Family of Robust and Strongly Luminescent Cul-Based Hybrid Networks Made of Ionic and Dative Bonds

The CuI-derived inorganic-organic hybrid compounds are considered as promising phosphors for the lighting industry. Herein, exploiting N-monoalkylated hexaminium salts, [R-HMTA]X (R = Me, Et, Pr, and propargyl; X = Cl and I), as multibridging ligands, we have designed and synthesized a unique class of one-dimensional and two-dimensional hybrid CuI-materials. The reactions of these salts with CuI give rise to Allin-One (MO) type compounds combining ionic and dative bonds between inorganic and organic components. The latter is formed by structurally unique inorganic [CuxIy]((y-x)-) clusters, chains, or sheets interconnected through [R-HMTA](+) cations via multiple Cu-N bonds. The so-designed compounds at ambient temperature exhibit tunable luminescence spanning from deep blue to red color (lambda(em) = 430-625 nm) with microsecond lifetimes and the quantum efficiency of up to 78%. Remarkably, the MO materials feature nontrivial excitation- (ED) and temperature-dependent (TD) luminescence, allowing their emission color to be finely adjusted from deep blue to red through changing the excitation wavelength and/or temperature. Based on the TD emission spectroscopy and theoretical calculations, a possible mechanism of the luminescence has been proposed. The very interesting luminescence characteristics coupled with good thermal and photostability render these MO hybrid materials possible candidates for applications in energy-efficient lighting devices.