Na6Mg3P4S16 and RbMg2PS4Cl2: two Mg-based thiophosphates with ultrawide bandgaps resulting from [MgS6] and [MgSxCl6−x] octahedra

Designing wide-bandgap chalcogenides is one of the most important ways of obtaining high-performance infrared (IR) functional materials. In this work, two Mg-based metal thiophosphates, namely Na₆Mg₃P₄S₁₆ (NMPS) and RbMg₂PS₄Cl₂ (RMPSC), were successfully obtained by introducing [MgS₆] and [MgS_xCl_6-x] octahedra into thiophosphates. In addition, their crystal structures were determined, a first for Mg-containing [PS₄]-based thiophosphates to the best of our knowledge. Their bandgaps were investigated in theoretical ways and verified by taking experimental measurements, and determined to be 3.80 eV for NMPS and 3.93 eV for RMPSC, values greater than those of the other investigated thiophosphate halides. The wide bandgaps of NMPS and RMPSC were attributed, based on theoretical calculations, to the [MgS_xCl_6-x] (x = 0-6) octahedron.