New Approach toward Dual-Emissive Organic–Inorganic Hybrids by Integrating Mn(II) and Cu(I) Emission Centers in Ionic Crystals

Inorganic–organic hybrid luminescent materials have received great attention for their potential applications in a wide range of clean/renewable energy-related areas, including photovoltaics and solid-state lighting. Herein, we present a unique and general “Mn + Cu” approach by blending two earth-abundant luminogenic metals, manganese and copper, within a single ionic structure to construct a remarkable family of low-cost and multifunctional hybrid materials featuring dual emission, as well as triboluminescence and second-harmonic generation response. The novel hybrid materials are made of diphosphine dioxide-chelated [Mn­(O∧O)3]2+ cations and various anionic [CuxIy](y−x)– clusters, ensuring manifestation of dual phosphorescence streamed from octahedral Mn2+ ions (605–648 nm) and iodocuprate anions (480–728 nm). Noteworthily, the relative ratio of the emission bands, and hence a resulting emission chromaticity, can be tuned in a wide range through modification of cluster [CuxIy](y−x)– modules. The structural diversity, enhanced robustness, and up to 100% luminescence quantum yield make the designed materials promising phosphors for lighting and sensing applications.