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

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.

Bridging the Salt-Inclusion and Open-Framework Structures: The Case of Acentric Ag4B4O7X2 (X = Br, I) Borate Halides.

An acentric borate family, Ag4B4O7X2 (X = Br, I), has been prepared by slow cooling stoichiometric melts in evacuated silica ampules. Their crystal structure is comprised of two porous interpenetrating frameworks and demonstrates a further development of the "salt-inclusion" architecture toward a "covalent-inclusion" structure. The (Ag2X)+ sublattice shows strong anharmonic vibrations. Thermal expansion is strongly anisotropic because of the presence of condensed rigid kernite boron-oxygen chains aligned perpendicular to the c axes.

The first silver bismuth borate, AgBi2B5O11.

The first silver bismuth borate, AgBi2B5O11 (silver dibismuth pentaborate), has been prepared via glass crystallization in the Ag2O-Bi2O3-B2O3 system and characterized by single-crystal X-ray diffraction. Its structure is derived from that of centrosymmetric Bi3B5O12 by ordered substitution of one Bi3+ ion for Ag+, which results in the disappearance of the mirror plane and inversion centre. Second harmonic generation (SHG) measurements confirm the acentric crystal structure. It is formed by [Bi2B5O11]∞ layers stretched along c and comprised of vertex-sharing B5O10 and BiO3 groups which incorporate the Ag+ cations. The new compound was characterized by thermal analysis, high-temperature powder X-ray diffraction, and vibrational and UV-Vis-NIR (near infrared) spectroscopy. Its thermal expansion is strongly anisotropic due to the presence of rigid B5O10 groups aligned in a parallel manner. The minimal value is observed along their axis [parallel to c, αc = 3.1 (1) × 10-6 K-1], while maximal values are observed in the ab plane [αa = 20.4 (2) and αb = 7.8 (2) × 10-6 K-1]. Upon heating, AgBi2B5O11 starts to decay above 684 K due to partial reduction of silver; incongruent melting is observed at 861 K. According to density functional theory (DFT) band-structure calculations, the new compound is a semiconductor with an indirect energy gap of 3.57 eV, which agrees with the experimental data (absorption onset at 380 nm).