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RESEARCH PAPER · Chemistry - A European Journal · 2019

Lone‐Pair Enhanced Birefringence in an Alkaline‐Earth Metal Tin(II) Phosphate BaSn 2 (PO 4 ) 2

Yi Jin Yang, Yi Qiu, Pifu Gong, Lei Kang, Gaomin Song, Xiaomeng Liu, Junliang Sun, Zheshuai Lin

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Lone‐Pair Enhanced Birefringence in an Alkaline‐Earth Metal Tin(II) Phosphate BaSn 2 (PO 4 ) 2OriginalA 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 materials98Two new tin( iv )-containing phosphate fluorides with two types of Sn( iv )–P–O–F frameworks and short cutoff edges0Highly Polarizable Hg2+ Induced a Strong Second Harmonic Generation Signal and Large Birefringence in LiHgPO4265Ba 8 SrPb 24 O 24 Cl 18 : the first alkali-earth metal lead( ii ) oxyhalide with an intriguing multimember-ring layer9Sn2B5O9Cl: A Material with Large Birefringence Enhancement Activated Prepared via Alkaline‐Earth‐Metal Substitution by Tin255Sn2B5O9Cl: A Material with Large Birefringence Enhancement Activated Prepared via Alkaline‐Earth‐Metal Substitution by Tin33Cation Modulation on the Crystal Structure and Band Gap of Fluorooxoborates A3B3O3F6 (A = Alkali and Mixed Alkali Metal)17A new iodate-phosphate Pb 2 (IO 3 )(PO 4 ) achieving great improvement in birefringence activated by (IO 3 ) − groups53(NH 4 ) 3 [B(OH) 3 ] 2 (COOH) 3 : a graphite-like UV nonlinear optical material with a large birefringence via structural optimization31From BaAl 2 (BO 3 ) 2 O to SnAl 2 (BO 3 ) 2 F 2 : structure transformation based on ion regulation3Te 3 O 3 (PO 4 ) 2 : a phosphate crystal with large birefringence activated by the highly distorted [TeO 5 ] group and antiparallel [PO 4 ] pseudo-layer33Two new ammonium/alkali-rare earth metal difluorophosphates ALa(PO 2 F 2 ) 4 (A = NH 4 and K) with moderate birefringence and short cutoff edges26PbB5O7F3: A High-Performing Short-Wavelength Nonlinear Optical Material120K4Sb(SO4)3Cl: The first apatite-type sulfate ultraviolet nonlinear optical material with sharply enlarged birefringence61High Coordinate Metal Iodate Chlorides with Diverse Structural Motifs and Tunable Birefringence10LiGaF2(IO3)2: A mixed-metal gallium iodate-fluoride with large birefringence and wide band gap39K 2 Sb(P 2 O 7 )F: Cairo Pentagonal Layer with Bifunctional Genes Reveal Optical Performance297K2Sb(P2O7)F: Cairo Pentagonal Layer with Bifunctional Genes Reveal Optical Performance38The study of structure evolvement of KTiOPO4 family and their nonlinear optical properties98NaTePO5, SrTeP2O8 and Ba2TeP2O9: Three tellurite-phosphates with large birefringence22Na3AMg7(PO4)6 (A = K, Rb and Cs): Structures, properties and theoretical studies of alkali metal magnesium orthophosphates14Y 2 (Te 4 O 10 )(SO 4 ): a new sulfate tellurite with a unique Te 4 O 10 polyanion and large birefringence36α‐SnF 2 : A UV Birefringent Material with Large Birefringence and Easy Crystal Growth24α‐SnF 2 : A UV Birefringent Material with Large Birefringence and Easy Crystal Growth210KSnI 3 ⋅ H 2 O: A New Compound with One‐Dimensional SnI 3 Chains of Pyramidal SnI 5 Polyhedra2Sn2B5O9Br as an Outstanding Bifunctional Material with Strong Second‐Harmonic Generation Effect and Large Birefringence84Synergism of multiple functional chromophores significantly enhancing the birefringence in layered non-centrosymmetric chalcohalides20An antimony( iii ) borate with large birefringence exhibiting unwonted [B 5 O 11 ] fundamental building blocks and dimeric [Sb 2 O 6 ] clusters26BaTi(BO 3 ) 2 : an excellent birefringent material with highly coplanar isolated [BO 3 ] groups16Centrosymmetric RbSnF 2 NO 3 vs. noncentrosymmetric Rb 2 SbF 3 (NO 3 ) 254K 2 ZnMoP 2 O 10 : a novel nonlinear optical molybdophosphate with a strong second harmonic generation response and moderate birefringence24SrTi(IO 3 ) 6 ·2H 2 O and SrSn(IO 3 ) 6 : distinct arrangements of lone pair electrons leading to large birefringences11Ba3Sb2(PO4)4 and Cd3Sb2(PO4)4(H2O)2: Two New Antimonous Phosphates with Distinct [Sb(PO4)2] Structure Types and Enhanced Birefringence37A2(TeO)P2O7 (A = K, Rb, Cs): Three new tellurite-pyrophosphates with large birefringence17Different mechanism of stereochemical activity and birefringence in post-transition metal halides: A first-principles investigation1Large Second-Harmonic Response and Giant Birefringence of CeF 2 (SO 4 ) Induced by Highly Polarizable Polyhedra248Molecular Engineering toward an Enlarged Optical Band Gap in a Bismuth Sulfate via Homovalent Cation Substitution26Fluorine‐Driven Enhancement of Birefringence in the Fluorooxosulfate: A Deep Evaluation from a Joint Experimental and Computational Study139Cs2ZnSn3S8: A Sulfide Compound Realizes a Large Birefringence by Modulating the Dimensional Structure24Hydroxyfluorooxoborate Na[B3O3F2(OH)2]⋅[B(OH)3]: Optimizing the Optical Anisotropy with Heteroanionic Units for Deep Ultraviolet Birefringent Crystals146Hydroxyfluorooxoborate Na[B3O3F2(OH)2]⋅[B(OH)3]: Optimizing the Optical Anisotropy with Heteroanionic Units for Deep Ultraviolet Birefringent Crystals16SnPQ3 (Q = S, Se, S/Se): A Series of Lone-Pair Cationic Chalcogenophosphates Exhibiting Balanced NLO Activity Originating from SnQ8 Units49Sn2PO4I: An Excellent Birefringent Material with Giant Optical Anisotropy in Non π‐Conjugated Phosphate212Sn2PO4I: An Excellent Birefringent Material with Giant Optical Anisotropy in Non π‐Conjugated Phosphate22Tin(II)-Induced Large Birefringence Enhancement in Metal Phosphates22Enhancement of band gap and birefringence induced via π -conjugated chromophore with “tail effect”28NaSb3O2(SO4)3·H2O: A New Alkali-Metal Antimony(III) Sulfate with a Unique Sb6O20H4 Unit and Moderate Birefringence19[C(NH 2 ) 3 ]BiCl 2 SO 4 : an excellent birefringent material obtained by multifunctional group synergy40Halogen regulation triggers structural transformation from centrosymmetric to noncentrosymmetric switches in tin phosphate halides Sn 2 PO 4 X (X = F, Cl)47Large optical anisotropy differentiation induced by the anion-directed regulation of structures29LiSrSbS 3 : parallel configurations of lone pair electrons inducing a large birefringence16PNO: a promising deep-UV nonlinear optical material with the largest second harmonic generation effect17From Pb(H 2 C 3 N 3 O 3 )(OH) to Pb(H 2 C 3 N 3 O 3 )F: Homovalent Anion Substitution-Induced Band Gap Enlargement and Birefringence Enhancement26HgTeO2F(OH): A Nonlinear Optical Oxyfluoride Constructed of Active [TeO2F(OH)]2– Pyramids and V-Shaped [HgO2]2– Groups36Potential optical functional crystals with large birefringence: Recent advances and future prospects322A Hybrid Halide Perovskite Birefringent Crystal14A Hybrid Halide Perovskite Birefringent Crystal149Lone Pair-Driven Enhancement of Birefringence in Polar Alkali Metal Antimony Phosphates46RbLiZn5(PO4)4 and BaLiZn3(PO4)3: two new zinc orthophosphates with all tetrahedra-based anion frameworks11Enhancement of Birefringence in Borophosphate Pushing Phase-Matching into the Short-Wavelength Region150Yin–Yang Complementarity Strategy Achieving Giant Optical Anisotropy in a Metal-free Birefringent Material C(NH2)3(HC4O4)14Cation-anion synergetic interactions achieving tunable birefringence in quasi-one-dimensional antimony(III) fluoride oxalates58Sharp Enhancement of Birefringence in Antimony Oxalates Achieved by the Cation–Anion Synergetic Interaction Strategy38Design of a new ultraviolet nonlinear optical material KNO3SO3NH3 exhibiting an unexpected strong second harmonic generation response44Finding a Deep‐UV Borate BaZnB4O8 with Edge‐sharing [BO4] Tetrahedra and Strong Optical Anisotropy20Li2PbB2O5: A Pyroborate with Large Birefringence Induced by the Synergistic Effect of Stereochemical Active Lone Pair Cations and π-Conjugated [B2O5] Groups14Noncentrosymmetric versus Centrosymmetric: Halogen Induced Variable Coordination Modes of Sn2+ and Structural Transition in Sn3B3O7X (X = Cl and Br)17A hybrid halide lead-free pseudo-perovskite with large birefringence37Anisotropic structure building unit involving diverse chemical bonds: a new opportunity for high-performance second-order NLO materials181Low temperature molten salt synthesis of noncentrosymmetric (NH 4 ) 3 SbF 3 (NO 3 ) 3 and centrosymmetric (NH 4 ) 3 SbF 4 (NO 3 ) 234Structure and optical property evolution in PbM(PO 4 )X (M = Zn, Sn; X = halogen): SHG effect and birefringence21Deep Eutectic Solvents Synthesis of A2Sb(C2O4)Cl3 (A = NH4, K, Rb) with Superior Optical Performance26Recent Development of Sn II , Sb III ‐based Birefringent Material: Crystal Chemistry and Investigation of Birefringence130Recent Development of SnII, SbIII‐based Birefringent Material: Crystal Chemistry and Investigation of Birefringence6Sb4O3(TeO3)2(HSO4)(OH): An Antimony Tellurite Sulfate Exhibiting Large Optical Anisotropy Activated by Lone Pair Stereoactivity30Stereochemically Active Tin(II)‐Induced Enhancement of Birefringence in SnIISnIV(PO4)2 and SrSn(PO4)PO2(OH)23Birefringence Regulation by Clarifying the Relationship Between Stereochemically Active Lone Pairs and Optical Anisotropy in Tin‐based Ternary Halides56Birefringence Regulation by Clarifying the Relationship Between Stereochemically Active Lone Pairs and Optical Anisotropy in Tin‐based Ternary Halides2Atomic Substitution to Tune ScO6 Distortion in Ba2MSc2(BO3)4 (M = Na, K, Ba) to Acquire a Large Birefringence15(NH4)3(H3O)Zn4(PO4)4: A nonlinear optical zinc orthophosphate crystal9Pb(OH)I: A lead(II)-based oxyhalide with a large birefringence5Centrosymmetric Rb2Sb(C2O4)2.5(H2O)3 and Noncentrosymmetric RbSb2(C2O4)F5: Two Antimony (III) Oxalates as UV Optical Materials20K2Sr4(PO3)10: A Polyphosphate with Deep-UV Cutoff Edge and Enlarged Birefringence6Hydroxyl-Driven Enhanced Birefringence in Borophosphates3Chiral amino acid-templated tin fluorides tailoring nonlinear optical properties, birefringence, and photoluminescence17CsSn2(HPO3)2I: The first inorganic metal phosphite iodide as a promising birefringent material exhibits a large birefringence with ideally layered framework24K 2 RbB 8 PO 16 : A Borophosphate with Moderate Birefringence and Deep-Ultraviolet Transmission10Rational Design of the Alkali Metal Sn‐Based Mixed Halides with Large Birefringence and Wide Transparent Range44[Sn 3 OF]PO 4 vs. [Sn 3 F 3 ]PO 4 : enhancing birefringence by breaking the R 3 symmetry and realigning lone pairs12Explorations of highly birefringent materials in the vanadium oxyfluoride–iodate system by fluoride ion modulation8Greatly enhanced optical anisotropy in thiophosphates inspired by rational coupling of tetrahedra and ethane-like [P 2 S 6 ] 4− groups7HgBr 2 : an easily growing wide-spectrum birefringent crystal38Li 3 Na 7 B 4 P 6 O 26 : a new ultraviolet transparent congruently melting non-linear optical crystal3NaVSeO 5 : synergistic combinations to synthesize excellent birefringent materials8New antimony fluorooxoborates with strong birefringence and unprecedented structural characterisation19New ultraviolet transparent rare-earth borates with enhanced birefringence induced by cation chemical substitution15The effect of co-substitution of heterovalent ions Ga 3+ and Sb 5+ on nonlinear optical properties of phosphate crystals0Sb4O5I2: Enhancing Birefringence through Optimization of Sb/I Ratio for Alignment of Stereochemically Active Lone Pairs18Exceptional Optical Anisotropy Enhancement Achieved Through Dual‐Ions Cosubstitution Strategy in Novel Hybrid Bismuth Halides23Giant Optical Anisotropy in a Covalent Molybdenum Tellurite via Oxyanion Polymerization43Stereochemically Active Lone Pair Leads to Birefringence in the Vacancy Ordered Cs3Sb2Cl9 Perovskite Single Crystals13Unleashing the potential of π-conjugated [B2O3(OH)2] to enhance birefringence in DUV crystals9Enhancement of Birefringence in π-Conjugated Oxyfluorides Achieved via van der Waals Layered Structural Optimization10Crystal structure, electronic structure and thermal stability of new phosphate Sr2In(PO4)(P2O7)3Edge-Sharing Tetrahedra Realizing Superior Birefringence and High Deep-Ultraviolet Transmittance in α-Be3(H2O)2(PO4)2 Crystal Synthesized by Mild Chemistry14Tunable Optical Anisotropy in Rare‐Earth Borates with Flexible [BO3] Clusters7(C 8 H 7 N 2 O 2 ) 2 [Bi 2 Br 8 ]·2H 2 O and (C 8 H 7 N 2 O 2 ) 6 [Bi 2 Cl 10 ]Cl 2 ·2H 2 O: Exploring Birefringent Crystals in Hybrid Halide Systems5Enhanced 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 Construction116Review on birefringence in borates based on birefringence-active functional groups and arrangements57[B3O3F4(OH)]2–: A Versatile Hydroxyfluorooxoborate Heteroanion Producing Compounds with Highly Tunable Optical Anisotropy19(C3N2H5)B3O3F2(OH)2: Realizing Large Birefringence via a Synergistic Effect between Anion F/OH‐Ratio Optimization and Cation Activation25Photoluminescence and Refractive Index Dispersion Properties of Zn3−xMx(PO4)2 (M=Co, Ni; x = 1) Nanoparticles0The electronic structure and optical properties of BaBiBO4, a promising compound with high birefringence1First-principles study of three isomers of the large birefringent crystal Sb4O4F4: electronic structure and optical properties0Functional assembly and modification of nonlinear optical fundamental motifs in phosphates27Strategically designed anisotropic organic–inorganic metal halides (OIMHs) with superior balance between bandgap and birefringence12A 3 Sc(PO 4 ) 2 (A = Li, Na): rare earth cations effectively regulate phosphate structures for enhanced birefringence4SnHPO4: A Layered Tin(II) Phosphate with Enhanced Birefringence51Sb2(TeO4)(SO4): An Anhydrous Tellurite Sulfate with Large Birefringence and Enhanced Thermal Stability8(NH4)Na3Zn4(PO4)4:An open-framework zincophosphate exhibiting well-balanced optical and thermal performance1High‐Throughput Discovery of Large Birefringence Materials in Mixed‐N Hf‐O Systems0A 2 Sb 2 SO 4 F 6 (A = NH 4 + , Na + ): two sulfate fluoride crystals exhibiting enhanced birefringence driven by stereochemically active antimony( iii )1Na 2 SnSO 4 F 2 : an ultraviolet-transparent sulfate crystal with large birefringence driven by stereochemically active tin( ii )1The electronic structurs, refractive indices and Berry curvature induced by the spin-orbit coupling in BiOX compounds: A first-principles investigation0NH 4 B 3 PO 6 (OH) 3 : A Hydroxyborophosphate with Short DUV Cutoff Edge and Large Birefringence2Structural Anion Geometry-Regulated Molecular Alignment in [C 10 H 8 NO 2 ]-Based Crystals for Enhancing Ultraviolet Birefringence0The electronic structures, refractive indices and Berry curvature induced by the spin-orbit coupling in BiOX compounds: A first-principles investigation0A Strategy for Enhancing the Optical Anisotropy of Phosphates via Tetrahedral Unit Modification0Non-π-conjugated tetrahedra-based optical crystals: The improvement of the linear and nonlinear optical properties by the combination of trigonal pyramidal [XO3] (X = I, Se, Te) units1

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  1. A 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 materials

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  2. Two new tin( iv )-containing phosphate fluorides with two types of Sn( iv )–P–O–F frameworks and short cutoff edges

    New Journal of Chemistry · 2019-01-01

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  3. Highly Polarizable Hg2+ Induced a Strong Second Harmonic Generation Signal and Large Birefringence in LiHgPO4

    Journal of the American Chemical Society · 2019-06-16

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  4. Ba 8 SrPb 24 O 24 Cl 18 : the first alkali-earth metal lead( ii ) oxyhalide with an intriguing multimember-ring layer

    Dalton Transactions · 2019-08-19

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  5. Sn2B5O9Cl: A Material with Large Birefringence Enhancement Activated Prepared via Alkaline‐Earth‐Metal Substitution by Tin

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  6. Sn2B5O9Cl: A Material with Large Birefringence Enhancement Activated Prepared via Alkaline‐Earth‐Metal Substitution by Tin

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  7. Cation Modulation on the Crystal Structure and Band Gap of Fluorooxoborates A3B3O3F6 (A = Alkali and Mixed Alkali Metal)

    Inorganic Chemistry · 2019-09-18

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  8. A new iodate-phosphate Pb 2 (IO 3 )(PO 4 ) achieving great improvement in birefringence activated by (IO 3 ) − groups

    Chemical Communications · 2019-12-04

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  9. (NH 4 ) 3 [B(OH) 3 ] 2 (COOH) 3 : a graphite-like UV nonlinear optical material with a large birefringence via structural optimization

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  10. From BaAl 2 (BO 3 ) 2 O to SnAl 2 (BO 3 ) 2 F 2 : structure transformation based on ion regulation

    New Journal of Chemistry · 2020-01-01

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  11. Te 3 O 3 (PO 4 ) 2 : a phosphate crystal with large birefringence activated by the highly distorted [TeO 5 ] group and antiparallel [PO 4 ] pseudo-layer

    Journal of Materials Chemistry C · 2020-01-01

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  12. Two new ammonium/alkali-rare earth metal difluorophosphates ALa(PO 2 F 2 ) 4 (A = NH 4 and K) with moderate birefringence and short cutoff edges

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  13. PbB5O7F3: A High-Performing Short-Wavelength Nonlinear Optical Material

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  14. K4Sb(SO4)3Cl: The first apatite-type sulfate ultraviolet nonlinear optical material with sharply enlarged birefringence

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  15. High Coordinate Metal Iodate Chlorides with Diverse Structural Motifs and Tunable Birefringence

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  16. LiGaF2(IO3)2: A mixed-metal gallium iodate-fluoride with large birefringence and wide band gap

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  17. K 2 Sb(P 2 O 7 )F: Cairo Pentagonal Layer with Bifunctional Genes Reveal Optical Performance

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  18. K2Sb(P2O7)F: Cairo Pentagonal Layer with Bifunctional Genes Reveal Optical Performance

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  19. The study of structure evolvement of KTiOPO4 family and their nonlinear optical properties

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  20. NaTePO5, SrTeP2O8 and Ba2TeP2O9: Three tellurite-phosphates with large birefringence

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  21. Na3AMg7(PO4)6 (A = K, Rb and Cs): Structures, properties and theoretical studies of alkali metal magnesium orthophosphates

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  22. Y 2 (Te 4 O 10 )(SO 4 ): a new sulfate tellurite with a unique Te 4 O 10 polyanion and large birefringence

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  23. α‐SnF 2 : A UV Birefringent Material with Large Birefringence and Easy Crystal Growth

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  24. α‐SnF 2 : A UV Birefringent Material with Large Birefringence and Easy Crystal Growth

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  25. KSnI 3 ⋅ H 2 O: A New Compound with One‐Dimensional SnI 3 Chains of Pyramidal SnI 5 Polyhedra

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  26. Sn2B5O9Br as an Outstanding Bifunctional Material with Strong Second‐Harmonic Generation Effect and Large Birefringence

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  27. Synergism of multiple functional chromophores significantly enhancing the birefringence in layered non-centrosymmetric chalcohalides

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  28. An antimony( iii ) borate with large birefringence exhibiting unwonted [B 5 O 11 ] fundamental building blocks and dimeric [Sb 2 O 6 ] clusters

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  29. BaTi(BO 3 ) 2 : an excellent birefringent material with highly coplanar isolated [BO 3 ] groups

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  30. Centrosymmetric RbSnF 2 NO 3 vs. noncentrosymmetric Rb 2 SbF 3 (NO 3 ) 2

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  31. K 2 ZnMoP 2 O 10 : a novel nonlinear optical molybdophosphate with a strong second harmonic generation response and moderate birefringence

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  32. SrTi(IO 3 ) 6 ·2H 2 O and SrSn(IO 3 ) 6 : distinct arrangements of lone pair electrons leading to large birefringences

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  33. Ba3Sb2(PO4)4 and Cd3Sb2(PO4)4(H2O)2: Two New Antimonous Phosphates with Distinct [Sb(PO4)2] Structure Types and Enhanced Birefringence

    Inorganic Chemistry · 2021-01-12

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  34. A2(TeO)P2O7 (A = K, Rb, Cs): Three new tellurite-pyrophosphates with large birefringence

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  35. Different mechanism of stereochemical activity and birefringence in post-transition metal halides: A first-principles investigation

    Journal of Solid State Chemistry · 2021-02-06

    Kui Wang, Qun Jing, Zhenzhen Wan, Ming‐Hsien Lee, Haiming Duan, Haibin Cao, Jun Zhang

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  36. Large Second-Harmonic Response and Giant Birefringence of CeF 2 (SO 4 ) Induced by Highly Polarizable Polyhedra

    Journal of the American Chemical Society · 2021-02-24

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  37. Molecular Engineering toward an Enlarged Optical Band Gap in a Bismuth Sulfate via Homovalent Cation Substitution

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  38. Fluorine‐Driven Enhancement of Birefringence in the Fluorooxosulfate: A Deep Evaluation from a Joint Experimental and Computational Study

    Advanced Science · 2021-06-04

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  39. Cs2ZnSn3S8: A Sulfide Compound Realizes a Large Birefringence by Modulating the Dimensional Structure

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