The Phosphidosilicates SrSi₇P₁₀ and BaSi₇P₁₀

Abstract

The new phosphidosilicates SrSi7P10 and BaSi7P10 were synthesized by solid‐state reactions, and their crystal structures determined by single‐crystal X‐ray diffraction [P1, Z = 1, SrSi7P10: a = 6.1521(1) Å, b = 8.0420(2) Å, c = 8.1374(2) Å, α = 106.854(1)°, β = 99.020(1)°, γ = 105.190(1)°; BaSi7P10: a = 6.1537(1) Å, b = 8.0423(2) Å, c = 8.1401(2) Å, α = 106.863(1)°, β = 99.050(1)°, γ = 105.188(1)°]. The compounds crystallize in a new triclinic structure type with vertex sharing SiP4 tetrahedra, which assemble a non‐centrosymmetric diamond‐like network of T2 supertetrahedra. The alkaline earth cations reside in cuboctahedral voids. 31P solid‐state MAS‐NMR spectra confirm the crystal structure. SrSi7P10 and BaSi7P10 exhibit the lowest charged SiP network in phosphidosilicates so far. Full‐potential DFT calculations classify both compounds as semiconductors with small indirect bandgaps of 1.1 eV.

Synthesis, Crystal structure, electronic structure, and Raman spectra of Li4Sr2SiP4

“…Condensed polyhedra can form one-dimensional chains as in K 2 SiP 2 , [6] two-dimensional layers as in Ca 2 Si 2 P 4 [7] or three-dimensional networks as in Li 2 SiP 2 , [2,8] Li 2 SiP 3 , [8] KSi 2 P 3 [9] or SrSi 7 P 10 . [10] Furthermore, more complex phosphidosilicates have been reported. They exhibit motifs ranging from Si 4 P 5 cages as in Ba 3 Si 4 P 6 [11] to SiP 4 tetrahedra linked to each other via PÀ P bonds as in Ea 2 SiP 4 [12,13] (Ea = Sr, Ba, Eu) or connected by PÀ P bonds as well as shared vertices and/ or corners as in Ba 4 Si 3 P 8 [12] or LaSiP 3 .…”

“…While isolated SiP 4 tetrahedra are also a known feature of compounds like Sr 4 SiP 4 , [5] most other members of the phosphido silicate family exhibit different structural motives. Condensed polyhedra can form one‐dimensional chains as in K 2 SiP 2 , [6] two‐dimensional layers as in Ca 2 Si 2 P 4 [7] or three‐dimensional networks as in Li 2 SiP 2 , [2,8] Li 2 SiP 3 , [8] KSi 2 P 3 [9] or SrSi 7 P 10 [10] . Furthermore, more complex phosphidosilicates have been reported.…”

BaSi7P10 and SrSi7P10: Two Infrared Nonlinear Optical Phosphides with T2 Supertetrahedra Exhibiting Strong Second‐Harmonic Generation Effects

“…In order to explore T2‐type pnictides with superior NLO performances, two pnictides, BaSi 7 P 10 and SrSi 7 P 10 , were studied based on the following reasons: i) both compounds were constructed by vertex‐sharing T2 supertetrahedra, which might enhance the SHG effect; ii) both structures having zigzag chains from the dual‐T2 supertetrahedra connected through sharing corners, led to the paralleled arrangement of dual‐T2 supertetrahedra; and iii) although both compounds were first discovered by Haffner et al., [ 14 ] physical properties especially NLO properties had not been reported. In this study, their NLO properties were investigated experimentally and theoretically for the first time.…”

Semiconducting silicon–phosphorus frameworks for caging exotic polycations

“…11 Ternary Si-P semiconductors, such as Ba 2 Si 3 P 6 , MgSiP 2 , ZnSiP 2 , CdSiP 2 , IrSi 3 P 3 , RuSi 4 P 4 , and BaSi 7 P 10 , exhibit a diverse variety of the silicon-phosphorus bonding motifs. [12][13][14][15][16][17] The compositional space of phosphides is less explored than the oxide and chalcogenide phase spaces, thus making it an underexplored frontier for finding new semiconductors.…”