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Quaternary metal‐chalcogenides combining rare‐earth cations with late transition metal cations are attracting growing attention for their optical properties, such as for solar energy conversion or second harmonic generation. Synthetic explorations of theII₃‐I₂‐IV₂‐Ch₈family (II = Eu;I = Cu or Ag;IV = Si, Ch = S or Se) have yielded Eu₃Ag₂Si₂S₈(1) and Eu₃Cu_1.08(1)Si_2.42(1)Se₈(2). Their structures have been characterized by X‐ray diffraction to form in the noncentrosymmetric space groupI3dand to exhibit two distinct types of mixed‐site occupancies, for the Ag(I) cations in1and mixed Cu(I)/Si(IV) cations in2. In both, the cation disorder occurs to achieve charge balancing with the chalcogenide anions. A high yield of1can be achievedwith optical measurements showing indirect and direct band transitions of ≈2.2(1) and ≈2.4(1) eV, respectively. Its second harmonic generation response is found to be relatively strong, approximately 0.9 × AgGaS₂, confirming its noncentrosymmetric structure. Band structure calculations reveal the valence and conduction band edges stem predominantly from the filled Ag(I)/Cu(I)‐based states and empty Si(IV)‐based states, respectively, with additional contributions from the chalcogenide anions. Calculation results also show that cation disorder facilitates a reduction in the antibonding interactions between the Ag(I)/Cu(I)d‐based and chalcogenidep‐based states. 

Pb₂Ga₃F₆(SeO₃)₂X₃·2H₂O achieve a better balance between the large SHG effect and wide band gap in the current HTO family. 

Abstract Birefringent materials are widely used in various advanced optical systems, owing to their vital role in creating and controlling polarized light. Currently, Sn²⁺‐based compounds containing stereochemically active lone‐pair (SCALP) cations are extensively investigated and considered as one class of promising birefringent materials. To solve the problem of relatively narrow bandgap of Sn²⁺‐based compounds, alkali metals and multiple halogens are introduced to widen the bandgap during the research. Based on this strategy, four new Sn²⁺‐based halides, A₂Sn₂F₅Cl and ASnFCl₂(A = Rb and Cs), with large birefringence, short ultraviolet (UV) cutoff edge, and wide transparent range are successfully found. The birefringences of A₂Sn₂F₅Cl (A = Rb and Cs) are 0.31 and 0.28 at 532 nm, respectively, which are among the largest in Sn‐based halide family. Remarkably, A₂Sn₂F₅Cl possess relatively shorter UV cutoff edge (<300 nm) and broad infrared (IR) transparent range (up to 16.6 µm), so they can become promising candidates as birefringent materials applied in both UV and IR regions. In addition, a comprehensive analysis on crystal structures and structure–property relationship of metal Sn²⁺‐based halides is performed to fully understand this family. Therefore, this work provides insights into designing birefringent materials with balanced optical properties.