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RESEARCH PAPER · Angewandte Chemie International Edition · 2021

A Deep‐UV Nonlinear Optical Borosulfate with Incommensurate Modulations

Yanqiang Li, Zhengyang Zhou, Sangen Zhao, Fei Liang, Qingran Ding, Junliang Sun, Zheshuai Lin, Maochun Hong, Junhua Luo

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A Deep‐UV Nonlinear Optical Borosulfate with Incommensurate ModulationsOriginalPeriodic B- and N-doped phenalenyl π-aggregates: unexpected nonlinear optical properties by tuning pancake π–π bonding6Eckenverknüpfung von drei (BO4)‐Tetraedern in einem Borosulfat: Synthese, Kristallstruktur und quantenchemische Untersuchung von Sr[B3O(SO4)4(SO4H)]6Triple‐Vertex Linkage of (BO4)‐Tetrahedra in a Borosulfate: Synthesis, Crystal Structure, and Quantum‐Chemical Investigation of Sr[B3O(SO4)4(SO4H)]13Achieving Short‐Wavelength Phase‐Matching Second Harmonic Generation in Boron‐Rich Borosulfate with Planar [BO3] Units102Achieving Short‐Wavelength Phase‐Matching Second Harmonic Generation in Boron‐Rich Borosulfate with Planar [BO3] Units9Noncentrosymmetric Ba6In2Q10 (Q = S, Se): Structural Chemistry and Nonlinear-Optical Activity11Anion-Tuned Synthesis of Ag Coordination Compounds: Approaches for Optimizing Second-Harmonic-Generation (SHG) Response5AZn 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 edge25An excellent lead oxyiodide with a strong second-harmonic generation response and a large birefringence induced by the oriented arrangement of highly distorted [PbO 4 I 2 ] polyhedra13APb 2 (C 7 H 3 NO 4 ) 2 I (A = K, Rb, Cs): rare stable nonlinear optical crystals with second-harmonic generation response and highly distorted lead core coordination polyhedra2Cd[B 2 (SO 4 ) 4 ] and H 2 [B 2 (SO 4 ) 4 ] – a phyllosilicate-analogous borosulfate and its homeotypic heteropolyacid11Exploration of the Crystal Structure, Thermal and Spectroscopic Properties of Monoclinic Praseodymium Sulfate Pr2(So4)34From oxides to oxysulfides: the mixed-anion GeS 3 O unit induces huge improvement in the nonlinear optical effect and optical anisotropy for potential nonlinear optical materials19Polymorphism and optical, magnetic and thermal properties of the either phyllo- or inosilicate-analogous borosulfate Cu[B 2 (SO 4 ) 4 ]8Two lead borate-nitrates with anion-centered [OPb 4 ] tetrahedra and two types of π-conjugated planar units showing large birefringence20HgSO4: An excellent mid-infrared sulfate nonlinear optical crystal with wide band gap and strong second harmonic generation response19A2BeS2O8 (A = NH4, K, Rb, Cs) Deep Ultraviolet Nonlinear Optical Crystals33An Optimized KBe2BO3F2‐Like Structure: The Unity of Deep‐Ultraviolet Transparency, Nonlinear Optical Property, and Ferroelectricity22The Kurtz-Perry powder technique revisited: A case study on the importance of reference quality and broadband nonlinear optical measurements using LiInSe232Eu 2 P 2 S 6 : The First Rare‐Earth Chalcogenophosphate Exhibiting Large Second‐Harmonic Generation Response and High Laser‐Induced Damage Threshold143Eu2P2S6: The First Rare‐Earth Chalcogenophosphate Exhibiting Large Second‐Harmonic Generation Response and High Laser‐Induced Damage Threshold7Exploration of the Crystal Structure and Thermal and Spectroscopic Properties of Monoclinic Praseodymium Sulfate Pr2(SO4)334Difluoro(oxalato)borates as Short-Wavelength Optical Crystals with Bifunctional [BF 2 C 2 O 4 ] Units38Chalcohalides: A Rising Type of Second‐Order Nonlinear Optical Materials28Growth, Structure, and Optical Properties of a Nonlinear Optical Niobium Borate Crystal CsNbOB2O5 with Distorted NbO5 Square Pyramids13Local Polarity-Induced Assembly of Second-Order Nonlinear Optical Materials128A promising ultraviolet nonlinear optical crystal: Rb 3 Ba 3 Li 2 Al 4 B 6 O 20 F—crystal growth, physical properties, and 266 nm laser generation17From Cs8Sb4Nb5O5F35 to Cs6Sb4Mo3O5F26: The first noncentrosymmetric fluoroantimonite with d0 transition metal30Recent progress in borate-based short-wavelength nonlinear optical crystals with boron–oxygen skeleton modification28Tetrahedron-based deep-ultraviolet nonlinear optical crystal with optimized KBe 2 BO 3 F 2 -like structure and disordered cations2Two Acentric Aluminoborates Incorporated d10 Cations: Syntheses, Structures, and Nonlinear Optical Properties24Recent Progress in Crystalline Borates with Edge-Sharing BO4 Tetrahedra21Design Principles for Noncentrosymmetric Materials23Ultraviolet Crystal with Strong Optical Nonlinearity by Creating Halogen-Centered Secondary Building Blocks15The Strategy to Improve the Phase Matching Ability in Tetrahedron‐Based Deep‐Ultraviolet Nonlinear Optical Crystals21Deep‐Ultraviolet Transparent Mixed Metal Sulfamates with Enhanced Nonlinear Optical Properties and Birefringence11Deep‐Ultraviolet Transparent Mixed Metal Sulfamates with Enhanced Nonlinear Optical Properties and Birefringence75A nonlinear optical crystal with deep-ultraviolet transparency and appropriate birefringence achieved using π-conjugated confined [B 3 O 3 F 4 (OH)] 2−14M6[Cd2(CO3)2(B12O18)(OH)6] (M = K, Rb): Borate–Carbonates with Two CdCO3 Embedded in a Cyclic Oxoboron Anion10NaK5La2(SO4)6: Enhanced Birefringence of Multiple-Alkali Metal Sulfate Systems via Rare Earth Metal-Centered Polyhedra5Li2NaB3S2O12: A Deep-UV Transparent Borosulfate with Moderate Birefringence Derived from the [B3S2O12]∞ Infinite Chain Designed by the High Boron-to-Sulfur Ratio Strategy6Breaking Symmetry for SHG Response: Lanthanide Acetate Crystals via Water Molecule Regulation Strategy5Looking Back the Nonlinear Optical Crystals in a Functionalized Unit's Perspective109Above Room‐Temperature Reversible Phase Transition and Nonlinear Optical Material PO(CH2CH2CH2CF3)3 with Hirshfeld Surface Analyses0A strongly birefringent sulfate crystal with a wide second-harmonic generation phase-matching range4Bulk crystal growth and optical properties of a novel organic–inorganic hybrid nonlinear optical thiocyanate: [Mn(CH 3 CONH 2 ) 2 ] [Hg(SCN) 4 ]10Phase transition engineering to break the symmetry of diamond-like chalcogenide for second-order nonlinear optics2A HTO‐Type Nonlinear Optical Fluorophosphate with Ultrawide Bandgap16Die ersten Antimon‐Borosulfate offenbaren das Baukastensystem M III M I [B(SO 4 ) 2 ] 4 (M III =Bi 3+ , Sb 3+ , Lu 3+ ; M I =H 3 O + , NO 2 + , Li + , Na + , K + , Rb + , Cs + )0The First Antimony Borosulfates Unveil a Modular System M III M I [B(SO 4 ) 2 ] 4 (M III =Bi 3+ , Sb 3+ , Lu 3+ ; M I =H 3 O + , NO 2 + , Li + , Na + , K + , Rb + , Cs + )7Lithium Borate-Squarate: An Organic–Inorganic Groups-Mixed Nonlinear Optical Crystal with Large Birefringence4A Promising Deep Ultraviolet Nonlinear Optical Crystal Activated by the Ordered Structure Design40A Promising Deep Ultraviolet Nonlinear Optical Crystal Activated by the Ordered Structure Design3Pd[B(S 2 O 7 ) 2 ] 2 and Pd[B(SO 4 ) (S 2 O 7 )] 2 : Two Borosulfates with Pd 2+ in Octahedral and One with Pd 2+ in Square Planar Oxygen Coordination2Non-equivalent terminating roles of hydroxyl and fluorine in hydroxy/fluorooxo-borate optical functional materials2Cs2CdV2O6Br2: A Mid-Infrared Nonlinear Optical Vanadate Containing Both d0/d10 Transition Metal Cations and Bromine Anions5Borosilicates as deep-ultraviolet transparent nonlinear optical crystals: Structural motifs, performance limits and future directions9Variability of a Non‐Centrosymmetric Tecto‐Borosulfate: Introduction of Various Molecular Cations into BiX[B(SO 4 ) 2 ] 4 (X = H 3 O + , NO 2 + , NH 4 + , NO + )5Synthesis and Crystal Structure of Rb[B(SO 4 ) 2 ]: A Borosulfate Obtained from a Reaction with Chlorosulfuric Acid0Mössbauer Spectroscopy on Antimony Borosulfates Reveals Weak Coordination Behavior1Mößbauer‐Spektroskopie an Antimon‐Borosulfaten belegt deren schwache Koordinationskraft1Charge-order-induced directional enhancement of non-diagonal second-order nonlinear optical tensor components2RbLa(SO 4 ) 2 : A KBBF-like Deep-UV Transparent Rare Earth Sulfate with Strong SHG Response and High Thermal Stability Enabled by Multicomponent Structural Design2Significant Enhancement of Birefringence Resulting from the Introduction of [BO 2 (OH)] Groups into Borosulfates0LiK4B(SO4)4: a potential optical crystal for deep ultraviolet zero-order waveplates1Enhancing Birefringence of Sulphates by Polarity Modification in Planar Cations0Hierarchical Ordering Decouples the SHG–Birefringence–LIDT Trade‐Off in a Single‐Phase Mid‐Infrared Nonlinear Optical Crystal0Rational Design of a Strong Nonlinear Optical Crystal With Ultrawide Bandgap via Fine‐Tuning of Channel Structures0Coordination-Mode-Modulated Symmetry Breaking for Nonlinear Optical Crystals0Borophosphate-based second-order nonlinear optical materials: Advances in structural diversity and optical performance0Enhancing the third order nonlinear optical performances of bi-porphyrin derivatives through strategic B,N-substitution and metal-coordination0

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  1. Periodic B- and N-doped phenalenyl π-aggregates: unexpected nonlinear optical properties by tuning pancake π–π bonding

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  2. Eckenverknüpfung von drei (BO4)‐Tetraedern in einem Borosulfat: Synthese, Kristallstruktur und quantenchemische Untersuchung von Sr[B3O(SO4)4(SO4H)]

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  3. Triple‐Vertex Linkage of (BO4)‐Tetrahedra in a Borosulfate: Synthesis, Crystal Structure, and Quantum‐Chemical Investigation of Sr[B3O(SO4)4(SO4H)]

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  4. Achieving Short‐Wavelength Phase‐Matching Second Harmonic Generation in Boron‐Rich Borosulfate with Planar [BO3] Units

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  5. Achieving Short‐Wavelength Phase‐Matching Second Harmonic Generation in Boron‐Rich Borosulfate with Planar [BO3] Units

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  6. Noncentrosymmetric Ba6In2Q10 (Q = S, Se): Structural Chemistry and Nonlinear-Optical Activity

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  7. Anion-Tuned Synthesis of Ag Coordination Compounds: Approaches for Optimizing Second-Harmonic-Generation (SHG) Response

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  8. AZn 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 edge

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  9. An excellent lead oxyiodide with a strong second-harmonic generation response and a large birefringence induced by the oriented arrangement of highly distorted [PbO 4 I 2 ] polyhedra

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  10. APb 2 (C 7 H 3 NO 4 ) 2 I (A = K, Rb, Cs): rare stable nonlinear optical crystals with second-harmonic generation response and highly distorted lead core coordination polyhedra

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  11. Cd[B 2 (SO 4 ) 4 ] and H 2 [B 2 (SO 4 ) 4 ] – a phyllosilicate-analogous borosulfate and its homeotypic heteropolyacid

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  12. Exploration of the Crystal Structure, Thermal and Spectroscopic Properties of Monoclinic Praseodymium Sulfate Pr2(So4)3

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  13. From oxides to oxysulfides: the mixed-anion GeS 3 O unit induces huge improvement in the nonlinear optical effect and optical anisotropy for potential nonlinear optical materials

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  14. Polymorphism and optical, magnetic and thermal properties of the either phyllo- or inosilicate-analogous borosulfate Cu[B 2 (SO 4 ) 4 ]

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  15. Two lead borate-nitrates with anion-centered [OPb 4 ] tetrahedra and two types of π-conjugated planar units showing large birefringence

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  16. HgSO4: An excellent mid-infrared sulfate nonlinear optical crystal with wide band gap and strong second harmonic generation response

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  17. A2BeS2O8 (A = NH4, K, Rb, Cs) Deep Ultraviolet Nonlinear Optical Crystals

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  18. An Optimized KBe2BO3F2‐Like Structure: The Unity of Deep‐Ultraviolet Transparency, Nonlinear Optical Property, and Ferroelectricity

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  23. Difluoro(oxalato)borates as Short-Wavelength Optical Crystals with Bifunctional [BF 2 C 2 O 4 ] Units

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  24. Chalcohalides: A Rising Type of Second‐Order Nonlinear Optical Materials

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  25. Growth, Structure, and Optical Properties of a Nonlinear Optical Niobium Borate Crystal CsNbOB2O5 with Distorted NbO5 Square Pyramids

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  27. A promising ultraviolet nonlinear optical crystal: Rb 3 Ba 3 Li 2 Al 4 B 6 O 20 F—crystal growth, physical properties, and 266 nm laser generation

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  28. From Cs8Sb4Nb5O5F35 to Cs6Sb4Mo3O5F26: The first noncentrosymmetric fluoroantimonite with d0 transition metal

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  29. Recent progress in borate-based short-wavelength nonlinear optical crystals with boron–oxygen skeleton modification

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  30. Tetrahedron-based deep-ultraviolet nonlinear optical crystal with optimized KBe 2 BO 3 F 2 -like structure and disordered cations

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  31. Two Acentric Aluminoborates Incorporated d10 Cations: Syntheses, Structures, and Nonlinear Optical Properties

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  32. Recent Progress in Crystalline Borates with Edge-Sharing BO4 Tetrahedra

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  33. Design Principles for Noncentrosymmetric Materials

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  34. Ultraviolet Crystal with Strong Optical Nonlinearity by Creating Halogen-Centered Secondary Building Blocks

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  35. The Strategy to Improve the Phase Matching Ability in Tetrahedron‐Based Deep‐Ultraviolet Nonlinear Optical Crystals

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  36. Deep‐Ultraviolet Transparent Mixed Metal Sulfamates with Enhanced Nonlinear Optical Properties and Birefringence

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  38. A nonlinear optical crystal with deep-ultraviolet transparency and appropriate birefringence achieved using π-conjugated confined [B 3 O 3 F 4 (OH)] 2−

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  39. M6[Cd2(CO3)2(B12O18)(OH)6] (M = K, Rb): Borate–Carbonates with Two CdCO3 Embedded in a Cyclic Oxoboron Anion

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  40. NaK5La2(SO4)6: Enhanced Birefringence of Multiple-Alkali Metal Sulfate Systems via Rare Earth Metal-Centered Polyhedra

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  41. Li2NaB3S2O12: A Deep-UV Transparent Borosulfate with Moderate Birefringence Derived from the [B3S2O12]∞ Infinite Chain Designed by the High Boron-to-Sulfur Ratio Strategy

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  42. Breaking Symmetry for SHG Response: Lanthanide Acetate Crystals via Water Molecule Regulation Strategy

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  44. Above Room‐Temperature Reversible Phase Transition and Nonlinear Optical Material PO(CH2CH2CH2CF3)3 with Hirshfeld Surface Analyses

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  45. A strongly birefringent sulfate crystal with a wide second-harmonic generation phase-matching range

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  46. Bulk crystal growth and optical properties of a novel organic–inorganic hybrid nonlinear optical thiocyanate: [Mn(CH 3 CONH 2 ) 2 ] [Hg(SCN) 4 ]

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  47. Phase transition engineering to break the symmetry of diamond-like chalcogenide for second-order nonlinear optics

    Inorganic Chemistry Frontiers · 2025-01-01

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  48. A HTO‐Type Nonlinear Optical Fluorophosphate with Ultrawide Bandgap

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  49. Die ersten Antimon‐Borosulfate offenbaren das Baukastensystem M III M I [B(SO 4 ) 2 ] 4 (M III =Bi 3+ , Sb 3+ , Lu 3+ ; M I =H 3 O + , NO 2 + , Li + , Na + , K + , Rb + , Cs + )

    Angewandte Chemie · 2025-02-12

    Erich Turgunbajew, Henning A. Höppe

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  50. The First Antimony Borosulfates Unveil a Modular System M III M I [B(SO 4 ) 2 ] 4 (M III =Bi 3+ , Sb 3+ , Lu 3+ ; M I =H 3 O + , NO 2 + , Li + , Na + , K + , Rb + , Cs + )

    Angewandte Chemie International Edition · 2025-02-12

    Erich Turgunbajew, Henning A. Höppe

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