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RESEARCH PAPER · Angewandte Chemie International Edition · 2021

Strong SHG Responses in a Beryllium‐Free Deep‐UV‐Transparent Hydroxyborate via Covalent Bond Modification

Chao Wu, Xingxing Jiang, Lin Lin, Wenyan Dan, Zheshuai Lin, Zhipeng Huang, Mark Graeme Humphrey, Chi Zhang

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Strong SHG Responses in a Beryllium‐Free Deep‐UV‐Transparent Hydroxyborate via Covalent Bond ModificationOriginalA Lanthanum Ammonium Sulfate Double Salt with a Strong SHG Response and Wide Deep‐UV Transparency15A Lanthanum Ammonium Sulfate Double Salt with a Strong SHG Response and Wide Deep‐UV Transparency96An 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 polyhedra2CsB 3 O 4 (OH) 2 : a new deep-ultraviolet birefringent crystal with [B 3 O 4 (OH) 2 ] anionic group8KLi 2 CO 3 F: a beryllium-free KBBF-type deep-UV carbonate with an enhanced interlayer interaction and large birefringence20KSb(BeF 3 )F 3 : a totally fluorine strategy for achieving wide bandgap and large birefringence23Na 3 B 6 O 10 (HCOO): an ultraviolet nonlinear optical sodium borate-formate33Nain(C2o4)(Hpo4)(H2o)5: An Ultraviolet Transparent Nonlinear Optical Oxalate-Phosphate with Large Birefringence0Synergistic effect of 2 [V 2 P 2 O 14 ] ∞ layers and hydrogen bonds inducing large birefringence in M(VO) 2 (PO 4 ) 2 ·4H 2 O (M = Ca, Sr, Ba) systems4Variable dimensionality of the anion framework in four new borophosphates and fluoroborophosphates with short cutoff edges13Wide bandgaps and strong SHG responses of hetero-oxyfluorides by dual-fluorination-directed bandgap engineering28MM′B3O4F3 (M = K; M′ = Na, K, Cs): Alkali-Metal Fluorooxoborates with ∞1[B3O4F3] Chains and Deep-Ultraviolet Cutoff Edges12Layered Perovskite-like Nitrate Cs2Pb(NO3)2Br2 as a Multifunctional Optical Material40Ba2B10O16(OH)2·(H3BO3)(H2O): A Possible Deep-Ultraviolet Nonlinear-Optical Barium Borate36Sr3[SnOSe3][CO3]: A Heteroanionic Nonlinear Optical Material Containing Planar π‐conjugated [CO3] and Heteroleptic [SnOSe3] Anionic Groups78Sr3[SnOSe3][CO3]: A Heteroanionic Nonlinear Optical Material Containing Planar π‐conjugated [CO3] and Heteroleptic [SnOSe3] Anionic Groups7Double‐Modification Oriented Design of a Deep‐UV Birefringent Crystal Functionalized by [B12O16F4(OH)4] Clusters9Double‐Modification Oriented Design of a Deep‐UV Birefringent Crystal Functionalized by [B12O16F4(OH)4] Clusters139The Kurtz-Perry powder technique revisited: A case study on the importance of reference quality and broadband nonlinear optical measurements using LiInSe232Difluoro(oxalato)borates as Short-Wavelength Optical Crystals with Bifunctional [BF 2 C 2 O 4 ] Units38Two New Nonaborates with {B9} Cluster Open-Frameworks and Short Cutoff Edges4Cs2B4O5(OH)4: A new hydrated borate with a short UV cutoff edge2Isoreticular Design of KTiOPO 4 -Like Deep-Ultraviolet Transparent Materials Exhibiting Strong Second-Harmonic Generation68Exploring Short-Wavelength Phase-Matching Nonlinear Optical Crystals by Employing KBe2BO3F2 as the Template95Rb 3 B 11 P 2 O 23 : Materials Design of a New Chemically Benign Deep-Ultraviolet Nonlinear Optical Material58A 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 generation17Ce 3 F 4 (SO 4 ) 4 : cationic framework assembly for designing polar nonlinear optical material through fluorination degree modulation23Hydroxyfluorooxoborate (NH 4 )[C(NH 2 ) 3 ][B 3 O 3 F 4 (OH)] for exploring the effects of cation substitution on structure and optical properties26Recent progress in borate-based short-wavelength nonlinear optical crystals with boron–oxygen skeleton modification28Two Acentric Aluminoborates Incorporated d10 Cations: Syntheses, Structures, and Nonlinear Optical Properties24Toward Large Second-Harmonic Generation and Deep-UV Transparency in Strongly Electropositive Transition Metal Sulfates112Rational Design of the First Ammonium Magnesium Borate with Deep-Ultraviolet Cutoff Edge and Moderate Birefringence and Further Investigation into the Nature of Ammonium in the Borate System15The Kurtz–Perry Powder Technique Revisited: A Study of the Effect of Reference Selection on Powder Second-Harmonic Generation Response20FILLING OF CHANNELS OF THE ZEOLITE FRAMEWORK IN TRIGONAL POLAR NONABORATE Ва3Na0.9(OH)1.9[B9O16][B(OH)3]0The dubious origin of beryllium toxicity44Two Mixed-Alkali-Metal Selenates as Short-Wave Ultraviolet Nonlinear-Optical Materials10Filling of Channels of the Zeolite Framework in Trigonal Polar Nonaborate Ва3Na0.9(OH)1.9[B9O16][B(OH)3]0Cs 3 [(BOP) 2 (B 3 O 7 ) 3 ]: A Deep-Ultraviolet Nonlinear Optical Crystal Designed by Optimizing Matching of Cation and Anion Groups169Recent Progress in Crystalline Borates with Edge-Sharing BO4 Tetrahedra21Quadruple‐Bidentate Nitrate‐Ligated A 2 Hg(NO 3 ) 4 (A=K, Rb): Strong Second‐Harmonic Generation and Sufficient Birefringence59Quadruple‐Bidentate Nitrate‐Ligated A 2 Hg(NO 3 ) 4 (A=K, Rb): Strong Second‐Harmonic Generation and Sufficient Birefringence2Na1.5Cs0.5[Al{BO3}{B9O15(OH)3}1/3]: An Acentric Layered Aluminoborate with Nonlinear-Optical Properties9Characterization of organic crystals for second-harmonic generation13Ba 4 B 14 O 25 : A Deep Ultraviolet Transparent Nonlinear Optical Crystal with Strong Second Harmonic Generation Response Achieved by a Boron‐Rich Closed‐Loop Strategy12Preparation of novel silver borates by soft hydrothermal synthesis in sealed tubes: New representatives of larderellite and veatchite families17Secondary‐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 Birefringence41“One stone two birds” design of borates featuring edge-sharing [BO 4 ] and different B–O configurations in one structure utilizing covalent tetrahedra8NaB(OH) 3 CH 3 : a deep-ultraviolet optical crystal with unprecedented methyl-modified [B(OH) 3 CH 3 ] units6Toward the ultraviolet (UV) or deep-UV nonlinear optical crystals: The combination of π-conjugated planar [XY3] and tetrahedral [XY4]80Record Second-Harmonic Generation and Birefringence in an Ultraviolet Antimonate by Bond Engineering157Extending Unique 1D Double-Chains to 2D Layers with Birefringent Gain by Introducing a Hydroxyl Group5Sr2[B5O8(OH)]2 ⋅ [B(OH)3] ⋅ H2O: A Strontium Borate That Shows Deep‐Ultraviolet‐Transparent Nonlinear Optical Properties17Two Hydroxyfluorooxoborates Achieving Deep‐Ultraviolet Cutoff Edges and Moderate Birefringence by Assembling Multi‐Anionic Groups6NaRbB10O14(OH)4 and Na3CsB10O16(OH)2: Two Cases of Hydroxyborates with [B5Om(OH)n] Units and Deep Ultraviolet Cutoff Edges6An Unprecedented [BO2]‐Based Deep‐Ultraviolet Transparent Nonlinear Optical Crystal by Superhalogen Substitution33An Unprecedented [BO2]‐Based Deep‐Ultraviolet Transparent Nonlinear Optical Crystal by Superhalogen Substitution1M6[Cd2(CO3)2(B12O18)(OH)6] (M = K, Rb): Borate–Carbonates with Two CdCO3 Embedded in a Cyclic Oxoboron Anion10Structural Regulations of Layered Borates: From Centric Layers to Chiral Porous Layers3Enhanced UV Nonlinear Optical Properties in Layered Germanous Phosphites through Functional Group Sequential Construction11Enhanced UV Nonlinear Optical Properties in Layered Germanous Phosphites through Functional Group Sequential Construction116Toward Strong UV–Vis–NIR Second-Harmonic Generation by Dimensionality Engineering of Zinc Thiocyanates32Structural Evolution and Optical Properties of Hydroxyfluorooxoborates MM′2n-1[B3O3F4(OH)]n (M = K, Cs, and Rb; M′ = K, NH4, and Cs; n = 1, 2, and 3)12Computer‐Aided Development of New Nonlinear Optical Materials38Computer‐Aided Development of New Nonlinear Optical Materials14Structural modification of hydroxyborates by adjusting the number of shared oxygen atoms and hydroxyl groups for further performance enhancement1Rational design of a series of non-centrosymmetric antiperovskite and double antiperovskite borate fluorides13CsBO(OH) 2 : a new hydroxyborate with the rare [BO(OH) 2 ] group and a deep ultraviolet cutoff edge3RbB 7 O 10 (OH) 2 and NaB 11 O 16 (OH) 2 : alkali metal hydroxyborates with two-dimensional layered structures and large birefringence1Two mixed P–O anionic phosphates with a distinctive structural transformation and deep ultraviolet cutoff edge0Non-equivalent terminating roles of hydroxyl and fluorine in hydroxy/fluorooxo-borate optical functional materials2Structures and Nonlinear Optical Properties of Two Acentric Borates with Cubic Cage-like Frameworks5NH4B5O7(OH)2 and CsRbB10O14(OH)4·H2O: Two Hydroxyborates Feature Significant Optical Anisotropy and Contain 1∞[B5O7(OH)2] Chains1Hydroxyl-induced structural reconstruction: two new potassium hepta-borates with deep-UV transparency and enhanced birefringence1Asymmetry-driven organic–inorganic hybrid strategy for constructing structures with exceptional organofunctionalized B–O units2A multi-scale birefringence modulation strategy in DUV/UV crystals induced by organic cations1A New Short-Wavelength UV NLO Material based on Dual Alkaline-Earth Metal Borophosphate with 1D Helical Anionic Chains0CsB(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 properties0[Sr(H 2 O)]{Sr[B(OH) 3 ]}[B 5 O 8 (OH)] 2 : A Deep-Ultraviolet Second-Order Nonlinear Optical Strontium Borate Constructed by Mixing π-Conjugated and Non-π-Conjugated Units11D Cobalt‐Cytidine Monophosphate Coordination Polymer Exhibiting Efficient Ultraviolet Second‐Harmonic Generation7[C 3 N 2 H 5 ]B 7 O 10 F 2 : Demonstrating a New Hydrogen‐Bond‐Induced Intralayer Charge‐Balanced Structure Model with Large Birefringence3F−/OH− terminal modification of [B3O6] clusters: Constructing deep-ultraviolet hydroxyfluorooxoborates with tunable optical performance0Assembly of Functional Units for Constructing an Ultraviolet-Transparent Nonlinear Optical Mixed Alkaline Metal Borate-Formate1Metal–organic framework-based second-order nonlinear optical materials: From structural design to functional applications0Two Acentric Borates with 2-/3-D Frameworks: Syntheses, Structures, and Nonlinear Optical Properties0Unlocking Hidden Potential via Reprogrammed Mineral Structures: How Anionic Transformation Achieves Ultraviolet Nonlinear Optical Performance0Influence of the Cation Size on Symmetry Breaking and Optical Performances in Ae2Mg3(BO3)2F4 (Ae = Sr, Ba)0Cation‐Regulated [CH 3 BO 2 F]‐Derived Borates: Synergistic Fluorination and Organic Functionalization for High‐Birefringence UV NLO Materials0

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  1. A Lanthanum Ammonium Sulfate Double Salt with a Strong SHG Response and Wide Deep‐UV Transparency

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  2. A Lanthanum Ammonium Sulfate Double Salt with a Strong SHG Response and Wide Deep‐UV Transparency

    Angewandte Chemie International Edition · 2021-12-11

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  3. 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

    Inorganic Chemistry Frontiers · 2022-01-01

    Ziqi Zhou, Ruibiao Fu, Hong‐Xin Tang, Zuju Ma, Xin‐Tao Wu

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  4. 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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  5. CsB 3 O 4 (OH) 2 : a new deep-ultraviolet birefringent crystal with [B 3 O 4 (OH) 2 ] anionic group

    Dalton Transactions · 2022-01-01

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  6. KLi 2 CO 3 F: a beryllium-free KBBF-type deep-UV carbonate with an enhanced interlayer interaction and large birefringence

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  7. KSb(BeF 3 )F 3 : a totally fluorine strategy for achieving wide bandgap and large birefringence

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  8. Na 3 B 6 O 10 (HCOO): an ultraviolet nonlinear optical sodium borate-formate

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  9. Nain(C2o4)(Hpo4)(H2o)5: An Ultraviolet Transparent Nonlinear Optical Oxalate-Phosphate with Large Birefringence

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  10. Synergistic effect of 2 [V 2 P 2 O 14 ] ∞ layers and hydrogen bonds inducing large birefringence in M(VO) 2 (PO 4 ) 2 ·4H 2 O (M = Ca, Sr, Ba) systems

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  11. Variable dimensionality of the anion framework in four new borophosphates and fluoroborophosphates with short cutoff edges

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  12. Wide bandgaps and strong SHG responses of hetero-oxyfluorides by dual-fluorination-directed bandgap engineering

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  13. MM′B3O4F3 (M = K; M′ = Na, K, Cs): Alkali-Metal Fluorooxoborates with ∞1[B3O4F3] Chains and Deep-Ultraviolet Cutoff Edges

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  14. Layered Perovskite-like Nitrate Cs2Pb(NO3)2Br2 as a Multifunctional Optical Material

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  15. Ba2B10O16(OH)2·(H3BO3)(H2O): A Possible Deep-Ultraviolet Nonlinear-Optical Barium Borate

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  16. Sr3[SnOSe3][CO3]: A Heteroanionic Nonlinear Optical Material Containing Planar π‐conjugated [CO3] and Heteroleptic [SnOSe3] Anionic Groups

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  17. Sr3[SnOSe3][CO3]: A Heteroanionic Nonlinear Optical Material Containing Planar π‐conjugated [CO3] and Heteroleptic [SnOSe3] Anionic Groups

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  18. Double‐Modification Oriented Design of a Deep‐UV Birefringent Crystal Functionalized by [B12O16F4(OH)4] Clusters

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  19. Double‐Modification Oriented Design of a Deep‐UV Birefringent Crystal Functionalized by [B12O16F4(OH)4] Clusters

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  20. The Kurtz-Perry powder technique revisited: A case study on the importance of reference quality and broadband nonlinear optical measurements using LiInSe2

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

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  22. Two New Nonaborates with {B9} Cluster Open-Frameworks and Short Cutoff Edges

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  23. Cs2B4O5(OH)4: A new hydrated borate with a short UV cutoff edge

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  24. Isoreticular Design of KTiOPO 4 -Like Deep-Ultraviolet Transparent Materials Exhibiting Strong Second-Harmonic Generation

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  25. Exploring Short-Wavelength Phase-Matching Nonlinear Optical Crystals by Employing KBe2BO3F2 as the Template

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  26. Rb 3 B 11 P 2 O 23 : Materials Design of a New Chemically Benign Deep-Ultraviolet Nonlinear Optical Material

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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. Ce 3 F 4 (SO 4 ) 4 : cationic framework assembly for designing polar nonlinear optical material through fluorination degree modulation

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  29. Hydroxyfluorooxoborate (NH 4 )[C(NH 2 ) 3 ][B 3 O 3 F 4 (OH)] for exploring the effects of cation substitution on structure and optical properties

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

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

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  32. Toward Large Second-Harmonic Generation and Deep-UV Transparency in Strongly Electropositive Transition Metal Sulfates

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  33. Rational Design of the First Ammonium Magnesium Borate with Deep-Ultraviolet Cutoff Edge and Moderate Birefringence and Further Investigation into the Nature of Ammonium in the Borate System

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  34. The Kurtz–Perry Powder Technique Revisited: A Study of the Effect of Reference Selection on Powder Second-Harmonic Generation Response

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  35. FILLING OF CHANNELS OF THE ZEOLITE FRAMEWORK IN TRIGONAL POLAR NONABORATE Ва3Na0.9(OH)1.9[B9O16][B(OH)3]

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  36. The dubious origin of beryllium toxicity

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  37. Two Mixed-Alkali-Metal Selenates as Short-Wave Ultraviolet Nonlinear-Optical Materials

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  38. Filling of Channels of the Zeolite Framework in Trigonal Polar Nonaborate Ва3Na0.9(OH)1.9[B9O16][B(OH)3]

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  39. Cs 3 [(BOP) 2 (B 3 O 7 ) 3 ]: A Deep-Ultraviolet Nonlinear Optical Crystal Designed by Optimizing Matching of Cation and Anion Groups

    Journal of the American Chemical Society · 2023-05-26

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

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  41. Quadruple‐Bidentate Nitrate‐Ligated A 2 Hg(NO 3 ) 4 (A=K, Rb): Strong Second‐Harmonic Generation and Sufficient Birefringence

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  42. Quadruple‐Bidentate Nitrate‐Ligated A 2 Hg(NO 3 ) 4 (A=K, Rb): Strong Second‐Harmonic Generation and Sufficient Birefringence

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  43. Na1.5Cs0.5[Al{BO3}{B9O15(OH)3}1/3]: An Acentric Layered Aluminoborate with Nonlinear-Optical Properties

    Inorganic Chemistry · 2023-08-21

    Chong‐An Chen, Guo‐Yu Yang

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  44. Characterization of organic crystals for second-harmonic generation

    Optics Letters · 2023-10-18

    Kayla M. Holland, Aldair Alejandro, Daisy J. H. Ludlow, Paige Petersen, Melodie A. Wright, Caitlin C. Chartrand, David J. Michaelis, Jeremy A. Johnson, James E. Patterson

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  45. Ba 4 B 14 O 25 : A Deep Ultraviolet Transparent Nonlinear Optical Crystal with Strong Second Harmonic Generation Response Achieved by a Boron‐Rich Closed‐Loop Strategy

    Small · 2023-11-08

    Weijie Xie, Ru‐Ling Tang, Shengnan Yan, Nan Ma, Chun‐Li Hu, Jiang‐Gao Mao

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  46. Preparation of novel silver borates by soft hydrothermal synthesis in sealed tubes: New representatives of larderellite and veatchite families

    Solid State Sciences · 2023-12-15

    Sergey N. Volkov, Sergey M. Aksenov, Dmitri O. Charkin, A. M. Banaru, Daria A. Banaru, Yulia A. Vaitieva, Maria Georgievna Krzhizhanovskaya, N. A. Yamnova, Vadim E. Kireev, Alevtina N. Gosteva, Nikita Sergeyevich Tsvetov, Yevgeny E. Savchenko, Р. С. Бубнова

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  47. Secondary‐Bond‐Driven Construction of a Polar Material Exhibiting Strong Broad‐Spectrum Second‐Harmonic Generation and Large Birefringence

    Angewandte Chemie · 2023-12-20

    Tianhui Wu, Xingxing Jiang, Kaining Duanmu, Chao Wu, Zheshuai Lin, Zhipeng Huang, Mark Graeme Humphrey, Chi Zhang

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  48. Secondary‐Bond‐Driven Construction of a Polar Material Exhibiting Strong Broad‐Spectrum Second‐Harmonic Generation and Large Birefringence

    Angewandte Chemie International Edition · 2023-12-20

    Tianhui Wu, Xingxing Jiang, Kaining Duanmu, Chao Wu, Zheshuai Lin, Zhipeng Huang, Mark Graeme Humphrey, Chi Zhang

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  49. “One stone two birds” design of borates featuring edge-sharing [BO 4 ] and different B–O configurations in one structure utilizing covalent tetrahedra

    Journal of Materials Chemistry C · 2024-01-01

    Haoran Wang, Jiahao Jiao, Abudukadi Tudi, Shilie Pan, Min Zhang

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  50. NaB(OH) 3 CH 3 : a deep-ultraviolet optical crystal with unprecedented methyl-modified [B(OH) 3 CH 3 ] units

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