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

Abstract

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 [Cu_<i>x</i>I_<i>y</i>]^{(<i>y</i>-<i>x</i>)-} 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 [Cu_<i>x</i>I_<i>y</i>]^{(<i>y</i>-<i>x</i>)-} modules. The structural diversity, enhanced robustness, and up to 100% luminescence quantum yield make the designed materials promising phosphors for lighting and sensing applications.