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Abstract Designing and synthesizing multifunctional hybrid copper halides with near ultraviolet (NUV) light‐excited high‐energy emission (<500 nm) remains challenging. Here, a pair of broadband‐excited high‐energy emitting isomers, namely, α‐ / β‐ (MePh 3 P) 2 CuI 3 (MePh 3 P=methyltriphenylphosphonium), were synthesized. α‐ (MePh 3 P) 2 CuI 3 with blue emission peaking at 475 nm is firstly discovered wherein its structure contains regular CuI 3 2− triangles and crystallizes in centrosymmetric space group P 2 1 / c . While β ‐(MePh 3 P) 2 CuI 3 featuring distorted CuI 3 2− planar triangles shows inversion symmetry breaking and crystallizes in the noncentrosymmetric space group P 2 1 , which exhibits cyan emission peaking at 495 nm with prominent near‐unity photoluminescence quantum yield and the excitation band ranging from 200 to 450 nm. Intriguingly, β ‐(MePh 3 P) 2 CuI 3 exhibits phase‐matchable second‐harmonic generation response of 0.54×KDP and a suitable birefringence of 0.06@1064 nm. Furthermore, β ‐(MePh 3 P) 2 CuI 3 also can be excited by X‐ray radioluminescence with a high scintillation light yield of 16193 photon/MeV and an ultra‐low detection limit of 47.97 nGy/s, which is only 0.87 % of the standard medical diagnosis (5.5 μ Gy/s). This work not only promotes the development of solid‐state lighting, laser frequency conversion and X‐ray imaging, but also provides a reference for constructing multifunctional hybrid metal halides.
Qi et al. (Tue,) studied this question.