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RESEARCH PAPER · Chemical Society Reviews · 2024

Recent advances in rational structure design for nonlinear optical crystals: leveraging advantageous templates

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Recent advances in rational structure design for nonlinear optical crystals: leveraging advantageous templatesOriginal“One stone two birds” design of borates featuring edge-sharing [BO 4 ] and different B–O configurations in one structure utilizing covalent tetrahedra8Computer-aided screening of bismuth molybdates nonlinear optical crystals γ -Bi 2 MoO 63Large second harmonic generation and birefringence from extended octupolar π-conjugated structures35Research progress in optical materials with cationic organic planar π-conjugated groups containing CN bonds34Enhancement of growth perfection and optical transmission in rhodamine B-doped KDP single crystal for photonic applications8Exploiting Deep‐Ultraviolet Nonlinear Optical Material Rb 2 ScB 3 O 6 F 2 Originated from Congruously Oriented [B 3 O 6 ] Groups61Exploiting Deep‐Ultraviolet Nonlinear Optical Material Rb 2 ScB 3 O 6 F 2 Originated from Congruously Oriented [B 3 O 6 ] Groups4A2Cd(PO3)4 (A = K, Rb, Cs): Series of cadmium polyphosphates with infinite 1[(PO3)4]ꝏ chains and deep ultraviolet transparency windows2Carbonatoperoxovanadates with Strong Second‐Harmonic Generation: Insights from First‐Principles Calculations on Anisotropic Structures and Optical Parameters0Breaking Symmetry for SHG Response: Lanthanide Acetate Crystals via Water Molecule Regulation Strategy5From [Ba3S][GeS4] to [Ba3CO3][MS4] (M = Ge, Sn): Enhancing optical anisotropy in IR birefringent crystals via functional group implantation11From HgGa2(SeO3)4 to Hg2Ga(SeO3)2F: The first HgI-based selenite birefringent crystal triggered by linear groups and fluoride ions29Nonlinear optical properties and structural characterization of a series of carboxyanilinium hydrogen selenite hybrids: Synthesis, first-principles calculations and correlation analysis for advanced photonic applications14From β-KB3O4F2 to α-KB3O4F2: Phase Transition-Directed Great Changes in Structure and Optical Anisotropy4Impact of lanthanum doping on growth, thermal stability, linear and nonlinear optical properties of metal coordinated amino acid based single crystals of glycine copper chloride1Flexibility index: a general descriptor of polarization ability in crystalline materials3Structural modification of hydroxyborates by adjusting the number of shared oxygen atoms and hydroxyl groups for further performance enhancement1Strategically designed anisotropic organic–inorganic metal halides (OIMHs) with superior balance between bandgap and birefringence12Deep 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 response4Crystalline salt synthesis from p-dimethylaminobenzaldehyde and o-phenylenediamine, single crystal XRD study along with computational investigation103Pb 8 O 7 I 2 ·2CsI: the salt-inclusion strategy enriches the structural chemistry in lead oxyhalides1Cationic substitution engineering induces a new quaternary chalcogenide in the A–M IIIA –M IVA –Q system for optical crystal applications1Coordinated assembly of alkali and alkaline earth metals with the perfluorinated [AlF 6 ] group to design deep-ultraviolet zero-order waveplate materials2Isovalent cation substitution drives structural transformation and infrared nonlinear optical activity in Eu-based chalcogenides11Li 2 CeRbB 18 O 30 and Li 2 Cs 2 SrB 18 O 30 : promising low-birefringence materials for UV and deep UV zero-order waveplates4M 3 MoO 4 (HCO 3 ) (M = Rb and Cs): cation-tuned synthesis of two noncentrosymmetric molybdate-carbonates with isolated [MoO 4 ] and [HCO 3 ] groups0Na 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 frameworks0Optimizing optical anisotropy in low-dimensional structures via intralayer hydrogen bonding modulation and anionic substitution17Pb 2 B 10 O 16 (OH) 2 ·B(OH) 3 ·H 2 O: significantly enhanced second harmonic generation via substituting metal cations in isostructural compounds with Pb 2+2RbB 7 O 10 (OH) 2 and NaB 11 O 16 (OH) 2 : alkali metal hydroxyborates with two-dimensional layered structures and large birefringence1Synthesising a series of promising ultraviolet nonlinear optical materials with the aid of the flexibility of isolated [B 5 O 10 ] groups3The role of anionic design in modulating material properties: from SHG switching to ferroelastic switching5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)4Hot-pressing boosted nonlinear optical properties in a new ferroelectric plastic crystalline material3Mechanical Twisting-Induced Enhancement of Second-Order Optical Nonlinearity in a Flexible Molecular Crystal36Chemical Substitution‐Driven Design of a High‐Performance Noncentrosymmetric Bismuth Molybdenum Selenite10AI2Mg3Ga12S22 (AI = K, Rb): T2-type supertetrahedra coupled with [MgS6] octahedra for designing wide-band gap infrared nonlinear optical materials with well-balanced properties16Pb 4 O 3 I 2 : A Lead Oxyhalide IR Optical Crystal with an Unprecedented 1 ∞ [O 3 Pb 4 ] Chain Featuring a Wide Transmittance Range and Large Birefringence3Highly Polarizable Phosphorus‐Centered Tetrahedra and π‐Conjugated Carbon‐Centered Triangular Moieties Inducing Large Anisotropy and Short‐Wavelength Phase‐Matching23Synergistic studies on stilbazolium derivative crystal with a 4-ethylbenzaldehyde donor group for nonlinear optical systems1A Wide Band Gap Germanate with the Largest Second Harmonic Generation Response Created by Hypoxic Strategy22A Wide Band Gap Germanate with the Largest Second Harmonic Generation Response Created by Hypoxic Strategy5Na3Y2F3P2O8 and K4Y3F5P4O14: [YOF] Polyhedra Inducing Birefringence Enhancement in Non-π-Conjugated Phosphate Systems3Prediction of New Functional Fluorooxoborates with Expected Anionic Framework: A Case of CaB3O5F4Inch‐sized K[NH2(CH2COO)2]: a High‐Performance UV Nonlinear Optical Crystal Enabled by Novel Flexible π‐Conjugated Building Units, [NH2(CH2COO)2]−13Rb 7 PbY 2 (B 5 O 10 ) 3 : A Noncentrosymmetric Rare-Earth Borate Nonlinear Optical Crystal with [B 5 O 10 ] Unit16Engineering 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 relationships13Metal Cation Engineered UV Birefringent Crystals in π‐Conjugated Sulfonates with Record‐High Optical Anisotropy17From AgHgI(SO4) to AgHg3I3.2Cl1.8(SO4): Symmetry Breaking of the Belousovite‐Type Topology by Mixed Halides to Achieve Strong Nonlinear Optical Effect14Investigation into the third-order nonlinear optical properties of a three-dimensional cobalt(II) coordination polymer constructed from naphthalene-1,4-dicarboxylic acid and 4,4′-({2,2-bis[(pyridin-4-yloxy)methyl]propane-1,3-diyl}bis(oxy))dipyridine0[CON3H6BF4]: An Efficient Metal‐Free Borate with Optimized Birefringence Achieved by Structural Design Strategy15Structural and Vibrational Properties of Calcium, Strontium, Barium, and Lead Borophosphates from First Principles2[C(NH2)3]Y(HCOO)4: Constructing 3D Framework for Guanidine-Based UV Nonlinear Optical Crystals with Good Performance8Machine Learning Prediction on Birefringence of Nonlinear Optical Crystals and Polymorphs with Different Birefringence Activities2Supercontinuum generation: A comprehensive review of experimental and material advances5[C( NH2 )3] 2SiF6 : Design of Deep Ultraviolet Crystals with Large Birefringence Based on a Fluorination‐Oriented Strategy13Achieving excellent nonlinear optical performance via “dimensionality elevation”-driven transformation from centrosymmetric to non-centrosymmetric structures1NH4B5O7(OH)2 and CsRbB10O14(OH)4·H2O: Two Hydroxyborates Feature Significant Optical Anisotropy and Contain 1∞[B5O7(OH)2] Chains1Cation-modulated aligned arrangement of [B3O7] units in an unprecedented 2∞[B3O5] layer with remarkable birefringence10Giant Birefringence and Strong Third-Order Nonlinear Optical Response in a Hybrid Crystal Templated by a Push–Pull π-Conjugated System6Strongly Polar [H2PO3]− Induced π-Conjugated Group Arrangement for Balanced UV Nonlinear Optical Performance3Resonant Raman scattering and optical absorption studies of Zn(II) impurities in L-alanine single crystal0Anion-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 borates20First-principles study of structural, electronic and nonlinear optical properties under pressure for trigonal borophosphatesABPO5 (A=Ca, Sr, Pb, Ba)1Borosilicates as deep-ultraviolet transparent nonlinear optical crystals: Structural motifs, performance limits and future directions9Glass-Forming Ionic Liquid Crystal Gold–Carbon Nanocomposites with Ultrafast Optical Nonlinearity Sign Reversal1Tuning the Anionic Configuration in ASc2(P2O7)2 (A = Ba, Pb) through A-Site Cationic Coordination Engineering0[C(NH2)3]Pb(C2O4)Cl·H2O: A halogen- and lone-pair-tuned UV crystal with large birefringence originated from cooperative π-conjugation6Experimental and theoretical analysis of CuO-Doped N Cyanomethyl-N-methyl-4-nitroaniline: structural modelling, spectroscopic, and quantum chemical investigation on metal-organic hybridization towards nonlinear optical enhancement0Resonant Second-Harmonic Generation in a Hybrid Manganese Bromide: [3-Quinuclidinone]2MnBr43Study of Cleavage Fracture Strength of Cation-Tuned Yttrium Calcium Oxyborate Crystals0Triple Integration of π‐Conjugated Building Blocks: Unprecedented Assembly for Large Optical Anisotropy11A Triazole–Thiophene‐Based Compound with Potential Nonlinear Optical Properties and β‐Lactamase Inhibitory Activity to Protect β‐Lactam Antibiotics0Effect of Multiple Hydrogen Bonding on the π-Conjugated Groups and Optical Properties in Molecular Crystals5Tuning birefringence in alkaline-earth metal oxyhalides through diverse mixed-cation coordination architectures1K 6 Mo 8 PO 29 OH·H 2 O and K 6 Mo 5 P 2 O 23 ·7H 2 O: strongly distorted [MoO 6 ] octahedral groups effectively enhance birefringence0REXCO3 (RE = La, Ce, Y; X = OH, F) with circular alignment of anionic motifs induced extraordinary nonlinear optical effects0Achieving Ultra‐High Optical Anisotropy via Structural Regulation and Coplanar Engineering of Extended π‐Conjugated [H 2–x C 3 N 3 S 3 ] (x = 1, 2) Groups3Asymmetry-driven organic–inorganic hybrid strategy for constructing structures with exceptional organofunctionalized B–O units2Templating Methods for Materials Fabrication Across Scales19Navigating the Landscape of Next-Generation Nonlinear Optical Materials Discovery: Opportunities and Challenges Driven by Artificial Intelligence4[Rb 4 Cl][Cd 11 In 9 Se 26 ]: a salt inclusion chalcogenide with a diamond-like framework for infrared nonlinear optics0A promising mid-infrared nonlinear optical crystal with well-balanced properties0Achieving an optimal performance balance in UV nonlinear optical crystals via hydrogen-bond regulation1Chemical memory in nanostructured transducers for scalable biosensing: from synthesis to device-ready interfaces0Chiral Eu–K Metal–organic Framework Based on Lactate Derivative and Its Second-Order Nonlinear Optical Properties0CsB(OH) 4 (H 2 O) 2 and Na(NH 4 ) 2 B 10 O 16 OH(H 2 O): a hydroxylation modification strategy regulates the borate structures and optical properties0Design of benzoxazolium-based nonlinear optical crystals with large second-order harmonic generation responses0Effect of the cation-to-silicon ratio on structural transformation and optical performance in [NaSr 3 Cl 3 ][SiS 4 ] and [NaSr 4 SCl][Si 3 S 9 ]0Internally and externally induced chiral hybrid metal halide materials for advanced chiroptoelectronic applications23Synthesis and characterization of mixed carbonate and bicarbonate materials as candidates for deep-UV applications1The condensation of π-conjugated units: a new paradigm for designing high-performance optical crystals4Realizing Phase‐Matching of Nonlinear Optical [ABa 3 Br 2 ][Ga 5 Se 10 ] (A = Cs, Rb, K, Na) Through Large Anisotropic Lattice Distortion6Realizing Phase‐Matching of Nonlinear Optical [ABa 3 Br 2 ][Ga 5 Se 10 ] (A = Cs, Rb, K, Na) Through Large Anisotropic Lattice Distortion11Bonding-type-driven structural transformation toward novel fluoroiodosulfates: Achieving non-centrosymmetry and enhanced optical properties in K2(IO3F)SO30[C(NH 2 ) 3 ]SbCl 4 : An NLO Material with Enhanced Second Harmonic Response and Birefringence3Discovering Structure-Adaptive Oxides for Embedded Epitaxial Growth of Perovskite Nanocrystals1Zn 4 (BO 3 ) 2 (CO 2 CH 2 NH 2 ) 2 ·H 2 O: An Organic–Inorganic Hybridized KBe 2 BO 3 F 2 -like Ultraviolet Nonlinear Optical Crystal3Sn 4+ /Sn 2+ Aliovalent Substitution: A Strategy for Local Structure Engineering to Enhance Birefringence and Trigger Structural Symmetry Transition0Harnessing tetrahedral diversity: The path to superior diamond-like IR NLO crystals13Unlocking Strong SHG Response and Large Birefringence in Hybrid Antimony Halides via a Three-in-One Strategy7Coordination Geometry-Directed Optical Anisotropy and Phase-Matched Nonlinear Optics in Chiral Metal–Organic Frameworks2[C 3 N 2 H 5 ]B 7 O 10 F 2 : Demonstrating a New Hydrogen‐Bond‐Induced Intralayer Charge‐Balanced Structure Model with Large Birefringence3LiK4B(SO4)4: a potential optical crystal for deep ultraviolet zero-order waveplates1Hydrogen-Bond-Directed Assembly of an Intramolecular Charge-Transfer Compound for Second-Order Nonlinear Optics1Mg Substitution in BaGa 4 Se 7 : Synthesis, Structure, and Property Modulation2Disentangling solvent effects on optical response via p-π and sp² lone-pair contributions in non-aromatic fused systems5NH 4 B 3 PO 6 (OH) 3 : A Hydroxyborophosphate with Short DUV Cutoff Edge and Large Birefringence2(C 5 H 7 N 2 ) (C 8 H 4 O 4 ) PbBr: Jahn–Teller Distortion‐Induced Tilting of π‐Conjugated Planes Resolving the Second‐Order Polarizability–Structural Anisotropy Conflicts13(C 5 H 7 N 2 ) (C 8 H 4 O 4 ) PbBr: Jahn–Teller Distortion‐Induced Tilting of π‐Conjugated Planes Resolving the Second‐Order Polarizability–Structural Anisotropy Conflicts1Boosting Ultraviolet Phase‐Matching Performance of B 3 O 7 ‐Based Systems via Synergistic Fluorination and Organic Modification Strategy1Structural, vibrational, and proton-conducting properties of LiH2PO4 single crystals: a multifunctional wide-bandgap solid-state electrolyte1Enantiomeric Cd-based coordination polymers with multilevel helical structures and significant second NLO response constructed from lactic acid derivatives2Minimizing Oscillator Strength: A Strategy for Engineering Deep-Ultraviolet Nonlinear Optical Crystals with Optimized Refractive-Index Dispersion0Hydrogen‐Bond‐Directed Assembly of Urea Derivatives: Exceptional Birefringence Achieved by π ‐Conjugated Unit Alignment3Strong Optical Nonlinearity in Polar Hypophosphites via Chiral Cation Assembly1Positional Isomerism Controls Polarity and Nonlinear Optical Properties in One‐Dimensional Hybrid Germanium Halides0Circumventing the Eg–SHG trade-off in selenides: Salt-inclusion [X4Br2][MGa4Se10] with concurrent large band gap and strong nonlinear optical response1Investigation of heat-induced grown KDP single crystal and modified optical and thermophysical properties for optoelectronics applications0F−/OH− terminal modification of [B3O6] clusters: Constructing deep-ultraviolet hydroxyfluorooxoborates with tunable optical performance0Reverse Weak Polarity‐Induced Ordered Layer Control for Enhanced Second‐Harmonic Generation in Ultraviolet Nonlinear Optical Crystals2Investigation of the growth, optical and thermal properties, and cleavage fracture strength of Mg2+-doped YCOB crystals0Chirality transfer in helical supramolecular frameworks: Structures and SHG response modulation of Zinc(II) coordination polymers based on lactic derivatives1Assembly of Functional Units for Constructing an Ultraviolet-Transparent Nonlinear Optical Mixed Alkaline Metal Borate-Formate1Noncentrosymmetric monomeric nickel(II) complexes with second-harmonic generation and high iodine capture capacity0Lock‐and‐Key Assembly Enables Record Birefringence in Monocyclic π‐Conjugated Crystals via Spatial Confinement of Linear Polyhalide5Lock‐and‐Key Assembly Enables Record Birefringence in Monocyclic π‐Conjugated Crystals via Spatial Confinement of Linear Polyhalide0Engineering Three-Chamber Core–Sheath Cellulose Acetate Nanofibers via Multifluid Electrospinning for Enhanced Wettability and Tunable Initial Drug Release Behavior0Unlocking Nonlinear Optics and Photoluminescence with Simultaneous Enhancement of Bandgap and Birefringence in Hybrid Sb-Based Halides2A Strategy for Enhancing the Optical Anisotropy of Phosphates via Tetrahedral Unit Modification0Seed-assisted growth, structural, thermal, and linear/nonlinear optical properties of potassium 18-crown-6 ether cadmium trithiocyanate (KCCTC) single crystal0Prediction of deep-ultraviolet nonlinear optical material in borosilicate system: a case of RbSiB3O70Parallel arrangement of functional building blocks: toward performance synergy in oxalate borate ultraviolet nonlinear optical crystals0From High Symmetry to High Symmetry: A Self‐Assembly Strategy for Synthesizing Large Birefringent Borates0Growth of High-Quality CLBO Crystals for High-Power 266 nm DUV Laser0MZnCO3OH: A family of hydroxycarbonate nonlinear optical crystals in the UV and DUV regions0Entropy‐Driven Precursor Symmetry Breaking for Phase‐Selective Synthesis of Noncentrosymmetric Rb 2 CdCl 2 I 20Crystal structure and supramolecular organization of D-phenylalaninium chloride: hydrogen-bond topology, Hirshfeld surface analysis, and thermally induced crystal-to-crystal phase transitions1Multidimensional Cation Modulation toward Phase-Matchable Nonlinear Optical Fluorides with Short UV Cutoff Edges0Chiral dinuclear EuIII enantiomeric pairs: simultaneously showing photoluminescences, circularly polarized luminescences, second- and third-harmonic generations with enhanced performances0Advancing optoelectronic material: Growth and functional property assessment of Imidazolium malonate (IML) single crystal with enhanced third order nonlinear optical response0Structure, bonding and nonlinear optical (NLO) properties of noble gas (Ng)-inserted [Be(C4H4)] half-sandwich complexes0A Polar Magnetic Tetrachloroferrate Hybrid Crystal Enabling Piezoelectric Energy Harvesting and Nonlinear Optical Functionality0Potential Deep Ultraviolet Phosphate With Y‐Based: 1 [(PO 3 ) 4 ] ∞ Chains AYP 4 O 12 (A = K, NH 4 ) and the First [P 3 O 10 ] Anionic Framework KLiYP 3 O 100Three Rare‐Earth Metal Borates Synthesized via a Cation Substitution Strategy as Potential Zero‐Order Waveplate Materials0FBB-directed open framework evolution in alkali metal borates: Synthesis and structure property relationships of NaRb2B9O150Coordination chemistry of Sb(III)-based optical crystals: from lone-pair-induced distortion to birefringence and second-harmonic generation0

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  2. Computer-aided screening of bismuth molybdates nonlinear optical crystals γ -Bi 2 MoO 6

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  3. Large second harmonic generation and birefringence from extended octupolar π-conjugated structures

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