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RESEARCH PAPER · Journal of the American Chemical Society · 2023

Cs 3 [(BOP) 2 (B 3 O 7 ) 3 ]: A Deep-Ultraviolet Nonlinear Optical Crystal Designed by Optimizing Matching of Cation and Anion Groups

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Cs 3 [(BOP) 2 (B 3 O 7 ) 3 ]: A Deep-Ultraviolet Nonlinear Optical Crystal Designed by Optimizing Matching of Cation and Anion GroupsOriginalBa 3 (BS 3 )(PS 4 ): the first alkaline-earth metal thioborate–thiophosphate with strong optical anisotropy originating from planar [BS 3 ] units8Hydroxyfluorooxoborate (NH 4 )[C(NH 2 ) 3 ][B 3 O 3 F 4 (OH)] for exploring the effects of cation substitution on structure and optical properties26Synthesis, structure and characterization of Cd 2 TeO 3 Cl 2 with unprecedented [Cd 2 O 6 Cl 4 ] octahedral dimers5Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit38Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit1Four UV Transparent Linear and Nonlinear Optical Materials Explored from Pure Selenite Compounds22Mixed Anionic Tetrahedra Guided Design of New Infrared Nonlinear Optical Material Cs 3 Ga 8 S 13 Cl with High Laser‐Induced Damage Threshold26Excellent Nonlinear Optical M[M4Cl][Ga11S20] (M = A/Ba, A = K, Rb) Achieved by Unusual Cationic Substitution Strategy20Ln 2 F 2 (OH 2 )(MoO 3 ) 2 (SeO 3 ) 2 : Promising Multifunctional Nonlinear Optical Materials Created by Partial Fluorination Strategy under Corrosion Resistant Supercritical Reactions25A I B 3 II C 2 III Q 6 VI X VII : A Thioborate Halide Family for Developing Wide Bandgap Infrared Nonlinear Materials by Coupling Planar [BS 3 ] and Polycations25Advances in Solid-State Nonlinear Optical Materials: From Fundamentals to Applications61K 2 RbB 8 PO 16 : A Borophosphate with Moderate Birefringence and Deep-Ultraviolet Transmission10Cd8(BO3)4SiO4: Metal Cation Inducing the Formation of Isolated [BO3] and [SiO4] Units in Borate Silicate15Secondary‐Bond‐Driven Construction of a Polar Material Exhibiting Strong Broad‐Spectrum Second‐Harmonic Generation and Large Birefringence9Secondary‐Bond‐Driven Construction of a Polar Material Exhibiting Strong Broad‐Spectrum Second‐Harmonic Generation and Large Birefringence41K(NH4)Zn2(PO4)2: a Beryllium-Free Sr2Be2B2O7 Derivative with Enhanced Interlayer Connectivity7“One stone two birds” design of borates featuring edge-sharing [BO 4 ] and different B–O configurations in one structure utilizing covalent tetrahedra8[(C 5 H 6 N 2 ) 2 H](Sb 4 F 13 ): a polyfluoroantimonite with a strong second harmonic generation effect60A UV non-hydrogen pure selenite nonlinear optical material for achieving balanced properties through framework-optimized structural transformation41A-site cation manipulation of exemplary second harmonic generation response and optical anisotropy in rare-earth borates18Approach for quality deep-ultraviolet nonlinear optical crystals via a substitution strategy of channel species in zeolite3Ba 2 GeF 2 Q 3 (Q = S, Se) and Ba 3 GeF 2 Se 4 : new F-based chalcohalides with enhanced birefringence9Design of alkali lead oxybromides with a strong second-harmonic generation response and large birefringence1Effectively designing infrared nonlinear optical materials with magnetism, MMn 6 Ga 6 S 16 (M = Ca, Sr, Ba, and Pb), aided by stable open frameworks13Fully tricoordinated assembly unveils a pioneering nonlinear optical crystal (SbTeO 3 )(NO 3 )25Galloborates as ultraviolet nonlinear optical crystals: advances and perspectives8Halide-driven polarity tuning and optimized SHG-bandgap balance in (C 4 H 11 N 2 )ZnX 3 (X = Cl, Br, I)34Large optical anisotropy in noncentrosymmetric phosphate with pseudo 2D intercalated layer16Li 3 Na 7 B 4 P 6 O 26 : a new ultraviolet transparent congruently melting non-linear optical crystal3N 2 H 4 Zn(HC 3 N 3 O 3 ): exceptionally strong second harmonic generation and ultra-long phosphorescence16New ultraviolet transparent rare-earth borates with enhanced birefringence induced by cation chemical substitution15Recent advances in rational structure design for nonlinear optical crystals: leveraging advantageous templates153Reconstructing nearly isotropic microstructures to construct a one-dimensional framework causing record birefringence in thiophosphates13Reticular chemistry-aided effective design of new second-order nonlinear optical selenites11Strategically designed metal-free deep-ultraviolet birefringent crystals with superior optical properties18Wide band gap selenide infrared nonlinear optical materials A II Mg 6 Ga 6 Se 16 with strong SHG responses and high laser-induced damage thresholds31新型深紫外非线性光学晶体研究进展(特邀)9Design of Deep-Ultraviolet Zero-Order Waveplate Materials by Rational Assembly of [AlO2F4] and [SO4] Groups9New opportunities for ferroelectric deep-UV nonlinear optical crystals12Design of deep-ultraviolet zero-order waveplate materials using LiB3O5 as the template8Toward the ultraviolet (UV) or deep-UV nonlinear optical crystals: The combination of π-conjugated planar [XY3] and tetrahedral [XY4]80Hg3Se(SeO3)(SO4): A Mixed-Valent Selenium Compound with Mid-Infrared Transmittance Obtained by In Situ Reaction26AYSO4F2 (A = K, Rb): [YO4F4] Polyhedra Enhancement of Birefringence in Non-π-Conjugated Sulfate Systems9Record Second-Harmonic Generation and Birefringence in an Ultraviolet Antimonate by Bond Engineering157A2Pb3[H2N(CH2COO)2]3Cl5 (A = K, Rb): Porous Crystals Constructed on [Pb3Cl5O6] Clusters with Comprehensive Nonlinear Optical Performance3UV-Transparent SHG Material Explored in an Alkali Metal Sulfate Selenite System16Unleashing the potential of π-conjugated [B2O3(OH)2] to enhance birefringence in DUV crystals9Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O: A Strontium Borate That Shows Deep‐Ultraviolet‐Transparent Nonlinear Optical Properties17[Na2PbI][Ga7S12]: Combining Diamond-Like Anionic Framework with Polycationic Chain toward Achieving Remarkable Nonlinear Optical Response21A perspective on deep-ultraviolet nonlinear optical materials13A Noncentrosymmetric Metal‐Free Borophosphate: Achieving a Large Birefringence and Excellent Stability by Covalent‐Linkage27Two Hydroxyfluorooxoborates Achieving Deep‐Ultraviolet Cutoff Edges and Moderate Birefringence by Assembling Multi‐Anionic Groups6Edge-Sharing Tetrahedra Realizing Superior Birefringence and High Deep-Ultraviolet Transmittance in α-Be3(H2O)2(PO4)2 Crystal Synthesized by Mild Chemistry14Assembly of π‐Conjugated [B 3 O 6 ] Units by Mer‐Isomer [YO 3 F 3 ] Octahedra to Design a UV Nonlinear Optical Material, Cs 2 YB 3 O 6 F 211Assembly of π‐Conjugated [B3O6] Units by Mer‐Isomer [YO3F3] Octahedra to Design a UV Nonlinear Optical Material, Cs2YB3O6F297Na3[Al2B6P4O22(OH)3](H2O)6 and Na3[Al2BP2O11](H2O)0.5: Two Remarkable Complex Aluminum Borophosphates8M6[Cd2(CO3)2(B12O18)(OH)6] (M = K, Rb): Borate–Carbonates with Two CdCO3 Embedded in a Cyclic Oxoboron Anion10PbBeB2O5: A High-Performance Ultraviolet Nonlinear-Optical Crystal with Functional [BeB2O8]8– Group3Structure‐Prediction‐Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials24Structure‐Prediction‐Oriented Synthesis of Thiophosphates as Promising Infrared Nonlinear Optical Materials1Old tree blossoms anew: Research progress on the structures and optical properties of ultraviolet selenites56Recent advances and future perspectives on rare-earth-based nonlinear optical materials with π-conjugated [XO3] (X = B, C, N) units66A3Sc(SO4)3 (A = K, Rb, Cs): Three Deep‐Ultraviolet Transparent Alkali‐Scandium Sulfates with Strong Second‐Harmonic Generation Response and High Thermal Stability14La3Ga5M0.5Sn0.5O14, (M = Ge, Si): Design and Synthesis of Two Langasite Nonlinear Optical Materials with Large Second Harmonic Generation and Birefringence Induced by Distorted (Sn/M)O6 Octahedra4Breaking through the ‘‘200 nm deep-ultraviolet wall’’ of phase matching region by cation structural modulation27The Directional Design of the Quasi‐Phase‐Matching Short‐Wave Ultraviolet Nonlinear Optical Crystal25Ba2ScBSi2O9: A Mixed-Coordination Borosilicate with a Low B/Si Ratio Exhibiting Enhanced Second Harmonic Generation Response7Tetrahedra Modification of Phosphates for Optical Anisotropy Enhancement13Na(C2H10N2)2[Zn3(PO4)2(H0.5PO4)]2: A Short-Wave Ultraviolet Open-Framework Zincophosphate Exhibiting Substantial Optical Dispersion Ability4Toward Strong UV–Vis–NIR Second-Harmonic Generation by Dimensionality Engineering of Zinc Thiocyanates32RE(HSeO3)(SeO3)(H2O)·(H2O) (RE = Y, Gd): Two Rare-Earth Selenite Nonlinear Optical Crystals with Wide Band Gaps6Learning From Nature: The Rational Non‐Centrosymmetric Structural Design in the Honeycomb‐Like Gaudefroyite Family23A Giant Optically Anisotropic Phosphate Driven by Mixed Valence Mercury Units22Two α‐SiO 2 ‐Related Deep‐Ultraviolet Phase‐Matchable Optical Nonlinear Beryllium Silicate Crystals Na 2 BeSiO 4 and Li 2 BeSiO 4 with Enhanced SHG Effect10Rb 1.87 Cs 1.13 B 8 O 13 (NO 3 ): a new acentric borate-nitrate with two types of three-dimensional interpenetrating lattices1Designing a Heteroleptic Tetrahedral Group with an Ultrahigh Polarizability Anisotropy by Optimizing the Bonding Electrons Activity and Their Distribution14Li3[AlP2O7F(OH)](H2O)0.5 and A[Al2(PO4)2F(H2O)](A = K, Rb): Counter Cation Templates Derived Three Polar Alkaline Metal Fluoroaluminophosphates6La 3 (Ga 3 S 3 O 3 )(Si 2 O 7 ): An Oxychalcogenide Demonstrating Ultrawide Optical Bandgap and Favorable Birefringence Propelled by Divergent Anionic Groups6Breaking Performance Barriers in KBe 2 BO 3 F 2 (KBBF) Analogs by Functional Group Self‐Polymerization5Breaking Performance Barriers in KBe 2 BO 3 F 2 (KBBF) Analogs by Functional Group Self‐Polymerization48Deep ultraviolet transparent borophosphates LiAB 2 P 2 O 9 (A = NH 4 , K) and LiNaB 2 P 2 O 8 (OH) 2 ·H 2 O exhibiting a moderate second-harmonic generation response4A potential UV nonlinear-optical crystal with a strong second-harmonic response: RbNa 2 Eu 2 (BO 3 ) 35A remarkable solar-blind ultraviolet nonlinear optical crystal with comprehensive performance and enhanced thermal stability4An excellent ultraviolet nonlinear optical crystal derived from the polar methylphosphonate unit8Anion ratio-directed design of CaB 4 O 5 F 4 and CaB 6 O 8 F 4 : [BO 3 ]/[BO 2 F 2 ] hybridization tailoring deep-ultraviolet nonlinear optical performance2BaAlPO 4 F 2 : structure and properties of the first barium fluoroaluminophosphate with the mixed anion group [Al 2 PO 8 F 5 ]1Deep-ultraviolet nonlinear-optical crystals LiBePO 4 and BeP 2 O 6 synthesized by ionic potential modulation towards uniform arrangement of PO 4 groups5Designing infrared nonlinear optical crystals, Sr 2 MgSn 2 OS 6 and Sr 2 SnGa 2 OS 6 , with hybrid anionic frameworks via a double substitution strategy4Hg 2 (HTe 2 O 5 )(PO 4 ): a novel phosphate crystal with enhanced birefringence enabled by the synergistic modification of multiple functional groups12Low thermal expansion and high lattice thermal conductivity in β-sodalite Co 4 B 6 O 13 : enhancing the local rigidity of the cationic tetrahedral cluster4M 2 Al 2 Ti(PO 4 ) 4 (M = Rb, Cs): synthesis and optical property investigation of two titanium phosphates with a dissimilar structural configuration2Na 2 PbB 6 O 10 SO 4 and Ca 2.58 Pb 0.42 B 6 O 11 SO 4 : first borate–sulfates featuring 3D porous borate anionic frameworks0Synthesising a series of promising ultraviolet nonlinear optical materials with the aid of the flexibility of isolated [B 5 O 10 ] groups3Y(C 6 H 5 SO 3 ) 3 ·9H 2 O: strategic integration of ligand substitution and π-conjugated group linkage in sulfates for enhanced ultraviolet nonlinear optical properties4层状结构深紫外非线性光学晶体研究进展(特邀)2混合阴离子无水无机硼酸盐深紫外非线性光学晶体的研究进展(特邀)4Assembly of π-conjugated [B3O7] groups by unprecedented antiparallel triangles [ZnO3] to tailor a deep-UV zinc borate birefringent crystal6Hetero‐Anionic Oxychalcogenides with Structures and Properties Tuned by the O:S Ratio14Highly Polarizable Phosphorus‐Centered Tetrahedra and π‐Conjugated Carbon‐Centered Triangular Moieties Inducing Large Anisotropy and Short‐Wavelength Phase‐Matching23Sr2Zn(C3N3O3)2: An Alkaline Earth and d10 Transition Metal Based Ultraviolet Cyanurate with Large Birefringence6An alkali and rare earth metal mixed cyanurate KLa2(C3N3O3)2Cl with large birefringence: Synthesis and characterization2Soft–Rigid Structural Integration in KMgBO3: A Pathway to Negative Thermo-optic Coefficient via Positive Thermal Expansion and Negative Temperature-Dependent Optical Absorption Edge2Lithium Borate-Squarate: An Organic–Inorganic Groups-Mixed Nonlinear Optical Crystal with Large Birefringence4Na3Y2F3P2O8 and K4Y3F5P4O14: [YOF] Polyhedra Inducing Birefringence Enhancement in Non-π-Conjugated Phosphate Systems3K2PbB5P3O17: A Mixed-Coordinated Borophosphate with Enhanced Birefringence Driven by the [B2O5] Unit5Prediction of New Functional Fluorooxoborates with Expected Anionic Framework: A Case of CaB3O5F4Design of rare earth borate short-wave UV nonlinear optical crystals with strengthened second harmonic generation activities via cationic modification strategy11Size effect of cations in the A2B3O4F3 family: Based on the new member Cs2B3O4F34A Promising Deep Ultraviolet Nonlinear Optical Crystal Activated by the Ordered Structure Design40A Promising Deep Ultraviolet Nonlinear Optical Crystal Activated by the Ordered Structure Design3Engineering an Excellent β ‐BaB 2 O 4 ‐Inspired UV Nonlinear Optical Material Through Secondary Building Unit Substitution21Engineering an Excellent β ‐BaB 2 O 4 ‐Inspired UV Nonlinear Optical Material Through Secondary Building Unit Substitution6Review of KBe2BO3F2-like second-order nonlinear optical materials and their structure-performance relationships13Halogen-Driven Structural Engineering in Tellurium Oxyhalides: Enhanced SHG Response and Broad Optical Transparency6Breaking the Natural Tendency of Deep‐UV Polyborate Anion Clusters to Inducing Strong Optical Anisotropy13NH4PO3HCH3 and NH4PO3CH2NH3: Two Phosphate Derivatives with Deep-UV Cutoff Edges and Moderate Birefringence1Ca 7 (TeO 3 ) 6 (MoO 4 ): A Promising Mid-Infrared Nonlinear Optical Crystal Activated via a Module-Oriented Dimensionality Reduction Strategy34All-three-in-one: Pb2(H2PO4)2(C2O4) significantly enhanced birefringence in phosphate materials4Controllable Synthesis of a Strong Ultraviolet Nonlinear Optical Crystal by Tailoring the Lead Oxychloride Polyhedron3Non-equivalent terminating roles of hydroxyl and fluorine in hydroxy/fluorooxo-borate optical functional materials2Design and Synthesis of a Deep-Ultraviolet Nonlinear Optical Crystal KRb3B6Ge3O17 Composed of [B3O8] Units and [GeO4] Tetrahedra6Design, Synthesis, and Improvement of Nonlinear Optical Properties from Aluminophosphite to Aluminophosphate1Exceptional Second Harmonic Generation in Ultraviolet Nonlinear Optical Oxyfluoroniobate Crystals via Structural Fingerprint Optimization of Polar Chains22Exceptional Second Harmonic Generation in Ultraviolet Nonlinear Optical Oxyfluoroniobate Crystals via Structural Fingerprint Optimization of Polar Chains8Reversal Enhancement of Birefringence by Stereochemically Active Lone Pairs in Sn(II)-Based Mixed Halides0A-Site Cation Substitution toward Structural Transformation in Phosphates Exhibiting Short UV Transparency and Second Harmonic Response3Anion-Ordered [B3O5(OH)2] Induced by Crystal Water with Deep Ultraviolet Transparency and Large Birefringence in Boron-Rich Borophosphates4Promising UV/DUV nonlinear optical materials with X-membered (X = multiples of 6) rings in anhydrous inorganic borates20Rational Design of a Deep-Ultraviolet Nonlinear Optical Crystal25Borosilicates as deep-ultraviolet transparent nonlinear optical crystals: Structural motifs, performance limits and future directions9Ag3In3(SeO3)3(SO4)F4: A Sulfate Selenite Nonlinear Optical Material with a Wide Bandgap3Na6(SO4)2SiF6: A Stable Sulfate Fluosilicate with Wide Deep-Ultraviolet Transparency Window and Strong Second-Harmonic Generation Response4[Pb(ptz)(OH)(H2O)]: A Hybrid Nonlinear Optical Crystal with Large Birefringence0Ag(Te2O3)(PO4): The first Ag-containing phosphate-tellurite nonlinear optical crystal featuring novel zigzag layered structure0The functional capabilities of the CBPO (Cs3[(BOP)2(B3O7)3]) crystal for frequency conversion0pH‐Regulated Ring‐Opening/Closing Transformation in Polyoxometalates Enables High‐Performance Nonlinear Optical Crystals1pH‐Regulated Ring‐Opening/Closing Transformation in Polyoxometalates Enables High‐Performance Nonlinear Optical Crystals13Dual-anion synergy drives remarkable birefringence in sulfate–nitrate crystals1Chiral Lead-Oxyiodide Nonlinear Optical Crystals Constructed on l -Malate Groups5Novel [BO 2 ] superhalogen module-enabled deep-ultraviolet nonlinear optical material: rational design for tailored birefringence and phase matching0Asymmetry-driven organic–inorganic hybrid strategy for constructing structures with exceptional organofunctionalized B–O units2A Deep-Ultraviolet Transparent Nonlinear Optical Hydrogen-Bonded Organic Framework21Strong second-harmonic generation and wide temperature range switching behavior coexisting in an ultrawide-bandgap selenate0Functional Unit Design of Deep‐UV NLO Crystals With Short Phase‐Matching and Large SHG Response22Vacuum ultraviolet second-harmonic generation in NH4B4O6F crystal73Sn 4+ /Sn 2+ Aliovalent Substitution: A Strategy for Local Structure Engineering to Enhance Birefringence and Trigger Structural Symmetry Transition0Topology-Guided Discovery of BaIn 2 Si 7 P 12 : A Quaternary Diamond-like Framework Phosphide with Giant Second-Harmonic Generation and High Laser-Induced Damage Threshold22Rational design of a quasi-0D tungsten tellurite nonlinear optical crystal with exceptionally balanced properties1Magnesium Methylphosphonate Ultraviolet Nonlinear Optical Crystal With Ultrawide Bandgap and Strong Second‐Harmonic Generation Response0NH 4 B 3 PO 6 (OH) 3 : A Hydroxyborophosphate with Short DUV Cutoff Edge and Large Birefringence2

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  2. Hydroxyfluorooxoborate (NH 4 )[C(NH 2 ) 3 ][B 3 O 3 F 4 (OH)] for exploring the effects of cation substitution on structure and optical properties

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  3. Synthesis, structure and characterization of Cd 2 TeO 3 Cl 2 with unprecedented [Cd 2 O 6 Cl 4 ] octahedral dimers

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  4. Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit

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  6. Four UV Transparent Linear and Nonlinear Optical Materials Explored from Pure Selenite Compounds

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