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RESEARCH PAPER · Inorganic Chemistry Frontiers · 2020

Inorganic planar π-conjugated groups in nonlinear optical crystals: review and outlook

Pifu Gong, Xiaomeng Liu, Lei Kang, Zheshuai Lin

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Inorganic planar π-conjugated groups in nonlinear optical crystals: review and outlookOriginalSecond-order nonlinear optical materials with a benzene-like conjugated π system49A review on phase transition and structure-performance relationship of second-order nonlinear optical polymorphs107New Alkaline-Earth Metal Fluoroiodates Exhibiting Large Birefringence and Short Ultraviolet Cutoff Edge with Highly Polarizable (IO 3 F) 2– Units63Structure-property survey and computer-assisted screening of mid-infrared nonlinear optical chalcohalides113Mechanochemical Preparation and Solid-State Characterization of 1:1 and 2:1 Ionic Cocrystals of Cyanuric Acid with Alkali Halides12Ba3(BO3)(CO3)F: The First Borate Carbonate Fluoride Synthesized by the High‐Temperature Solution Method19Structural, spectral and nonlinear optical analysis of Sodium bis(2-methyllactato)borate: a new semiorganic crystal for photonic applications6Bi 32 Cd 3 P 10 O 76 : a new congruently melting nonlinear optical crystal with a large SHG response and a wide transparent region24Ba 2 B 7 O 12 F with novel FBB [B 7 O 16 F] and deep-ultraviolet cut-off edge31Comprehensive Density Functional Theory Studies of Vibrational Spectra of Carbonates63Borates: A Rich Source for Optical Materials1089Chiral Template‐Driven Macroscopic Chirality Control: Structure‐Second‐Harmonic Generation Properties Relationship24Synergism of multiple functional chromophores significantly enhancing the birefringence in layered non-centrosymmetric chalcohalides20A 3 Mn 2 Sb 3 S 8 (A = K and Rb): a new type of multifunctional infrared nonlinear optical material based on unique three-dimensional open frameworks53Ba 2 Ge 2 Te 5 : a ternary NLO-active telluride with unusual one-dimensional helical chains and giant second harmonic-generation tensors31BaTi(BO 3 ) 2 : an excellent birefringent material with highly coplanar isolated [BO 3 ] groups16Pb 2.28 Ba 1.72 B 10 O 19 featuring a three-dimensional B–O anionic network with edge-sharing [BO 4 ] obtained under ambient pressure6Recent progress in oxychalcogenides as IR nonlinear optical materials79Toward the Enhancement of Critical Performance for Deep-Ultraviolet Frequency-Doubling Crystals Utilizing Covalent Tetrahedra137Preparation, characterization, and nonlinear optical properties of graphene oxide thin film doped with low chirality metallic SWCNTs33Cyanurates consisting of intrinsic planar π-conjugated 6-membered rings: An emerging source of optical functional materials111From Centrosymmetry to Noncentrosymmetry: Tailoring the Structural Arrangements of Carbonates with Strong Nonlinear Optical Response through Partial Anion Substitution33Fluorine‐Driven Enhancement of Birefringence in the Fluorooxosulfate: A Deep Evaluation from a Joint Experimental and Computational Study139Structure-performance relationship in tri-coordinated nonlinear optical materials toward optimal second harmonic generation and phase matching31A 3D supramolecular framework assembled via π⋅⋅⋅π interactions and CH⋅⋅⋅Cl hydrogen-bonds with second-harmonic generation response2Centrosymmetric or Noncentrosymmetric? Transition Metals Talking in K 2 TGe 3 S 8 (T = Co, Fe)25Strain-Driven Polarized Electric Field-Promoted Photocatalytic Activity in Borate-Based CsCdBO3 Bulk Materials30Transition-metal-based chalcogenides: A rich source of infrared nonlinear optical materials184The Rise of Infrared Nonlinear Optical Pnictides: Advances and Outlooks36Synthesis, structure, and nonlinear optical property of Bi0.33Sb0.67SI1Chalcogen Bond Involving Zinc(II)/Cadmium(II) Carbonate and Its Enhancement by Spodium Bond9Superior nonlinear optical and optical limiting properties of cross-linked and thermally stable HiPCO-SWCNTs@PVA films17Guanidinium Fluorooxoborates as Efficient Metal-free Short-Wavelength Nonlinear Optical Crystals140Phase Matchability Transformation in the Infrared Nonlinear Optical Materials with Diamond‐Like Frameworks63(C 3 N 6 H 7 ) 2 SiF 6 ·H 2 O: an ultraviolet birefringent crystal exceeding the intrinsic energy gap of an organic reagent38(N 2 H 6 )[HPO 3 F] 2 : maximizing the optical anisotropy of deep-ultraviolet fluorophosphates33A 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 structure28A novel 2-(aminomethyl)pyridineH 2 PO 4 crystal with second-order nonlinear optical performance8Li 6.58 Na 7.43 Sr 4 (B 9 O 18 )(B 12 O 24 )Cl: unprecedented combination of the largest two highly polymerized isolated B–O clusters with novel isolated B 9 O 18 FBB18Na 3 B 6 O 10 (HCOO): an ultraviolet nonlinear optical sodium borate-formate33PbBe 2 B 2 O 6 : an ultraviolet nonlinear-optical crystal with unprecedented π–π interacting BeBO 5 group13Performance of optical materials with the derivative of planar π-conjugated groups: Recent advances and future prospects37Two porous-layered borates built by B 7 O 13 (OH) clusters and AlO 4 /GaO 4 tetrahedra7Review 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 Properties12Inorganic nonlinear optical materials7CsY(SO4)2·4H2O: A Deep-Ultraviolet Birefringent Crystal Induced by an Edge-Sharing Connection26Nonlinear Optical Benzoindolium-Based Single Crystals: H-Contacts Induced Noncentrosymmetric Alignment Approaching Efficient Terahertz-Wave Generation17Cooperative Enhancement of Second Harmonic Generation in an Organic–Inorganic Hybrid Antimony Halide63The Kurtz-Perry powder technique revisited: A case study on the importance of reference quality and broadband nonlinear optical measurements using LiInSe232Self-Assembled Nonlinear Optical Crystals Based on an Asymmetric Fluorenone Derivative17Computational study of 2N-atom functionalized corannulene by alkali metals doping: Towards the development of highly efficient nonlinear optical materials20A comprehensive review on metal chalcogenides with three-dimensional frameworks for infrared nonlinear optical applications114Difluoro(oxalato)borates as Short-Wavelength Optical Crystals with Bifunctional [BF 2 C 2 O 4 ] Units38Rearrangement of [B2O5] Dimers within [B7O14] Clusters Enables Enhanced Optical Anisotropy in Li3Cs6Al2B14O28F4Organic–Inorganic Hybrid Antimony(III) Halides for Second Harmonic Generation34Postsynthetic Modification of NU-1000 for Designing a Polyoxometalate-Containing Nanocomposite with Enhanced Third-Order Nonlinear Optical Performance86Characteristics of structure, thermal stability and optical properties for a novel NLO crystal (C5H12NO)H2PO48M(NH2SO3)2·xH2O (M = Ca, Pb, x = 0, 1, 4): Effect of Hydrogen Bonding on Structural Transformations and Second Harmonic Generation of Metal Sulfamates26d6versus d10, Which Is Better for Second Harmonic Generation Susceptibility? A Case Study of K2TGe3Ch8 (T = Fe, Cd; Ch = S, Se)18Enhancing birefringence of non-π-conjugated sulfate systems through rare-earth metal-centered polyhedra10Linear π-conjugated units of the D ∞h point group as superior ultraviolet birefringent units1Na 7 (SeO 4 ) 3 (IO 3 ) and K 2 (SeO 4 )[IO 2 (OH)]: two new iodate-selenates with short-wave UV cutoff edge and large birefringence8Nitrides: a promising class of nonlinear optical material candidates9Recent advances in F-containing iodate nonlinear optical materials6Spontaneous resolution of two chiral metal–organic frameworks through local geometric and lattice frustration effects7Tetrahedron-based deep-ultraviolet nonlinear optical crystal with optimized KBe 2 BO 3 F 2 -like structure and disordered cations2Expanding gaudefroyite family to Sr2MBi(REEO)3(BO3)4 (M = Ca, Sr, Ba; REE = Y, Eu) borates with large second harmonic generation responses8Recent progress in the design of IR nonlinear optical materials by partial chemical substitution: Structural evolution and performance optimization133Two Ultraviolet Optical Crystals K6B12O19F4 and K12B28O48: The Effects of Metal Cations Size and the F Ions on the Structure6“Cation Activation”: An Effective Strategy for the Enhancement of Birefringence36A review: An overview on third-order nonlinear optical and optical limiting properties of Schiff bases70From 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 Crystals21Nonlinear optical inorganic sulfates: The improvement of the phase matching ability driven by the structural modulation41C14H10BrNO2: A Birefringent Crystal with an Expanded π-Conjugated Group13Cs2Pb4Br10: A layered perovskite shows large birefringence11Strategy for a Rational Design of Deep-Ultraviolet Nonlinear Optical Materials from Zeolites2Ca2Ln(BS3)(SiS4) (Ln = La, Ce, and Gd): Mixed Metal Thioborate‐Thiosilicates as Well‐Performed Infrared Nonlinear Optical Materials29Novel Non-Centrosymmetric NdSr4O(BO3)3 Borate and Nd(Ca1−xSrx)4O(BO3)3 Solid Solutions: Preparation, Crystal Structures, Thermal Expansion and Optical Properties3Synthesis and characterization of photo-activatable systems0A 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 Polycations25Mg(C 3 O 4 H 2 )(H 2 O) 2 : A New Ultraviolet Nonlinear Optical Material Derived from KBe 2 BO 3 F 2 with High Performance and Excellent Water‐Resistance7Mg(C3O4H2)(H2O)2: A New Ultraviolet Nonlinear Optical Material Derived from KBe2BO3F2 with High Performance and Excellent Water‐Resistance43Compositional Deformations, Absorption Spectroscopy, and Low-Temperature X-Ray Diffraction of Sr1 – xBaxBi2B2O7 Solid Solutions2A Sharp Improvement of Sulfate's Birefringence Induced by the Synergistic Effect of Heteroleptic and Dimeric Strategies14A2Hgx(SeO3)y (A = K, Rb, Cs): Three Alkali Metal Mercury Selenites Featuring Unique 1D [HgOm(SeO3)n]∞ Chains13Advances in Solid-State Nonlinear Optical Materials: From Fundamentals to Applications61Ga-based IR nonlinear optical materials: Synthesis, structures, and properties65(C(NH2)3)2(I2O5F)(IO3)(H2O) and C(NH2)3IO2F2: Two Guanidine Fluorooxoiodates with Wide Band Gap and Large Birefringence20Advancing nonlinear optics: discovery and characterization of new non-centrosymmetric phenazine-based halides6Modulating the birefringence of two-dimensional hybrid lead bromide perovskites using pyridine derivative cations11RbY(SO4)2·4H2O: A new ultraviolet birefringent crystal3Two Short-Wave UV Antimony(III) Sulfates Exhibiting Large Birefringence18The Birefringence Modulation in Short‐Wave Ultraviolet Sulfates with Functional π‐Conjugated Cations and Polymerized Heteroleptic Tetrahedral Anions18Theoretical Investigation of Structural, Electronic and Optical Properties of Cs3MoO4(HCO3) with NLO Active Functional Units2Extending Unique 1D Double-Chains to 2D Layers with Birefringent Gain by Introducing a Hydroxyl Group5NLOphoric Anthraquinone Dyes – A Review11Nonlinear Optical Effects of Hybrid Antimony(III) Halides Induced by Stereoactive 5s 2 Lone Pairs and Trimethylammonium Cations23Optical and mechanical stability of Tutton’s salt crystal of Cu2+ doped ammonium cobalt(II) sulfate hexahydrate15Bi(SO4)F·H2O and Bi(SO4)(NO3)·3H2O: Chemical Substitution-Induced Birefringence Enhancement in Bismuth Sulfates6NH4Y(SO4)2·H2O and NH4YSO4F2: Two New Ammonium‐Rare Earth Metal Sulfates with Enhanced Optical Anisotropy and Deep Ultraviolet Transmission3A Rare-Earth-Based Borate Optical Crystal with Enlarged Dihedral Angles of Distinct [BO3] Groups Exhibiting a Wide UV Transparent Range8LiNa2Ca8B12O24F6Cl and Li1.2Na2.8B6O11: A Case of Cation-Induced Birefringence Enhancement via Dimensional Changes of Highly Polymerized [B12O24] Motifs10Investigations of structure, thermal stability and optical properties of a new NLO crystal (C3H5N2)+(CF3COO)-0Constructing Ultraviolet Nonlinear Optical Crystals with Superior Thermal Stability Based on Organic π-Conjugated [HCOO] Groups6Nonlinear optical cyanurate crystals15From [Ba3S][GeS4] to [Ba3CO3][MS4] (M = Ge, Sn): Enhancing optical anisotropy in IR birefringent crystals via functional group implantation11Rb 1.87 Cs 1.13 B 8 O 13 (NO 3 ): a new acentric borate-nitrate with two types of three-dimensional interpenetrating lattices1Stacking interactions in stabilizing supramolecular assembly of M[9C] 2 M complexes: dynamic stability with remarkable nonlinear optical features17Functional 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 Region14(C 14 H 14 N 2 )MCl 4 (M = Zn, Cd): two hybrid metal halides exhibiting strong second harmonic generation responses, large birefringence, and broadband photoluminescence12Broadband laser protection and enhanced nonlinear optical response of samarium-metal–organic framework-based white/black carbon hybrids4Enhancements of the first and second hyperpolarizability of a GMP coordination polymer: crystal structure and computational studies19Exploring quaternary vanadates containing alkali metals, alkaline earth metals, and [VO 4 ] in the quest for nonlinear optical materials1Novel red-emitting SrBi2B4O10:Eu3+ phosphors: Synthesis, crystal structure and luminescence4Insights into the optoelectronic, quantum chemical, NBO and dynamic nonlinear optical properties of meso-BODIPY dyes3BaLa4(SiS4)2(BS3)2: Structurally Ordered Thioborate-Thiosilicate Obtained by Adjusting the Cationic Size2Comprehensive investigation of structural, optical, thermal, and dielectric properties of malic acid-doped sulphamic acid single crystals for photonic device applications5Rational design of a high-efficiency lead halide organic-inorganic hybrid nonlinear optical switch via molecular engineering5Phase-Matching Second-Harmonic Generation in Zero-Dimensional Zinc Thiocyanates Ligated with Chiral Amino Acids6Advances in Nonlinear Optics of Twisted Push Pull Organic Chromophores5Hybrid Bismuth Halide with Rich Polymorphism and Second Harmonic Generation Response8Studies on Three 3D Bimetallic Tellurates: Including a Second-Order NLO Material with d10-Zn2+ and SOJT-Effect Te4+/Mo6+ Cations2Growth, structure and optical properties of PbBi3PO8 crystals0AN EXPERIMENTAL–THEORETICAL INSIGHT INTO SYNTHESIS AND OPTICAL PROPERTIES OF STRUCTURALLY TUNED Π-CONJUGATED SCHIFF BASES0Tetrakis(2,4,6-triaminopyrimidinium) tetrakis(4-nitrophenolate) 4-nitrophenol pentahydrate: a hydrous salt cocrystal for NLO applications1Asymmetry-driven organic–inorganic hybrid strategy for constructing structures with exceptional organofunctionalized B–O units2Synthesis, Crystal Growth, Linear, and Nonlinear Optical Properties of Water-Grown Giant Optical Anisotropic Thiocyanates ABi(SCN) 4 (A = Rb, Cs)3Achieving record birefringence in metal-free semiorganic sulfate crystals via tetrahedral anionic group substitution0CsB(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 properties0Synthesis, characterization, and enhanced nonlinear optical properties of octyloxy-substituted azo-imine copper(II) complex: Experimental and theoretical studies3Manganese-doped NaKSO4 single crystals for sustainable high-performance nonlinear optical, superior dielectric and photonic applications3The Achievement of a Strong Second Harmonic Generation Response and a Large Birefringence in Sulfates4Hydrogen-Bond-Directed Assembly of an Intramolecular Charge-Transfer Compound for Second-Order Nonlinear Optics1Control of Symmetry and Photophysical Properties of Hybrid Antimony Chlorides via Mixed Organic Cations0NaNO 3 [(NH 2 ) 2 SO 2 ] 2 : A Halogen‐Free KBBF‐Type Nitrate Crystal with Record Birefringence for Ultraviolet Applications0Deep-Ultraviolet Transparent Zr/Hf Fluorides with Second-Harmonic Generation Effects Induced by Alkali-Metal Modulation2Anion-Stabilized Incommensurate Modulation Enables Nonlinear Optical Response in Eu2SiO3.89N0.110Machine Learning for Second‐ and Third‐Harmonic Generation: Benchmarks, Challenges, and a Roadmap for Data‐Driven Photonic Materials0Designing 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 Crystals0

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  6. Ba3(BO3)(CO3)F: The First Borate Carbonate Fluoride Synthesized by the High‐Temperature Solution Method

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  12. Chiral Template‐Driven Macroscopic Chirality Control: Structure‐Second‐Harmonic Generation Properties Relationship

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  38. A novel 2-(aminomethyl)pyridineH 2 PO 4 crystal with second-order nonlinear optical performance

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