Magnesium cations as templates for the self-assembly of supramolecular luminescent {Mg@[Bφ]}-clusters.

Solvothermal reaction of magnesium nitrate and boron oxide in ,-dimethylformamide produced a number of particularly complex supramolecular magnesium borates. Five topologically different types of negatively charged {Mg@[Bφ]}-clusters, φ = O, OH, were observed with the magnesium cation as a core and octadecaborate anions as shells. The clusters assemble common borate polyhedra forming 1D chains, a 2D mesoporous layer, and 3D mesoporous frameworks with an effective channel width of up to 16 Å.

AgBOX (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, AgBOX, 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.