Boron Sulfide and Selenide – Synthesis and Refinement of Boron-Rich Compounds

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Boron is a rare chemical element with atomic number 5 that is most commonly found in minerals such as boron carbide and boron nitride. In crystalline form it is a black, hard, lustrous metalloid with a high melting point and chemical inertness.

Boronite (B2O6) is a common mineral in the Earth’s crust and is widely used as a chemical additive to salts, paints, plastics and other materials. It forms a complex network of regular B12 icosahedra that are bonded to each other through covalent bonds. This makes it one of the most stable minerals and has several interesting properties that make it suitable for industrial applications.

The chemical structure of boron is quite complicated and is often represented by multiple B12-icosahedra stacked on top of each other with different interstitial atoms. This multicenter metal-like bonding system allows for extremely stable and reversible molecular networks to be formed and is the main characteristic of boron-rich compounds.

In this study we report the synthesis and crystal structure refinement of new orthorhombic boron-rich sulfide o-B6S and selenide o-B6Se. The boron-rich chalcogenides were studied by powder X-ray diffraction and Raman spectroscopy at ambient pressure. Rietveld refinement of synchrotron X-ray diffraction data showed that both phases have orthorhombic symmetry and belong to the Pmna space group.

The boron-rich chalcogenides show unusual vibrational modes which can be attributed to the distortions of icosahedral inter-atom bonds associated with atomic movements within the unit cells. These vibrational modes were assigned to the phonon frequencies and normal modes at the G-point based on density functional theory.