TY - JOUR

T1 - Ag4B7O12X (X = Cl, Br, I) Heptaborate Family: Comprehensive Crystal Chemistry, Thermal Stability Trends, Topology, and Vibrational Anharmonicity

AU - Volkov, Sergey N.

AU - Charkin, Dmitry

AU - Firsova, V.A.

AU - Manelis, Lev S.

AU - Banaru, Alexander M.

AU - Povolotskiy, Alexey V.

AU - Yukhno, V. A.

AU - Arsent'Ev, Maxim Yu

AU - Savchenko, Y.

AU - Ugolkov, V. L.

AU - Krzhizhanovskaya, Maria G.

AU - Bubnova, Rimma S.

PY - 2023/1

Y1 - 2023/1

N2 - Using glass crystallization and solid-state techniques, we were able to complete the family of salt-inclusion silver halide borates, Ag4B7O12X, by the X = Cl and I members. The new compounds are characterized by differential scanning calorimetry, single-crystal and high-temperature powder X-ray diffraction, optical spectroscopy, and density functional theory calculations. In all structures, the silver atoms exhibit strong anharmonicity of thermal vibrations, which could be modeled using Gram-Charlier expansion, and its asymmetry was characterized by the skewness vector. The topology of the silver halide and borate sublattices has been analyzed separately for the first time. Along the I → Br → Cl series, we observe a decrease of the melting point and configuration entropy and an increase of thermal expansion and its anisotropy and thermal vibration anharmonicity, which indicates decreasing stability.

AB - Using glass crystallization and solid-state techniques, we were able to complete the family of salt-inclusion silver halide borates, Ag4B7O12X, by the X = Cl and I members. The new compounds are characterized by differential scanning calorimetry, single-crystal and high-temperature powder X-ray diffraction, optical spectroscopy, and density functional theory calculations. In all structures, the silver atoms exhibit strong anharmonicity of thermal vibrations, which could be modeled using Gram-Charlier expansion, and its asymmetry was characterized by the skewness vector. The topology of the silver halide and borate sublattices has been analyzed separately for the first time. Along the I → Br → Cl series, we observe a decrease of the melting point and configuration entropy and an increase of thermal expansion and its anisotropy and thermal vibration anharmonicity, which indicates decreasing stability.

UR - https://www.mendeley.com/catalogue/9a5805bb-a8fc-30dd-b65b-5e5cfc4c1ed2/

U2 - 10.1021/acs.inorgchem.2c03680

DO - 10.1021/acs.inorgchem.2c03680

M3 - Article

VL - 62

SP - 30

EP - 34

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 1

ER -