The ternary polyphosphide La₇Zn₂P₁₁ was synthesized from the elements by using a salt flux or via a ceramic method in sealed quartz ampoules. The obtained samples were investigated by X-ray powder and single crystal diffraction: own type, P, a = 775.33(13), b = 827.45(13), c = 1502.8(3) pm, α = 82.111(3), β = 77.034(3), γ = 89.996(3)°, wR₂ = 0.1553, 5852 F² values and 183 variables. This peculiar structure is characterized by the simultaneous presence of three distinct anionic phosphide species, namely P³⁻, P₂⁴⁻, and P₃⁵⁻ units. La₇Zn₂P₁₁ is an electron precise Zintl phase: (7La³⁺)²¹⁺(2Zn²⁺)⁴⁺(4P³⁻)¹²⁻(2P₂⁴⁻)⁸⁻(P₃⁵⁻). The P–P single bond distances range from 219.2 to 223.0 pm. The zinc sites show tetrahedral phosphorus coordination by three P³⁻ and one P₂⁴⁻ species. The tetrahedra are condensed to chains via common corners. The P₃⁵⁻ units with P–P–P angles of 113.7° have exclusively lanthanum coordination. ³¹P solid-state NMR was used to probe the phosphorus local environments, connectivities and spatial proximities. The eleven crystallographically distinct phosphorus atoms were assigned with the help of two-dimensional homonuclear dipolar correlation experiments. Even though the application of 2D measurements on such phosphorus-based polyanionic compounds is exceedingly challenging because of the wide dispersion of chemical shifts, the fast irreversible decay of the transverse magnetization, and slow spin–lattice relaxation, a complete assignment is possible using radiofrequency-driven dipolar recoupling (RFDR), J-RESOLVED and total-through-bond correlation with R-sequence (R-TOBSY) techniques.

中文翻译：

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具有 P3−、P24− 和 P35− 单元的三斜 La7Zn2P11：31P 固态 NMR 光谱和单晶 X 射线衍射的综合研究

通过使用盐熔剂或通过陶瓷方法在密封的石英安瓿中由元素合成三元多磷化物La ₇ Zn ₂ P ₁₁ 。所得样品经X射线粉末和单晶衍射分析：本型，P，a = 775.33(13)，b = 827.45(13)，c = 1502.8(3) pm，α = 82.111(3)，β = 77.034(3)，γ = 89.996(3)°，w R ₂ = 0.1553，5852 个F ²值和 183 个变量。这种奇特结构的特点是同时存在三种不同的阴离子磷化物物质，即P ³⁻、P ₂ ⁴⁻和P ₃ ⁵⁻单元。 La ₇ Zn ₂ P ₁₁是电子精密Zintl相：(7La ³⁺ ) ²¹⁺ (2Zn ²⁺ ) ⁴⁺ (4P ³⁻ ) ¹²⁻ (2P ₂ ⁴⁻ ) ⁸⁻ (P ₃ ⁵⁻ )。 P-P 单键距离范围为 219.2 至 223.0 pm。锌位点显示出由三个 P ³⁻和一个 P ₂ ⁴⁻物质组成的四面体磷配位。四面体通过公共角凝聚成链。P-P-P角为113.7°的P ₃ ^{5−单元仅具有镧配位。 31} P固态NMR用于探测磷的局部环境、连通性和空间邻近性。借助二维同核偶极相关实验，确定了十一个晶体学上不同的磷原子。尽管由于化学位移的广泛分散、横向磁化强度的快速不可逆衰减以及缓慢的自旋晶格弛豫，对此类磷基聚阴离子化合物进行二维测量的应用极具挑战性，但使用射频进行完整的分配是可能的。驱动偶极重耦合 (RFDR)、J -RESOLVED 和 R 序列 (R-TOBSY) 技术的全键关联。