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RESEARCH PAPER · Accounts of Chemical Research · 2016

Toward the Rational Design of Novel Noncentrosymmetric Materials: Factors Influencing the Framework Structures

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Toward the Rational Design of Novel Noncentrosymmetric Materials: Factors Influencing the Framework StructuresOriginalBa 5 CdGa 6 Se 15 , a congruently-melting infrared nonlinear optical material with strong SHG response52Structural Modulation of Nitrate Group with Cations to Affect SHG Responses in RE(OH)2NO3 (RE = La, Y, and Gd): New Polar Materials with Large NLO Effect after Adjusting pH Values of Reaction Systems151Bi3OF3(IO3)4: Metal Oxyiodate Fluoride Featuring a Carbon-Nanotube-like Topological Structure with Large Second Harmonic Generation Response121M4Mg4(P2O7)3 (M = K, Rb): Structural Engineering of Pyrophosphates for Nonlinear Optical Applications238Chemistry-Inspired Adaptable Framework Structures368CsB 4 O 6 F: A Congruent‐Melting Deep‐Ultraviolet Nonlinear Optical Material by Combining Superior Functional Units184CsB4O6F: A Congruent‐Melting Deep‐Ultraviolet Nonlinear Optical Material by Combining Superior Functional Units895New Compressed Chalcopyrite-like Li2BaMIVQ4 (MIV = Ge, Sn; Q = S, Se): Promising Infrared Nonlinear Optical Materials245Large Second-Harmonic Generation Responses Achieved by the Dimeric [Ge2Se4(μ-Se2)]4– Functional Motif in Polar Polyselenides A4Ge4Se12 (A = Rb, Cs)49Acentric La3(IO3)8(OH) and La(IO3)2(NO3): Partial Substitution of Iodate Anions in La(IO3)3 by Hydroxide or Nitrate Anion55Chemical Cosubstitution-Oriented Design of Rare-Earth Borates as Potential Ultraviolet Nonlinear Optical Materials267Cation-tuned synthesis of the A 2 SO 4 ·SbF 3 (A = Na + , NH 4 + , K + , Rb + ) family with nonlinear optical properties78Cs 3 VO(O 2 ) 2 CO 3 : an exceptionally thermostable carbonatoperoxovanadate with an extremely large second-harmonic generation response129New strategy for designing promising mid-infrared nonlinear optical materials: narrowing the band gap for large nonlinear optical efficiencies and reducing the thermal effect for a high laser-induced damage threshold142Oxyhalides: prospecting ore for optical functional materials with large laser damage thresholds76Cation‐Tuned Synthesis of Fluorooxoborates: Towards Optimal Deep‐Ultraviolet Nonlinear Optical Materials191Cation‐Tuned Synthesis of Fluorooxoborates: Towards Optimal Deep‐Ultraviolet Nonlinear Optical Materials714From AgGaS2 to Li2ZnSiS4: Realizing Impressive High Laser Damage Threshold Together with Large Second-Harmonic Generation Response134Functional Materials Design via Structural Regulation Originated from Ions Introduction: A Study Case in Cesium Iodate System90SrB 5 O 7 F 3 Functionalized with [B 5 O 9 F 3 ] 6− Chromophores: Accelerating the Rational Design of Deep‐Ultraviolet Nonlinear Optical Materials738SrB5O7F3 Functionalized with [B5O9F3]6− Chromophores: Accelerating the Rational Design of Deep‐Ultraviolet Nonlinear Optical Materials116Effect of Element Substitution on Structural Transformation and Optical Performances in I2BaMIVQ4 (I = Li, Na, Cu, and Ag; MIV = Si, Ge, and Sn; Q = S and Se)63A Series of Mixed-Metal Germanium Iodates as Second-Order Nonlinear Optical Materials71Recent advances in ultraviolet and deep-ultraviolet second-order nonlinear optical crystals257Polar Fluorooxoborate, NaB4O6F: A Promising Material for Ionic Conduction and Nonlinear Optics494Polar Fluorooxoborate, NaB4O6F: A Promising Material for Ionic Conduction and Nonlinear Optics67A Fluorooxosilicophosphate with an Unprecedented SiO2F4 Species56Fluorooxoborates: Ushering in a New Era of Deep Ultraviolet Nonlinear Optical Materials102Ba3Mg3(BO3)3F3 polymorphs with reversible phase transition and high performances as ultraviolet nonlinear optical materials470Centrosymmetric (NH4)2SbCl(SO4)2 and Non-centrosymmetric (NH4)SbCl2(SO4): Synergistic Effect of Hydrogen-Bonding Interactions and Lone-Pair Cations on the Framework Structures and Macroscopic Centricities89A review on structure-performance relationship toward the optimal design of infrared nonlinear optical materials with balanced performances252BaB2S4: An Efficient and Air-Stable Thioborate as Infrared Nonlinear Optical Material with High Laser Damage Threshold85Pb 2 GaF 2 (SeO 3 ) 2 Cl: Band Engineering Strategy by Aliovalent Substitution for Enlarging Bandgap while Keeping Strong Second Harmonic Generation Response178BaB8O12F2: a promising deep-UV birefringent material60Li 4 Na 2 CsB 7 O 14 : a new edge-sharing [BO 4 ] 5− tetrahedra containing borate with high anisotropic thermal expansion52A Facile Route to Nonlinear Optical Materials: Three‐Site Aliovalent Substitution Involving One Cation and Two Anions137A 2 Bi 2 (SO 4 ) 2 Cl 4 (A = NH 4 , K, Rb): achieving a subtle balance of the large second harmonic generation effect and sufficient birefringence in sulfate nonlinear optical materials98A 2 SrM IV S 4 (A = Li, Na; M IV = Ge, Sn) concurrently exhibiting wide bandgaps and good nonlinear optical responses as new potential infrared nonlinear optical materials78A new ferroelastic hybrid material with a large spontaneous strain: (Me 3 NOH) 2 [ZnCl 4 ]55ABaSbQ 3 (A = Li, Na; Q = S, Se): diverse arrangement modes of isolated SbQ 3 ligands regulating the magnitudes of birefringences50An energy band engineering design to enlarge the band gap of KTiOPO 4 (KTP)-type sulfates via aliovalent substitution66Centrosymmetric K 2 SO 4 ·(SbF 3 ) 2 and noncentrosymmetric Rb 2 SO 4 ·(SbF 3 ) 2 resulting from cooperative effects of lone pair and cation size63Functional layered materials with heavy metal lone pair cations, Pb 2+ , Bi 3+ , and Te 4+90LiMg(IO 3 ) 3 : an excellent SHG material designed by single-site aliovalent substitution68Y 8 O(OH) 15 (CO 3 ) 3 Cl: an excellent short-wave UV nonlinear optical material exhibiting an infrequent three-dimensional inorganic cationic framework61Rational Design via Synergistic Combination Leads to an Outstanding Deep-Ultraviolet Birefringent Li2Na2B2O5 Material with an Unvalued B2O5 Functional Gene284A Niobium Oxyiodate Sulfate with a Strong Second‐Harmonic‐Generation Response Built by Rational Multi‐Component Design114Targeting the Next Generation of Deep-Ultraviolet Nonlinear Optical Materials: Expanding from Borates to Borate Fluorides to Fluorooxoborates450CsSbF 2 SO 4 : An Excellent Ultraviolet Nonlinear Optical Sulfate with a KTiOPO 4 (KTP)‐type Structure87CsSbF2SO4: An Excellent Ultraviolet Nonlinear Optical Sulfate with a KTiOPO4 (KTP)‐type Structure432Module-Analysis-Assisted Design of Deep Ultraviolet Fluorooxoborates with Extremely Large Gap and High Structural Stability109HBa2.5(IO3)6(I2O5) and HBa(IO3)(I4O11): Explorations of Second-Order Nonlinear Optical Materials in the Alkali-Earth Polyiodate System49Two Polar Molybdenum(VI) Iodates(V) with Large Second-Harmonic Generation Responses67Deep-Ultraviolet Mixed-Alkali-Metal Borates with Induced Enlarged Birefringence Derived from the Structure Rearrangement of the LiB3O545KBiCl2SO4: The First Bismuth Chloride Sulfate Being Second-Order Nonlinear Optical Active44REI5O14 (RE=Y and Gd): Promising SHG Materials Featuring the Semicircle‐Shaped I5O143− Polyiodate Anion125REI5O14 (RE=Y and Gd): Promising SHG Materials Featuring the Semicircle‐Shaped I5O143− Polyiodate Anion62Prediction of Fluorooxoborates with Colossal Second Harmonic Generation (SHG) Coefficients and Extremely Wide Band Gaps: Towards Modulating Properties by Tuning the BO 3 /BO 3 F Ratio in Layers99Sn2B5O9Cl: A Material with Large Birefringence Enhancement Activated Prepared via Alkaline‐Earth‐Metal Substitution by Tin255CsAlB 3 O 6 F: a beryllium-free deep-ultraviolet nonlinear optical material with enhanced thermal stability153(NH4)Bi2(IO3)2F5: An Unusual Ammonium‐Containing Metal Iodate Fluoride Showing Strong Second Harmonic Generation Response and Thermochromic Behavior92A new family of quaternary thiosilicates SrA 2 SiS 4 (A = Li, Na, Cu) as promising infrared nonlinear optical crystals48Na2Mg1−xZnxSiO4 (0 ≤ x ≤ 1): Noncentrosymmetric Sodium Metal Silicate Solid Solutions with Ultraviolet Nonlinear Optical Properties71Novel ultraviolet (UV) nonlinear optical (NLO) materials discovered by chemical substitution-oriented design302Second-order nonlinear optical materials with a benzene-like conjugated π system49Infrared Nonlinear Optical Polymorphs α- and β-SrCu 2 SnS 4 Exhibiting Large Second Harmonic Generation Responses with Requisite Phase-Matching Behavior44BaF 2 TeF 2 (OH) 2 : A UV Nonlinear Optical Fluorotellurite Material Designed by Band-Gap Engineering157Rational Design of the Nonlinear Optical Response in a Tin Iodate Fluoride Sn(IO3)2F290Lead Mixed Oxyhalides Satisfying All Fundamental Requirements for High‐Performance Mid‐Infrared Nonlinear Optical Materials164Lead Mixed Oxyhalides Satisfying All Fundamental Requirements for High‐Performance Mid‐Infrared Nonlinear Optical Materials55Alignment of Polar Moieties Leading to Strong Second Harmonic Response in KCsMoP2O951Enhancement of Second-Order Optical Nonlinearity in a Lutetium Selenite by Monodentate Anion Partial Substitution58Designing a Deep-UV Nonlinear Optical Fluorooxosilicophosphate127K2Na(IO3)2(I3O8) with Strong Second Harmonic Generation Response Activated by Two Types of Isolated Iodate Anions46Recent Progress in 2D Metal‐Organic Frameworks for Optical Applications149A6Sb4F12(SO4)3 (A = Rb, Cs): Two Novel Antimony Fluoride Sulfates with Unique Crown-like Clusters50A review on phase transition and structure-performance relationship of second-order nonlinear optical polymorphs107[ABa2Cl][Ga4S8] (A = Rb, Cs): Wide-Spectrum Nonlinear Optical Materials Obtained by Polycation-Substitution-Induced Nonlinear Optical (NLO)-Functional Motif Ordering269New Alkaline-Earth Metal Fluoroiodates Exhibiting Large Birefringence and Short Ultraviolet Cutoff Edge with Highly Polarizable (IO 3 F) 2– Units63Two Pyrophosphates with Large Birefringences and Second‐Harmonic Responses as Ultraviolet Nonlinear Optical Materials137AGa 3 F 6 (SeO 3 ) 2 (A = Rb, Cs): A New Type of Phase-Matchable Hexagonal Tungsten Oxide Material with Strong Second-Harmonic Generation Responses63Bi 3 (SeO 3 ) 3 (Se 2 O 5 )F: A Polar Bismuth Selenite Fluoride with Polyhedra of Highly Distortive Lone Pair Cations and Strong Second-Harmonic Generation Response63Ba2[MoO3(OH)(IO3)2]IO3: A Promising SHG Material Featuring a Λ-Shaped Functional Motif Achieved by Universal Mono-Site Substitution50K 2 Sb(P 2 O 7 )F: Cairo Pentagonal Layer with Bifunctional Genes Reveal Optical Performance297CsHgNO3Cl2: A New Nitrate UV Birefringent Material Exhibiting an Optimized Layered Structure49Pb 18 O 8 Cl 15 I 5 : A Polar Lead Mixed Oxyhalide with Unprecedented Architecture and Excellent Infrared Nonlinear Optical Properties165A 3 BBi(P 2 O 7 ) 2 (A = Rb, Cs; B = Pb, Ba): Isovalent Cation Substitution to Sustain Large Second-Harmonic Generation Responses106α‐SnF 2 : A UV Birefringent Material with Large Birefringence and Easy Crystal Growth210Sn2B5O9Br as an Outstanding Bifunctional Material with Strong Second‐Harmonic Generation Effect and Large Birefringence84Recent Achievements in Lone-Pair Cation-Based Infrared Second-Order Nonlinear Optical Materials95Recent advances of oxyfluorides for nonlinear optical applications69Large Second-Harmonic Response and Giant Birefringence of CeF 2 (SO 4 ) Induced by Highly Polarizable Polyhedra248A Deep‐UV Nonlinear Optical Borosulfate with Incommensurate Modulations71Toward the Enhancement of Critical Performance for Deep-Ultraviolet Frequency-Doubling Crystals Utilizing Covalent Tetrahedra137Discovery of First Magnesium Fluorooxoborate with Stable Fluorine Terminated Framework for Deep‐UV Nonlinear Optical Application167Be2(BO3)(IO3): The First Anion‐mixed Van der Waals Member in the KBe2BO3F2 Family with a Very Strong Second Harmonic Generation Response130High-Performance Second-Harmonic-Generation (SHG) Materials: New Developments and New Strategies323Hydrogen‐Bond‐Driven Synergistically Enhanced Hyperpolarizability: Chiral Coordination Polymers with Nonpolar Structures Exhibiting Unusually Strong Second‐Harmonic Generation87A2MoO2F3(IO2F2) (A = Rb, Cs): Strong Nonlinear Optical Responses and Enlarged Band Gaps through Fluorine Incorporation50[Ag(NH3)2]2SO4: A Strategy for the Coordination of Cationic Moieties to Design Nonlinear Optical Materials**85Li 4 MgGe 2 S 7 : The First Alkali and Alkaline‐Earth Diamond‐Like Infrared Nonlinear Optical Material with Exceptional Large Band Gap213A Congruent‐Melting Mid‐Infrared Nonlinear Optical Vanadate Exhibiting Strong Second‐Harmonic Generation63Sn2PO4I: An Excellent Birefringent Material with Giant Optical Anisotropy in Non π‐Conjugated Phosphate212Achieving Short‐Wavelength Phase‐Matching Second Harmonic Generation in Boron‐Rich Borosulfate with Planar [BO3] Units102From CeF2(SO4)·H2O to Ce(IO3)2(SO4): Defluorinated Homovalent Substitution for Strong Second-Harmonic-Generation Effect and Sufficient Birefringence53β-BaGa 4 Se 7 : a promising IR nonlinear optical crystal designed by predictable structural rearrangement46Na4B8O9F10: A Deep‐Ultraviolet Transparent Nonlinear Optical Fluorooxoborate with Unexpected Short Phase‐Matching Wavelength Induced by Optimized Chromatic Dispersion133Recent Development of Non-π-Conjugated Deep Ultraviolet Nonlinear Optical Materials106Phase Matchability Transformation in the Infrared Nonlinear Optical Materials with Diamond‐Like Frameworks63Halogen regulation triggers structural transformation from centrosymmetric to noncentrosymmetric switches in tin phosphate halides Sn 2 PO 4 X (X = F, Cl)47Metal oxyhalides: an emerging family of nonlinear optical materials124Phase matching achieved by isomorphous substitution in IR nonlinear optical material Ba 2 SnSSi 2 O 7 with an undiscovered [SnO 4 S] functional motif47High‐Performance Sulfate Optical Materials Exhibiting Giant Second Harmonic Generation and Large Birefringence199Strong Nonlinearity Induced by Coaxial Alignment of Polar Chain and Dense [BO3] Units in CaZn2(BO3)2212Lone Pair-Driven Enhancement of Birefringence in Polar Alkali Metal Antimony Phosphates46Promising Deep‐Ultraviolet Birefringent Materials via Rational Design and Assembly of Planar π‐Conjugated [B(OH)3] and [B3O3(OH)3] Functional Species83Enhancement of Birefringence in Borophosphate Pushing Phase-Matching into the Short-Wavelength Region150RbBiP2S6: A Promising IR Nonlinear Optical Material with a Giant Second-Harmonic Generation Response Designed by Aliovalent Substitution80Two Metal Phosphate Nonlinear Optical Materials Simultaneously Exhibiting Ultraviolet Transparence and a Large Birefringence50Cation-anion synergetic interactions achieving tunable birefringence in quasi-one-dimensional antimony(III) fluoride oxalates58A comprehensive review on metal chalcogenides with three-dimensional frameworks for infrared nonlinear optical applications114Mixed-Anion-Oriented Design of LnMGa3S6O (Ln = La, Pr, and Nd; M = Ca and Sr) Nonlinear Optical Oxysulfides with Targeted Property Balance56Exploring Short-Wavelength Phase-Matching Nonlinear Optical Crystals by Employing KBe2BO3F2 as the Template95Local Polarity-Induced Assembly of Second-Order Nonlinear Optical Materials128Ag-based chalcogenides and derivatives as promising infrared nonlinear optical materials90Aluminoborates as Nonlinear Optical Materials79Evaluating refractive index and birefringence of nonlinear optical crystals: Classical methods and new developments45From H 12 C 4 N 2 CdI 4 to H 11 C 4 N 2 CdI 3 : a highly polarizable CdNI 3 tetrahedron induced a sharp enhancement of second harmonic generation response and birefringence50Intense d‐p Hybridization in Nb3O15 Tripolymer Induced the Largest Second Harmonic Generation Response and Birefringence in Germanates51Recent progress in the design of IR nonlinear optical materials by partial chemical substitution: Structural evolution and performance optimization133Rational Design of a Rare‐Earth Oxychalcogenide Nd3[Ga3O3S3][Ge2O7] with Superior Infrared Nonlinear Optical Performance64Unbiased Screening of Novel Infrared Nonlinear Optical Materials with High Thermal Conductivity: Long‐neglected Nitrides and Popular Chalcogenides48Recent Development of Sn II , Sb III ‐based Birefringent Material: Crystal Chemistry and Investigation of Birefringence130Unveiling the Superior Optical Properties of Novel Melamine‐Based Nonlinear Optical Material with Strong Second‐Harmonic Generation and Giant Optical Anisotropy74Birefringence Regulation by Clarifying the Relationship Between Stereochemically Active Lone Pairs and Optical Anisotropy in Tin‐based Ternary Halides56Advances in aliovalent substitution strategy for the design and synthesis of nonlinear optical materials: d0 transition metal/gallium iodates and selenites70Recent advances in IR nonlinear optical chalcogenides with well-balanced comprehensive performance56Achieving the full-wavelength phase-matching for efficient nonlinear optical frequency conversion in C(NH2)3BF4513Breaking Through the Trade‐Off Between Wide Band Gap and Large SHG Coefficient in Mercury‐Based Chalcogenides for IR Nonlinear Optical Application49A prediction-driven database to enable rapid discovery of nonlinear optical materials46Breaking the Inherent Interarrangement of [B3O6] Clusters for Nonlinear Optics with Orbital Hybridization Enhancement142Highly Birefringent d 0 Transition Metal Fluoroantimonite in the Mid Infrared Band: Order–Disorder Regulation by Cationic Size83New Functional Groups Design toward High Performance Ultraviolet Nonlinear Optical Materials95“Three‐in‐One”: A New Hg‐Based Selenide Hg 7 P 2 Se 12 Exhibiting Wide Infrared Transparency Range and Strong Nonlinear Optical Effect80[(C 5 H 6 N 2 ) 2 H](Sb 4 F 13 ): a polyfluoroantimonite with a strong second harmonic generation effect60Recent advances in rational structure design for nonlinear optical crystals: leveraging advantageous templates153Unearthing Superior Inorganic UV Second‐Order Nonlinear Optical Materials: A Mineral‐Inspired Method Integrating First‐Principles High‐Throughput Screening and Crystal Engineering124Rational Design of Novel Promising Infrared Nonlinear Optical Materials: Structural Chemistry and Balanced Performances156Assembly of π‐Conjugated [B3O6] Units by Mer‐Isomer [YO3F3] Octahedra to Design a UV Nonlinear Optical Material, Cs2YB3O6F297Recent advances and future perspectives on rare-earth-based nonlinear optical materials with π-conjugated [XO3] (X = B, C, N) units66

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