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1. Rb ₂ CuX ₃ (X = Cl, Br): 1D All‐Inorganic Copper Halides with Ultrabright Blue Emission and Up‐Conversion Photoluminescence

   https://doi.org/10.1002/adom.201901338  

   Creason, Tielyr_D; Yangui, Aymen; Roccanova, Rachel; Strom, Amanda; Du, Mao‐Hua; Saparov, Bayrammurad (November 2019, Advanced Optical Materials)

   Abstract All‐inorganic metal halides such as Cs₄PbX₆and CsPbX₃(X = Cl, Br, and I) are attracting global attention owing to their promise in optoelectronic applications. However, the presence of the toxic heavy metal lead (Pb) in these materials is a major concern. Here, a family of nontoxic high‐efficiency blue‐emitting all‐inorganic halides Rb₂CuX₃(X = Br and Cl) is reported; the compounds exhibit 1D crystal structures featuring anionic²⁻ribbons separated by Rb⁺cations. The measured record high photoluminescence quantum yield values range from 64% to 100% for Rb₂CuBr₃and Rb₂CuCl₃, respectively. Furthermore, the measured emission linewidths are quite narrow with full width at half maximum values of 54 and 52 nm for Rb₂CuBr₃and Rb₂CuCl₃, respectively. Single crystals of Rb₂CuCl₃demonstrate an anti‐Stokes photoluminescence signal, shown for the first time for Pb‐free metal halides. The discovery of highly efficient narrow blue emitters based on a nontoxic and inexpensive metal copper paves a way for the consideration of low‐cost and environmentally friendly copper halides for practical applications. 

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2. An effective pathway to design and synthesize UV birefringent crystals via rational assembly of π-conjugated [CO ₃ ] ²⁻ and [NO ₃ ] ⁻ triangles

   https://doi.org/10.1039/d2tc05374h  

   Hu, Zhaowei; Liu, Lili; Zhang, Ruixin; Jing, Qun; Wang, Huan; Tian, Jindan; Xu, Jiayue; Halasyamani, P. Shiv (March 2023, Journal of Materials Chemistry C)

   Planar MO 3 (M = B, C, N) units have frequently been considered important structural components of novel birefringent crystal materials. An efficient approach for constructing new functional crystals is to simultaneously assemble multiple structural motifs together. Two compounds, Na 3 Rb 6 (CO 3 ) 3 (NO 3 ) 2 X·6H 2 O (X = Br and Cl), were synthesized by the integration of three kinds of anionic groups. More interestingly, the [CO 3 ] 2− and [NO 3 ] − groups in Na 3 Rb 6 (CO 3 ) 3 (NO 3 ) 2 X·6H 2 O are all coplanar with the aid of [NaO 7 ] 13− polyhedra, which can enhance the anisotropic polarizability. Na 3 Rb 6 (CO 3 ) 3 (NO 3 ) 2 X·6H 2 O have a large theoretical birefringence of ∼0.165 at 1064 nm and possess a short UV cut-off edge of ∼230 nm. Additionally, the two compounds exhibit good crystal growth habits. These properties illustrate that Na 3 Rb 6 (CO 3 ) 3 (NO 3 ) 2 X·6H 2 O are promising UV birefringent crystals. 

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3. Composition‐Dependent Photoluminescence Properties and Anti‐Counterfeiting Applications of A ₂ AgX ₃ (A = Rb, Cs; X =  Cl, Br, I)

   https://doi.org/10.1002/adfm.202104941  

   Kumar, Pawan; Creason, Tielyr_D; Fattal, Hadiah; Sharma, Manila; Du, Mao‐Hua; Saparov, Bayram (September 2021, Advanced Functional Materials)

   Abstract Copper(I) halides are emerging as attractive alternatives to lead halide perovskites for optical and electronic applications. However, blue‐emitting all‐inorganic copper(I) halides suffer from poor stability and lack of tunability of their photoluminescence (PL) properties. Here, the preparation of silver(I) halides A₂AgX₃(A = Rb, Cs; X = Cl, Br, I) through solid‐state synthesis is reported. In contrast to the Cu(I) analogs, A₂AgX₃are broad‐band emitters sensitive to A and X site substitutions. First‐principle calculations show that defect‐bound excitons are responsible for the observed main PL peaks in Rb₂AgX₃and that self‐trapped excitons (STEs) contribute to a minor PL peak in Rb₂AgBr₃. This is in sharp contrast to Rb₂CuX₃, in which the PL is dominated by the emission by STEs. Moreover, the replacement of Cu(I) with Ag(I) in A₂AgX₃significantly improves photostability and stability in the air under ambient conditions, which enables their consideration for practical applications. Thus, luminescent inks based on A₂AgX₃are prepared and successfully used in anti‐counterfeiting applications. The excellent light emission properties, significantly improved stability, simple preparation method, and tunable light emission properties demonstrated by A₂AgX₃suggest that silver(I) halides may be attractive alternatives to toxic lead halide perovskites and unstable copper(I) halides for optical applications. 

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4. New germanate and mixed cobalt germanate salt inclusion materials: [(Rb ₆ F)(Rb ₄ F)][Ge ₁₄ O ₃₂ ] and [(Rb ₆ F)(Rb _3.1 Co _0.9 F _0.96 )][Co _3.8 Ge _10.2 O ₃₀ F ₂ ]

   https://doi.org/10.1039/D0CE01099E  

   Carone, Darren; Usman, Mohammad; Klepov, Vladislav V.; Smith, Mark D.; Kocevski, Vancho; Besmann, Theodore M.; zur Loye, Hans-Conrad (December 2020, CrystEngComm)

   null (Ed.)

   Single crystals of two new germanates, [(Rb 6 F)(Rb 4 F)][Ge 14 O 32 ] and [(Rb 6 F)(Rb 3.1 Co 0.9 F 0.96 )][Co 3.8 Ge 10.2 O 30 F 2 ], were synthesized via high temperature RbCl/RbF flux growth. Both compounds crystallize in the cubic space group F 4̄3 m and possess the germanium framework of the previously reported salt inclusion material (SIM), [(Cs 6 F)(Cs 3 AgF)][Ge 14 O 32 ], related to the Ge 7 O 16 zeolitic family. These materials demonstrate the ability to accommodate a variety of salt-inclusions, and exhibit chemical flexibility enabling modifications of the framework through incorporation of Co. Alteration of the salt-inclusion led to intrinsic luminescence of [(Rb 6 F)(Rb 4 F)][Ge 14 O 32 ] while modification of the framework resulted in an unanticipated Rb/Co salt/inclusion in [(Rb 6 F)(Rb 3.1 Co 0.9 F 0.96 )][Co 3.8 Ge 10.2 O 30 F 2 ]. Fluorescence measurements were performed on [(Rb 6 F)(Rb 4 F)][Ge 14 O 32 ]. First-principles calculations in the form of density functional theory (DFT) were performed for [(Rb 6 F)(Rb 3.1 Co 0.9 F 0.96 )][Co 3.8 Ge 10.2 O 30 F 2 ] to elucidate its electronic and magnetic properties, and stability at 0 K. 

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5. Luminescence from Self‐Trapped Excitons and Energy Transfers in Vacancy‐Ordered Hexagonal Halide Perovskite Cs ₂ HfF ₆ Doped with Rare Earths for Radiation Detection

   https://doi.org/10.1002/adom.202201374  

   Adhikari, Menuka; Shrivastava, Navadeep; McClain, Starfari_T; Adhikari, Chandra_M; Guzelturk, Burak; Khanal, Rabi; Gautam, Bhoj; Luo, Zhiping (August 2022, Advanced Optical Materials)

   Abstract Compared to halides Cs₂HfX₆(X = Cl, Br, I) with a vacancy‐ordered cubic double perovskite structure, the halide Cs₂HfF₆(CHF), with a hexagonal Bravais lattice, possesses a higher mass density and chemical stability for radiation detection. Luminescence properties and energy transfer mechanisms of rare‐earths‐doped CHF materials are studied here. The structure of CHF is identified as a new type of vacancy‐ordered hexagonal perovskite, with the same type of building blocks of the double perovskite but stacked with single layers. Density‐functional theory calculations reveal a large bandgap of CHF. A broad emission is observed from the pristine CHF host, which is suggested to be associated with self‐trapped excitons (STEs). A series of rare‐earths‐doped materials are designed utilizing the STE emissions, and efficient energy transfers from STEs and Tb³⁺to Eu³⁺are achieved for tunable emissions. The codoped material shows stable emission under X‐ray irradiation, with 10.2% reduction from its initial emission intensity, associated with possible structural evolution by radiation‐induced deformation of the soft host. The radiation responses of singly and codoped materials are evaluated, and the codoped material is found to be more sensitive to the radiation energy than the singly doped or pristine CHF for radiation detection. 

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