Research On The Structure Regulation And Luminescence Properties Of Hybrid Cuprous Halide Material

Excitedly,the new-emerged low-dimensional organic-inorganic hybrid metal halide（OIHMH）single crystals provide excellent remedy avenue with unique superiorities comparing than 3D PNC.The versatile organic components not only provide more opportunity to modulate the crystal structure and PL property,but also strongly protect the inorganic halide skeletons to prevent the structural decomposition.Apart from the toxic Pb²⁺,numerous environmentally friendly metal ions can also be introduced to construct OIHMH including Ag⁺,Mn²⁺,Zn²⁺,In³⁺,Sb³⁺,etc,with more abundant compositions and structures.Especially,the zero-dimensional（0D）copper halides composed of spatially discrete inorganic species possess strong quantum confinement effect and high PLQY.These reversible PL transition has been explored as luminescence switching with a broad range of applications in sensor,anti-counterfeiting,information security or rewritable paper,etc.From here we see that the 0D hybrid metal halide integrate multiple advantages of adjustable crystal structure,facile SC-SC transition and structural-sensitive PL property,which manifests as one of the most promising smart luminescence material to fabricate advanced dynamic optical devices.In addition,we also prepared two antimony-based hybrid halides with similar structure by solvent evaporation method to study the effect of organic cation on the luminescence property of hybrid metal halides.The specific research contents of this paper are as follows:1.Now,we turn our attention to the 0D hybrid cuprous halides,which possess high luminescence efficiency and multiple excitated light sources from UV,blue light to X-ray.In this work,by performing dynamic SC-SC transition as photonic engineering strategy,we demonstrate a pair of 0D hybrid cuprous halides,namely as,yellow-emissive[ETPP]₂Cu₄Br₆ and green-emissive[ETPP]CuBr₂with highly efficient PL and RL quantum yields.Under the stimuli of ethanol vapor and heating treatments,reversible SC-SC transformation between them is achieved with emitting-color transformation as PL and RL switching.Meanwhile,the transition is also accompanied by a SHG“silent-active”switching between centrosymmetric NLO-inactive[ETPP]₂Cu₄Br₆ and non-centrosymmetric NLO-active[ETPP]CuBr₂.As a consequence,a synchronous triple-mode reversible PL,RL and SHG switching is facilely realized with advanced applications in molecular-level dynamic photonic devices including data storage,information security,optical logic gate,etc.2.The diversified and tunable crystal structure as well as potential scintillation performance inspire us to further explore new kind of OIHCHs as excellent candidates of AICHs.Herein,we report a new family of 0D hybrid cuprous halides of A₂Cu₄X₆（A=PTPP,TPA,X=Br,I）based on[Cu₄X₆]^2-clusters as highly efficient broadband light emitters in yellow-red range with negligible self-absorption and near-unity PLQY.Remarkably,single-crystals of these halides display extraordinary RL properties with light yield up to 57000 photons Me V^-1.This work further highlights the excellent scintillation performance of 0D hybrid cuprous halides and advance the prospective applications in X-ray imaging and detection,etc.In summary,in these two works,we have prepared a series of low-dimensional organo-inorganic hybrid cuprous halide materials by using the solvent method,and studied their photoluminescence and radioluminescence properties in detail,and explored their applications in advanced optical fields such as optical switching,anti-counterfeiting encryption and decryption,and X-ray imaging.All of the above provide concrete examples of the photoluminescence and radioluminescence properties of low-dimensional organic-inorganic hybrid metal halides.