Metal-Rich Phosphides Obtained from the Lead Flux: Synthesis, Crystal, and Electronic Structure of Sr5Pt12P9 and BaPt3P2

Anastasiya Yu Makhaneva; Elena Yu Zakharova; Sergey N Nesterenko; Konstantin A Lyssenko; Vasiliy O Yapaskurt; Alexey N Kuznetsov

doi:10.1021/acs.inorgchem.2c00747

Metal-Rich Phosphides Obtained from the Lead Flux: Synthesis, Crystal, and Electronic Structure of Sr₅Pt₁₂P₉ and BaPt₃P₂

Inorg Chem. 2022 Jun 20;61(24):9173-9183. doi: 10.1021/acs.inorgchem.2c00747. Epub 2022 Jun 7.

Authors

Anastasiya Yu Makhaneva¹, Elena Yu Zakharova¹, Sergey N Nesterenko¹, Konstantin A Lyssenko¹, Vasiliy O Yapaskurt², Alexey N Kuznetsov¹

Affiliations

¹ Department of Chemistry, Lomonosov Moscow State University, Moscow 119991, Russia.
² Department of Geology, Lomonosov Moscow State University, Moscow 119991, Russia.

PMID: 35670830
DOI: 10.1021/acs.inorgchem.2c00747

Abstract

Using a high-temperature ampoule technique and lead metal as a flux, we have grown single crystals and determined crystal structures from single-crystal X-ray diffraction data of two metal-rich phosphides, Sr₅Pt₁₂P₉ (P 2₁/m, a = 6.1472(3) Å, b = 25.1713(13) Å, c = 6.4635(3) Å, β = 99.604(2)°, Z = 2, R₁ = 0.0326, wR₂ = 0.0786) and BaPt₃P₂ (P 2₁2₁2₁, a = 6.3605(6) Å, b = 6.8541(7) Å, c = 11.3493(12) Å, Z = 4, R₁ = 0.0231, wR₂ = 0.0501). Both compounds belong to their own structure types and feature 3D networks of Pt and P atoms, with the channels occupied by alkaline earth metal cations. Density functional theory calculations reveal Sr₅Pt₁₂P₉ to be a metal, while BaPt₃P₂ is a narrow-gap semiconductor with a band gap of 0.24 eV. Bonding analysis shows that both compounds feature networks of prominent covalent localized Pt-P bonds, responsible for their structural stability, as well as additional weaker and, likely, less localized Pt-Pt interactions.