(RPh3P)[Mn(dca)3]: A Family of Glass-Forming Hybrid Organic–Inorganic Materials

ABX₃-type hybrid organic–inorganic structures have recently emerged as a new class of meltable materials. Here, by the use of phenylphosphonium derivatives as A cation, we study liquid- and glass-forming behavior of a new family of hybrid structures, (RPh₃P)[Mn(dca)₃] (R = Me, Et, Ph; dca = dicyanamide). These new compounds melt at 196–237 °C (T_m) and then vitrify upon cooling to room temperature, forming glasses. In situ glass formation of this new family of materials was probed on a large scale using a variable-temperature PXRD experiment. Structure analyses of the crystalline and the glasses were carried out by solid-state nuclear magnetic resonance spectroscopy and synchrotron X-ray total scattering techniques for using the pair distribution function. The mechanical properties of the glasses produced were evaluated showing promising durability. Thermal and electrical conductivities showed low thermal conductivities (κ ∼ 0.07–0.09 W m^–1 K^–1) and moderate electrical conductivities (σ ∼ 10^–4–10^–6 S m^–1) at room temperature, suggesting that by the precise control of the A cation, we can tune meltable hybrid structures from moderate conductors to efficient thermal insulators. Our results raise attention on the practical use of this new hybrid material in applications including, e.g., photovoltaic devices to prevent light-deposited heat (owing to low κ_RT), energy harvesting thermoelectric, etc., and advance the structure–property understanding.