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-(MePh3P)2CuI3 (MePh3P = methyltriphenylphosphonium), were synthesized. α-(MePh3P)2CuI3 with blue emission peaking at 475 nm is firstly discovered wherein its structure contains regular [CuI3]2‒ triangles and crystallizes in centrosymmetric space group P21/c. While β-(MePh3P)2CuI3 featuring distorted [CuI3]2‒ planar triangles shows inversion symmetry breaking and crystallizes in the noncentrosymmetric space group P21, 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-(MePh3P)2CuI3 exhibits phase-matchable second-harmonic generation response of 0.54 × KDP and a suitable birefringence of 0.06@1064 nm. Furthermore, β-(MePh3P)2CuI3 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 μGy/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.
摘要:
设计和合成具有近紫外(NUV)光激发的高能发射(<500nm)的多功能混合卤化铜仍然具有挑战性。这里,一对宽带激发的高能异构体,即,α-/β-(MePh3P)2CuI3(MePh3P=甲基三苯基鳞),是合成的。首先发现了在475nm处具有蓝色发射峰值的α-(MePh3P)2CuI3,其中其结构包含规则的[CuI3]2-三角形,并在中心对称空间群P21/c中结晶。而具有扭曲的[CuI3]2平面三角形的β-(MePh3P)2CuI3显示出反转对称性破坏并在非中心对称空间群P21中结晶,该空间群表现出青色发射峰值在495nm处,具有显着的近统一光致发光量子产率和激发带范围从200到450nm。有趣的是,β-(MePh3P)2CuI3表现出0.54×KDP的相位匹配二次谐波产生响应和0.06@1064nm的合适双折射。此外,β-(MePh3P)2CuI3也可以通过X射线放射发光激发,具有16193光子/MeV的高闪烁光产量和47.97nGy/s的超低检测极限,这只是标准医学诊断(5.5μGy/s)的0.87%。这项工作不仅促进了固态照明的发展,激光频率转换和X射线成像,同时也为构建多功能混合金属卤化物提供了参考。