[Ge _3P _3] ~- layers separated by Na ~+ cations. An optical band gap of 2.06(2) eV was deduced from the diffuse reflectance spectrum. Based on the electronic structure calculation, NaGe _3P _3 is an indirect gap semiconductor with the Ge4s, Ge4p and P3p orbitals strongly hybridizing around the Fermi level.

机译：利用NaP作为反应性通量，首次获得了新的三元锗化磷化物NaGe _3P _3。它在正交空间群Pmc2 _1中结晶。基本结构单元是前所未有的[Ge _3P _7]环，由一个Ge（P）_4四面体，一个Ge（Ge）（P）_3四面体和一个Ge（Ge）（P）_2三角金字塔组成，Ge的化合价为4 +，3 +和1+。首次在无机化合物中观察到四面体配位的Ge原子和三角体配位的Ge原子（具有4s〜2个孤对电子）之间的键合。这些[Ge _3P _7]环彼此连接，形成被Na〜+阳离子隔开的二维2∞[Ge _3P _3]〜-层。从漫反射光谱中推导出了2.06（2）eV的光学带隙。根据电子结构计算，NaGe _3P _3是一种间接间隙半导体，Ge4s，Ge4p和P3p轨道在费米能级附近强烈杂化。

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《Dalton transactions: An international journal of inorganic chemistry》 |2012年第2期|共6页
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Feng K.; Yin W.; He R.; Lin Z.; Jin S.; Yao J.; Fu P.; Wu Y.;
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NaGe _3P _3: A new ternary germanium phosphide featuring an unusual [Ge _3P _7] ring

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