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RESEARCH PAPER · Coordination Chemistry Reviews · 2020

Structure-property relationship in nonlinear optical materials with π-conjugated CO3 triangles

Youchao Liu, Yaoguo Shen, Sangen Zhao, Junhua Luo

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Structure-property relationship in nonlinear optical materials with π-conjugated CO3 trianglesOriginal(Na0.60Ba0.70)Ga2Se4: An Infrared Nonlinear Optical Crystal Designed using AgGaSe2 as the Template38A review on phase transition and structure-performance relationship of second-order nonlinear optical polymorphs107Inherent laws between tetrahedral arrangement pattern and optical performance in tetrahedron-based mid-infrared nonlinear optical materials130Structure-property survey and computer-assisted screening of mid-infrared nonlinear optical chalcohalides113Comprehensive Density Functional Theory Studies of Vibrational Spectra of Carbonates63Synergism of multiple functional chromophores significantly enhancing the birefringence in layered non-centrosymmetric chalcohalides20Distinctive modulation of optical anisotropy by halogens in α/β-Cd–P–X (X = Cl, Br, and I)2From [B 6 O 13 ] 8− to [GaB 5 O 13 ] 8− to [Ga{B 5 O 9 (OH)}{BO(OH) 2 }] 2− : synthesis, structure and nonlinear optical properties of new metal borates10High-pressure synthesis and crystal structure of non-centrosymmetric K 2 Ca 3 (CO 3 ) 410Potassium L-ascorbate monohydrate: a new metal–organic nonlinear optical crystal6A comprehensive survey on nonlinear optical phosphates: Role of multicoordinate groups106Finding Short-Wavelength Birefringent Crystals with Large Optical Anisotropy Activated by π-Conjugated [C(NH2)3] Units45Second-order nonlinear optical property of the ultraviolet transparent alkali metal-rare earth metal carbonate Na3Y(CO3)3.3H2O5Molecular Engineering toward an Enlarged Optical Band Gap in a Bismuth Sulfate via Homovalent Cation Substitution26Cyanurates consisting of intrinsic planar π-conjugated 6-membered rings: An emerging source of optical functional materials111Polar polymorphism: β-Ca2[B5O8(OH)]2[B(OH)3]·H2O—synthesis, structure and nonlinear optical property11Te(CS(NH2)2)4SO4·2H2O: A Three-in-One Semiorganic Nonlinear Optical Crystal with an Unusual Quadrilateral (TeS4)6– Chromophore14From Centrosymmetry to Noncentrosymmetry: Tailoring the Structural Arrangements of Carbonates with Strong Nonlinear Optical Response through Partial Anion Substitution33Be2(BO3)(IO3): The First Anion‐mixed Van der Waals Member in the KBe2BO3F2 Family with a Very Strong Second Harmonic Generation Response130Be2(BO3)(IO3): The First Anion‐mixed Van der Waals Member in the KBe2BO3F2 Family with a Very Strong Second Harmonic Generation Response8High-Performance Second-Harmonic-Generation (SHG) Materials: New Developments and New Strategies323Structure-performance relationship in tri-coordinated nonlinear optical materials toward optimal second harmonic generation and phase matching31Group 12 Carbonates and their Binary Complexes with Nitrogen Bases and FH2Z Molecules (Z=P, As, Sb): Synergism in Forming Ternary Complexes11LiB2O3F: A Beryllium-Free Deep-Ultraviolet Nonlinear Optical Material Designed Based on a Boron-Rich Strategy61Centrosymmetric or Noncentrosymmetric? Transition Metals Talking in K 2 TGe 3 S 8 (T = Co, Fe)25KCs2[Pb2Br5(HCOO)2]: A Polar 3D Lead‐Bromide Framework Exhibiting Strong Second‐Harmonic Generation Response10Sr5(CO3)2(BO3)2: A new family member of isostructural mixed borate and carbonate Ba4M(BO3)2(CO3)2 (M = Ba, Sr) with isolated BO3 and CO3 groups7Synthesis, structure, and nonlinear optical property of Bi0.33Sb0.67SI1Enhancement of band gap and birefringence induced via π -conjugated chromophore with “tail effect”28Halogen-Ion-Induced Structural Phase Transition Giving a Polymorph of HgBr2 with Balanced Nonlinear Optical Properties8Complex coordinated functional groups: A great genes for nonlinear optical materials64AZn 2 (BO 3 )Si 2 O 5 (A = Rb, Cs): first examples of KBe 2 BO 3 F 2 structure type in the borosilicate family exhibiting a deep-ultraviolet cutoff edge25Phase Matchability Transformation in the Infrared Nonlinear Optical Materials with Diamond‐Like Frameworks63A 2 P 2 S 6 (A = Ba and Pb): a good platform to study the polymorph effect and lone pair effect to form an acentric structure28KF·B(OH) 3 : a KBBF-type material with large birefringence and remarkable deep-ultraviolet transparency33KRE(CO 3 ) 2 (RE = Eu, Gd, Tb): new mixed metal carbonates with strong photoluminescence and large birefringence15Linear unit BN 2 : a novel birefringence-enhanced fundamental module with sp orbital hybridization9Performance of optical materials with the derivative of planar π-conjugated groups: Recent advances and future prospects37Review of Heteroleptic Tetrahedra as Birefringent or Nonlinear Optical Motifs17Ba6(CuxZy)Sn4S16 (Z = Mg, Mn, Zn, Cd, In, Bi, Sn): High Chemical Flexibility Resulting in Good Nonlinear-Optical Properties12M@[12-crown-4] and M@[15-crown-5] where (M=Li, Na, and K); the very first examples of non-conventional one alkali metal-containing alkalides with remarkable static and dynamic NLO response21Promising Deep‐Ultraviolet Birefringent Materials via Rational Design and Assembly of Planar π‐Conjugated [B(OH)3] and [B3O3(OH)3] Functional Species6Promising Deep‐Ultraviolet Birefringent Materials via Rational Design and Assembly of Planar π‐Conjugated [B(OH)3] and [B3O3(OH)3] Functional Species83An Optimized KBe2BO3F2‐Like Structure: The Unity of Deep‐Ultraviolet Transparency, Nonlinear Optical Property, and Ferroelectricity22Directional Construction of New Nonlinear Optical Bifunctional Units through Molecular Engineering Design Inspired by the B 3 O 7 -Typed Configuration23A comprehensive review on metal chalcogenides with three-dimensional frameworks for infrared nonlinear optical applications114Crystal Growth of K2HCO3F·H2O with a Very Short Cutoff Edge and Large Birefringence17Oxychalcogenides as Promising Ultraviolet Nonlinear Optical Candidates: Experimental and Theoretical Studies of AEGeOS2(AE = Sr and Ba)24Chemical Bonding Effects and Physical Properties of Noncentrosymmetric Hexagonal Fluorocarbonates ABCO3F (A: K, Rb, Cs; B: Mg, Ca, Sr, Zn, Cd)10Achieving Large Second Harmonic Generation Effects via Optimal Planar Alignment of Triangular Units64Perfectly Encoding π‐Conjugated Anions in the RE5(C3N3O3)(OH)12 (RE=Y, Yb, Lu) Family with Strong Second Harmonic Generation Response and Balanced Birefringence91Perfectly Encoding π‐Conjugated Anions in the RE5(C3N3O3)(OH)12 (RE=Y, Yb, Lu) Family with Strong Second Harmonic Generation Response and Balanced Birefringence18New lead-iodide formates with a strong second-harmonic generation response and suitable birefringence obtained by the substitution strategy8M(NH2SO3)2·xH2O (M = Ca, Pb, x = 0, 1, 4): Effect of Hydrogen Bonding on Structural Transformations and Second Harmonic Generation of Metal Sulfamates26Ba5Ga2SiO4S6: a Phase-Matching Nonlinear Optical Oxychalcogenide Design via Structural Regulation Originated from Heteroanion Introduction25d6versus d10, Which Is Better for Second Harmonic Generation Susceptibility? A Case Study of K2TGe3Ch8 (T = Fe, Cd; Ch = S, Se)18Evaluating refractive index and birefringence of nonlinear optical crystals: Classical methods and new developments45Tetrahedron-based deep-ultraviolet nonlinear optical crystal with optimized KBe 2 BO 3 F 2 -like structure and disordered cations2Toward Large Second-Harmonic Generation and Deep-UV Transparency in Strongly Electropositive Transition Metal Sulfates112Recent progress in the design of IR nonlinear optical materials by partial chemical substitution: Structural evolution and performance optimization133Comprehensive review on multiple mixed-anion ligands, physicochemical performances and application prospects in metal oxysulfides32Four New Sb‐based Orthophosphates: Cation Regulation to Investigate Diversified Structural Architecture1Sb4O3(TeO3)2(HSO4)(OH): An Antimony Tellurite Sulfate Exhibiting Large Optical Anisotropy Activated by Lone Pair Stereoactivity30Enhanced charge separation and O2 activation over an anion-rich photocatalyst Ba3(BO3)(CO3)F for metronidazole removal in water10Synthesis, Structure, and optical properties of Y3GaGe0.5S7: A new member in the polar R3MTQ7 family4A three orders of magnitude increase in nonlinear optical response by external electric field on Cryptand[2.2.2] (C222) based alkaline earthides8Pb(OH)I: A lead(II)-based oxyhalide with a large birefringence5Synthesis, Crystal Structure, and Nonlinear-Optical Properties of a Diamond-Like Chalcogenide Cu 2 GeS 313From Centrosymmetry to Noncentrosymmetry: Precise Structural Regulation and Characterization on ZnHPO3·2H2O Polymorphs13From Monofluorophosphates A2PO3F to Difluorophosphates APO2F2 (A = alkali metal): Design of a Potential Deep-Ultraviolet Nonlinear Optical Materials System with a Shortened Phase-Matching Wavelength41The Strategy to Improve the Phase Matching Ability in Tetrahedron‐Based Deep‐Ultraviolet Nonlinear Optical Crystals21Introduction of the [B–O/F] Units Enhances the Band Gap and Birefringence from Na6Mg3B10O18F6 to K3NaB10O16F211Investigation of the Optical Spectra of Barium-Zinc (Aluminum) Fluoroborates and Barium-Zinc Fluorocarbonate from First Principles7A ll HgM IV S 4 (A ll = Sr, Ba, M IV = Si, Ge): A Series of Materials with Large Second Harmonic Generation Response and Wide Band Gaps27Double alkaline earth metals sulfide SrMgGeS4 with high laser-induced damage threshold and strong second-harmonic generation29New Functional Groups Design toward High Performance Ultraviolet Nonlinear Optical Materials95A Sharp Improvement of Sulfate's Birefringence Induced by the Synergistic Effect of Heteroleptic and Dimeric Strategies14Secondary‐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 Birefringence41Exploration of antimony( iii ) oxyhalides via single-site substitution in quest of large birefringence10Exploring a new short-wavelength nonlinear optical fluoride material featuring unprecedented polar cis -[Zr 6 F 34 ] 10− clusters48Exploring short-wavelength birefringent crystals via triggering cooperative arrangement between different π-conjugated groups8Rare-earth-based chalcogenides and their derivatives: an encouraging IR nonlinear optical material candidate70Toward the ultraviolet (UV) or deep-UV nonlinear optical crystals: The combination of π-conjugated planar [XY3] and tetrahedral [XY4]80The Birefringence Modulation in Short‐Wave Ultraviolet Sulfates with Functional π‐Conjugated Cations and Polymerized Heteroleptic Tetrahedral Anions18Centrosymmetric CaBaMF8 and Noncentrosymmetric Li2CaMF8 (M = Zr, Hf): Dimension Variation and Nonlinear Optical Activity Resulting from an Isovalent Cation Substitution-Oriented Design17Theoretical Investigation of Structural, Electronic and Optical Properties of Cs3MoO4(HCO3) with NLO Active Functional Units2Soaking the Rare-Earth Carbonates for a Change: An Alternative Approach to Explore Carbonate Nonlinear Optical Crystals2Coupling between cation and anion disorder in β-K 2 Ca 3 (CO 3 ) 44A Noncentrosymmetric Metal‐Free Borophosphate: Achieving a Large Birefringence and Excellent Stability by Covalent‐Linkage27Nonlinear optical, dielectric, and piezoelectric properties of hexagonal fluorocarbonates ABCO3F (A: K, Rb, Cs; B: Mg, Ca, Sr, Zn, Cd, Pb) from first principles3Na3K6(CO3)3(NO3)2X·6H2O (X = NO3, Cl, Br): Exploring High-Performance UV Birefringent Crystals Induced by Coplanar π-Conjugated CO3 and NO3 Groups15An Unprecedented [BO2]‐Based Deep‐Ultraviolet Transparent Nonlinear Optical Crystal by Superhalogen Substitution33An Unprecedented [BO2]‐Based Deep‐Ultraviolet Transparent Nonlinear Optical Crystal by Superhalogen Substitution1Theoretical design of alkaline earthides M+(36 adz) Be− (M+ = V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) with excellent nonlinear optical response and ultraviolet transparency10Recent advances and future perspectives on rare-earth-based nonlinear optical materials with π-conjugated [XO3] (X = B, C, N) units66Cs2Pb(CO3)2: a novel mixed-metal carbonate with rare Pb-C-O one-dimensional chain0Exploration of the structure, electronic and optical properties of AB 2(PO3)5 polyphosphates: a first-principle approach3From B 3 O 3 (OH) 3 to B 3 O 3 F 3 : Uncovering Series of New Functional Units Based on [BO 2 F] Beneficial for Deep‐Ultraviolet Birefringence1Toward Strong UV–Vis–NIR Second-Harmonic Generation by Dimensionality Engineering of Zinc Thiocyanates32Breaking 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 implantation11SbO(OH)2(IO3): The First Polar Sb5+‐Iodate with a Strong Second‐Harmonic Generation Response and a Wide Bandgap8Functional assembly and modification of nonlinear optical fundamental motifs in phosphates27The New Paradigm of Ligand Substitution-Driven Enhancement of Anisotropy from SO4 Units in Short-Wavelength Region14Emergent Mid‐Infrared Nonlinear Optical Candidates With Targeted Balance Performances17Deep-ultraviolet sulfamate halides with halogen-centered secondary building units for enhanced optical anisotropy4[C 2 N 4 H 7 O][NH 2 SO 3 ]: High‐Performance Ultraviolet Nonlinear Optical Crystal with Ditrigon Coupled Guanylurea Group9[C 2 N 4 H 7 O][NH 2 SO 3 ]: High‐Performance Ultraviolet Nonlinear Optical Crystal with Ditrigon Coupled Guanylurea Group48Lithium Borate-Squarate: An Organic–Inorganic Groups-Mixed Nonlinear Optical Crystal with Large Birefringence4K3[HCO3]2F: a new deep-UV birefringent crystal exhibiting strong optical anisotropy17Regulation of Refractive Index by Halogens in Two-Dimensional Layered Methylsulfonate Halides7Review of KBe2BO3F2-like second-order nonlinear optical materials and their structure-performance relationships13Second-Harmonic Generation Response in Nitridophosphates MP2N4 (M = Ge, Sn, Pb) and the Role of Stereochemically Active Lone Pairs6Recent progress in structural design strategies of high-birefringence optical crystals54CsLa(SO 4 ) 2 : A Lanthanum Sulfate Crystal for Nonlinear Optical Applications10Halide Ion-Directed Symmetry Control in π-Conjugated Molecular Crystals6Enhanced nonlinear optical response of alkaline earthides based on transition metals as a source of excess electrons in the presence of horizontally oriented external electric field8La(SO3NH2)2NO3·H2O: synergistic anion engineering of the first rare-earth nitrate sulfamate defying transparency-birefringence-nonlinearity trade-offs in ultraviolet nonlinear optics8A-Site Cation Substitution toward Structural Transformation in Phosphates Exhibiting Short UV Transparency and Second Harmonic Response3Ag(Te2O3)(PO4): The first Ag-containing phosphate-tellurite nonlinear optical crystal featuring novel zigzag layered structure0Symmetry‐Aware Equivariant Network for Discovering SHG‐Active Materials5REXCO3 (RE = La, Ce, Y; X = OH, F) with circular alignment of anionic motifs induced extraordinary nonlinear optical effects0Asymmetry-driven organic–inorganic hybrid strategy for constructing structures with exceptional organofunctionalized B–O units2Chiral-Unit-Driven Short-Wave Ultraviolet Nonlinear Optical Acetates with Balanced Overall Optical Properties3LiV 3 Se 2 O 12 : A Promising Giant‐Birefringent Crystal Enabled by Significant Structural Distortion3Synthesis, Crystal Growth, Linear, and Nonlinear Optical Properties of Water-Grown Giant Optical Anisotropic Thiocyanates ABi(SCN) 4 (A = Rb, Cs)3Ligand modification on organotin-oxo clusters for enhanced third-order nonlinear optical response0LiHgTeO 3 : a Hg( i )-containing tellurite crystal with typical Hg–Hg bonds0Synergism of [C 2 N 4 H 7 S] cations and anionic modulators: tailoring second-order nonlinear optics and birefringence in organic–inorganic crystals6Synthesis and characterization of mixed carbonate and bicarbonate materials as candidates for deep-UV applications1Truss bridge-like anhydrous stacking in hybrid crystals triggers ultra-high stability and robust birefringence0Unit Symmetry‐Breaking and Layered Linear Ordering Enabling Superior Short‐Wave Ultraviolet Birefringent Crystal8Unit Symmetry‐Breaking and Layered Linear Ordering Enabling Superior Short‐Wave Ultraviolet Birefringent Crystal21D Cobalt‐Cytidine Monophosphate Coordination Polymer Exhibiting Efficient Ultraviolet Second‐Harmonic Generation7First Principles Calculations of Structures, Mechanical and Vibrational Properties of Nonlinear Optical LiZnCO3(OH) and NaZnCO3(OH) Crystals0Water‐Facilitated Diamond Formation in the Deep Mantle0Zn(C 2 H 4 NO 2 ) 2 (SO 2 CH 3 NH 2 ) 2 and Zn(C 2 H 4 NO 2 ) 2 [SO 2 (NH 2 ) 2 ]: Regulation of Unique ZnO(C 2 H 4 NO 2 ) 2 Units by Polar Tetrahedrons for Balanced UV Nonlinear Optical Performance0An Integrated Machine Learning Workflow Based on Deep Generative Models for Discovery of Inorganic Nonlinear Optical Crystals0Molecular modeling of [15]anen5 based alkaline earthides to explore their electronic and nonlinear optical properties0Designing Novel Solar‐Blind Ultraviolet Nonlinear Optical Crystals Based on Local Proton Distribution Complementary Effect0Designing Novel Solar‐Blind Ultraviolet Nonlinear Optical Crystals Based on Local Proton Distribution Complementary Effect0The Multi‐Scale Paradigm: An Integrated Design Logic for Nonlinear Optical Crystals1The Multi‐Scale Paradigm: An Integrated Design Logic for Nonlinear Optical Crystals0Borophosphate-based second-order nonlinear optical materials: Advances in structural diversity and optical performance0Cation‐Regulated [CH 3 BO 2 F]‐Derived Borates: Synergistic Fluorination and Organic Functionalization for High‐Birefringence UV NLO Materials0

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  4. Structure-property survey and computer-assisted screening of mid-infrared nonlinear optical chalcohalides

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  5. Comprehensive Density Functional Theory Studies of Vibrational Spectra of Carbonates

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  35. KF·B(OH) 3 : a KBBF-type material with large birefringence and remarkable deep-ultraviolet transparency

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  36. KRE(CO 3 ) 2 (RE = Eu, Gd, Tb): new mixed metal carbonates with strong photoluminescence and large birefringence

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  37. Linear unit BN 2 : a novel birefringence-enhanced fundamental module with sp orbital hybridization

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