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RESEARCH PAPER · Inorganic Chemistry · 2021

Synergistic Effect of π-Conjugated [C(NH 2 ) 3 ] Cation and Sb(III) Lone Pair Stereoactivity on Structural Transformation and Second Harmonic Generation

Man Zhang, Bingbing Zhang, Daqing Yang, Ying Wang

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Synergistic Effect of π-Conjugated [C(NH 2 ) 3 ] Cation and Sb(III) Lone Pair Stereoactivity on Structural Transformation and Second Harmonic GenerationOriginalGuanidinium Fluorooxoborates as Efficient Metal-free Short-Wavelength Nonlinear Optical Crystals140[C(NH 2 ) 3 ] 2 S 2 O 8 : combining delocalized and localized π-conjugate units to achieve strong optical anisotropy21Performance of optical materials with the derivative of planar π-conjugated groups: Recent advances and future prospects37[C(NH2)3]2Zn(CO3)2: A Guanidinium-Templated Ultraviolet Nonlinear Optical Material20Pb5(GeO4)(Ge2O7) and Pb3.32Ca1.68(GeO4)(Ge2O7): Two Nonlinear Optical Germanates Induced by Diverse PbOx Polyhedra17[C(NH2)3]2MoO2F4·H2O: Unique Chinese-Knot Structure Revealing Superior Nonlinear-Optical Properties20M(NH2SO3)2·xH2O (M = Ca, Pb, x = 0, 1, 4): Effect of Hydrogen Bonding on Structural Transformations and Second Harmonic Generation of Metal Sulfamates26Recent advances on the synthesis of Sb(III)-based inorganic ultraviolet nonlinear optical materials47The synthesis, structure and photoluminescence of new (C8H18N)2CdCl4 crystals9Recent progress of newly developed functional building units and corresponding nonlinear optical materials14A survey of stereoactive oxysalts for linear and nonlinear optical applications40A two-fold interpenetrated mixed-ligands acentric 3D coordination polymer Zn(OBA)(DIB)·0.5H2O: Topological analysis, fluorescent and second-order NLO properties7A review of the relationship between the structure and nonlinear optical properties of organic-inorganic hybrid materials150[(C 5 H 6 N 2 ) 2 H](Sb 4 F 13 ): a polyfluoroantimonite with a strong second harmonic generation effect60Research progress in optical materials with cationic organic planar π-conjugated groups containing CN bonds34[C(NH2)3]6Mo7O24: A Guanidinium Molybdate as a UV Nonlinear Optical Crystal with Large Birefringence18[C(NH2)3][B(C2O2H4)2]: An Organic–Inorganic Hybrid Borate Containing Nonlinear-Optical Active Unit [B(C2O2H4)2]− with Solar-Blind-Region Optical Nonlinearity16Stereochemically Active Lone Pair Leads to Birefringence in the Vacancy Ordered Cs3Sb2Cl9 Perovskite Single Crystals13Rational Combination of π‐Conjugated and Non‐π‐Conjugated Groups Achieving Strong Nonlinear Optical Response, Large Optical Anisotropy, and UV Light‐Switchable Fluorescence65Nonlinear Optical Effects of Hybrid Antimony(III) Halides Induced by Stereoactive 5s 2 Lone Pairs and Trimethylammonium Cations23(C4H6N3O)(HSO4): A Cytosinium Bisulfate with Large Birefringence and Moderate Second Harmonic Generation Effect Produced via Combining a Promising Planar Nonlinear Optical-Active Motif with a Tetrahedral Group13Chiral Organic Cations and Distorted Inorganic Polyhedra Composing Metal Halide Nonlinear Optical Materials22[C(NH2)3]10(MoO3)10(PO4)2(HPO4)2·5H2O: Synergy effect of multiple functional units results in significant birefringence10Stereo‐Active Lone Pairs Induced Second Harmonic Generation Responses and Electrocatalytic Activity in Hybrid Material1Cs2Pb(CO3)2: a novel mixed-metal carbonate with rare Pb-C-O one-dimensional chain0Synthesis and growth of solution-processed chiral perovskites12Sulfate Derivatives with Heteroleptic Tetrahedra: New Deep‐Ultraviolet Birefringent Materials in which Weak Interactions Modulate Functional Module Ordering61Sulfate Derivatives with Heteroleptic Tetrahedra: New Deep‐Ultraviolet Birefringent Materials in which Weak Interactions Modulate Functional Module Ordering4Achieving the Birefringence Optimization by Methyl Modulation in Organic Nonlinear Optical Crystals15Constructing Ultraviolet Nonlinear Optical Crystals with Superior Thermal Stability Based on Organic π-Conjugated [HCOO] Groups6(C10N2H10)(HI2O6)(HIO3)(IO3): A Birefringent Material Featuring Large π-Conjugated Organic Cation and Two Types of Iodate Anions2[C(NH2)3]2S2O6: A SBBO-Like Dithionate Crystal with Large Optical Anisotropy14Cationic Modification in Hybrid Iodates: A Pathway to Superior Performance13Zwitterionic Glycine-Based Antimony Fluorides with Exceptional Ultraviolet Nonlinear Optical Properties11Designing Polar Covalent Hybrid Cadmium‐Based Chalcohalides Ultraviolet Nonlinear Optical Crystal with Strong Optical Anisotropy via Double‐Site Dual FBUs Tailoring25Inch‐sized K[NH2(CH2COO)2]: a High‐Performance UV Nonlinear Optical Crystal Enabled by Novel Flexible π‐Conjugated Building Units, [NH2(CH2COO)2]−13Toward the Strongest Nonlinear Optical Response and Largest Birefringence in Solvent‐Free Organic–Inorganic Metal Halides by Hydrogen Bond Engineering39(Sr9N1.33(8))(SrIn3)[CN3] and Sr4(Sr6N)2[In4][CN3]4: Two Fully Deprotonated Guanidinates Accessible from Pressureless Sodium Flux Synthesis5[C( NH2 )3] 2SiF6 : Design of Deep Ultraviolet Crystals with Large Birefringence Based on a Fluorination‐Oriented Strategy13Three-In-One: A Guanidinium-Containing Niobium Oxyfluoride with a Perovskite-like Structure Revealing Multifunctional Optical Properties2Designing Hybrid Sb-Based Nonlinear Optical Crystals with Large Birefringence by Combining the Lone Pair and π-Conjugated Genes10The birefringence optimization by hydroxyl in organic nonlinear optical crystals3Enhanced Birefringence in Hybrid Antimony Halides via π-Conjugated Organic Cation Design10Remarkable Birefringence Enhancement Enabled by π-Conjugated Cyanoguanidine Group Based on Anisotropic Molecule Coordination Approach8From centrosymmetric (C 4 H 8 N 5 )(SbF 4 ) to polar (C 4 H 7 N 4 O)(SbF 4 ): a new UV nonlinear optical material achieved by functional group modulation8Synergism of [C 2 N 4 H 7 S] cations and anionic modulators: tailoring second-order nonlinear optics and birefringence in organic–inorganic crystals6The modulation of structural polarity facilitating the gradient enhancement of second harmonic generation effects in hybrid metal halides5Zn 4 S(C 2 H 2 N 3 ) 3 (NCS) 3 : Coordination-Driven Structural Distortion Engineering Triggers Exceptional NLO Effect in Mixed-Bonding Zinc Isothiocyanate6[C(NH 2 ) 3 ]SbCl 4 : An NLO Material with Enhanced Second Harmonic Response and Birefringence3Halogen Anion-Mediated Substitution of Nitrate: Toward Polar Materials with Intense Second-Harmonic Generation Effects3Steric hindrance and hydrogen-bond networks synergistically directing molecular alignment for high-performance ultraviolet birefringent1Engineering Multiple Hydrogen‐Bond Sites With D‐π‐A Motifs for Strong Optical Nonlinearity and Giant Birefringence in Organic‐Inorganic Halides4Engineering Multiple Hydrogen‐Bond Sites With D‐π‐A Motifs for Strong Optical Nonlinearity and Giant Birefringence in Organic‐Inorganic Halides1Enhanced Birefringence in Organic–Inorganic Hybrid Antimony Halides via Partial Halogen Substitution1Unlocking Nonlinear Optics and Photoluminescence with Simultaneous Enhancement of Bandgap and Birefringence in Hybrid Sb-Based Halides2A Two‐Dimensional Organic Salt With a Deep‐Ultraviolet Cutoff Edge and Strong Second‐Harmonic Generation0A Two‐Dimensional Organic Salt With a Deep‐Ultraviolet Cutoff Edge and Strong Second‐Harmonic Generation0Coordination chemistry of Sb(III)-based optical crystals: from lone-pair-induced distortion to birefringence and second-harmonic generation0

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