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RESEARCH PAPER · Angewandte Chemie International Edition · 2021

Sn2PO4I: An Excellent Birefringent Material with Giant Optical Anisotropy in Non π‐Conjugated Phosphate

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Sn2PO4I: An Excellent Birefringent Material with Giant Optical Anisotropy in Non π‐Conjugated PhosphateOriginalA 6 Mo 2 P 4 O 19 (A = Rb, Cs) and Rb 2 MoP 2 O 9 : new molybdophosphates with distinct polyanionic configurations5AZn 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 edge25[C(NH 2 ) 3 ]BiCl 2 SO 4 : an excellent birefringent material obtained by multifunctional group synergy40Ba 2 Zn 2 B 6 O 13 : coplanar [B 2 O 5 ] in unnoted U-shaped [B 6 O 13 ] groups achieving large birefringence6Halogen regulation triggers structural transformation from centrosymmetric to noncentrosymmetric switches in tin phosphate halides Sn 2 PO 4 X (X = F, Cl)47KSb(BeF 3 )F 3 : a totally fluorine strategy for achieving wide bandgap and large birefringence23Large optical anisotropy-oriented construction of a carbonate-nitrate chloride compound as a potential ultraviolet birefringent material44Linear unit BN 2 : a novel birefringence-enhanced fundamental module with sp orbital hybridization9Na 4 Ga 8 S 14 : a Ga-enriched wide band gap ternary alkali-metal sulfide with unique [Ga 12 S 42 ] 12-membered rings2Nain(C2o4)(Hpo4)(H2o)5: An Ultraviolet Transparent Nonlinear Optical Oxalate-Phosphate with Large Birefringence0Performance of optical materials with the derivative of planar π-conjugated groups: Recent advances and future prospects37PNO: a promising deep-UV nonlinear optical material with the largest second harmonic generation effect17Sn 9O 4Br 9X (X = Cl, Br): Two New Sn(II) Oxyhalides Exhibiting Large Birefringence Derived from Highly Distortive Polyhedra of Lone Pair Cations0Sulfamide: A Promising Deep‐Ultraviolet Nonlinear Optical Crystal Assembled from Polar Covalent [SO2(NH2)2] Tetrahedra9Sulfamide: A Promising Deep‐Ultraviolet Nonlinear Optical Crystal Assembled from Polar Covalent [SO2(NH2)2] Tetrahedra84A 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 Region150NaBaBS3: A Promising Infrared Functional Material with Large Birefringence Induced by π-Conjugated [BS3] Units32Yin–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 oxalates58An Optically Anisotropic Crystal with Large Birefringence Arising from Cooperative π Orbitals81An Optically Anisotropic Crystal with Large Birefringence Arising from Cooperative π Orbitals22(C4H10NO)PbX3 (X = Cl, Br): Design of Two Lead Halide Perovskite Crystals with Moderate Nonlinear Optical Properties35A new birefringent material, HfF2(IO3)2, with a large birefringence and improved overall performances achieved by the integration of functional groups19SbHPO3F: 2D van der Waals Layered Phosphite Exhibiting Large Birefringence32Sn3B10O17Cl2 Achieving Birefringence Enhancement by Stereochemical Activity Lone Pair9Rb 3 B 5 O 8 F 2 and K 0.6 Rb 2.4 B 5 O 8 F 2 : two new deep-ultraviolet transparent nonlinear optical fluorooxoborates designed by cation regulation13M(NH2SO3)2·xH2O (M = Ca, Pb, x = 0, 1, 4): Effect of Hydrogen Bonding on Structural Transformations and Second Harmonic Generation of Metal Sulfamates26Noncentrosymmetric versus Centrosymmetric: Halogen Induced Variable Coordination Modes of Sn2+ and Structural Transition in Sn3B3O7X (X = Cl and Br)17(C 5 H 6.16 N 2 Cl 0.84 )(IO 2 Cl 2 ): a birefringent crystal featuring unprecedented (IO 2 Cl 2 ) − anions and π-conjugated organic cations56A series of novel phosphites/phosphates with deep-ultraviolet cut-off edges from 0D polar to 3D non-polar architectures13An effective pathway to design and synthesize UV birefringent crystals via rational assembly of π-conjugated [CO 3 ] 2− and [NO 3 ] − triangles32Anisotropic structure building unit involving diverse chemical bonds: a new opportunity for high-performance second-order NLO materials181Dramatically improved optical anisotropy by realizing stereochemically active lone pairs in a sulfate system, K 2 SO 4 ·HIO 323Heteroanion-introduction-driven birefringence enhancement in oxychalcogenide Ba 3 M II Ge 3 O 2 S 8 (M II = Mn, Cd)19Hg 3 O 2 (NO 3 )F: a mercury nitrate oxyfluoride with an unprecedented [(Hg 3 O 2 F) + ] ∞ cationic framework and excellent optical anisotropy21KRb 2 (NO 3 ) 2 Cl: a new birefringent crystal exhibiting a perovskite-related framework and a short cutoff edge6Mg 2 Pb 2 Si 2 O 7 F 2 : a new lead-containing alkali earth metal silicate fluoride with a short cutoff edge2Na 7 (SeO 4 ) 3 (IO 3 ) and K 2 (SeO 4 )[IO 2 (OH)]: two new iodate-selenates with short-wave UV cutoff edge and large birefringence8Stereochemically active lone-pair-driven giant enhancement of birefringence from three-dimensional CsZn 4 Ga 5 Se 12 to two-dimensional CsZnAsSe 319Structure and optical property evolution in PbM(PO 4 )X (M = Zn, Sn; X = halogen): SHG effect and birefringence21Synthesis, structure and characterization of Cd 2 TeO 3 Cl 2 with unprecedented [Cd 2 O 6 Cl 4 ] octahedral dimers5The transformation of a zero-dimensional cluster into a one-dimensional chain structure achieving a dramatically enhanced birefringence in tin( ii )-based oxalates33Pb2Cl2(HPO3)(H2O) and Pb3Br2(HPO3)2: Two Phosphite Halides with 3D Structural Networks and Enlarged Birefringence18Deep 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 Birefringence6Sn9O4Br9X (X = Cl, Br): Two new Sn(II) oxyhalides exhibiting large birefringence derived from highly distortive polyhedra of lone pair cations9Chain‐like [S x ] ( x =2–6) Units Realizing Giant Birefringence with Transparency in the Near‐Infrared for Optoelectronic Materials53Chain‐like [S x ] ( x =2–6) Units Realizing Giant Birefringence with Transparency in the Near‐Infrared for Optoelectronic Materials5Four New Sb‐based Orthophosphates: Cation Regulation to Investigate Diversified Structural Architecture1Sb4O3(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)23“Cation Activation”: An Effective Strategy for the Enhancement of Birefringence36Birefringence 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 Halides2ASb(SO4)2 (A = Rb, Cs): Two short-wave UV antimony sulfates exhibiting large birefringence43(NH4)3(H3O)Zn4(PO4)4: A nonlinear optical zinc orthophosphate crystal9Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit38Improved Birefringence Activated by Tetrahedra Decorated with a Single Linear Unit1Ultraviolet 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 Crystals21Centrosymmetric Rb2Sb(C2O4)2.5(H2O)3 and Noncentrosymmetric RbSb2(C2O4)F5: Two Antimony (III) Oxalates as UV Optical Materials20A survey of stereoactive oxysalts for linear and nonlinear optical applications40Heteroanionic LaBrVIO4 (VI = Mo, W): Excellence in Both Nonlinear Optical Properties and Photoluminescent Properties11Three Borates Belonging to the A(I)7Ae(II)Re(III)2B15O30 Family as Promising Nonlinear Optical Crystals12Cs2Pb4Br10: A layered perovskite shows large birefringence11A new layered potassium-based molybdenum–tungsten monophosphate: synthesis, crystal structure, XPS and magnetic studies3Ce(IO3)3F and Ce(IO3)2(NO3): Two Mixed-Anion Cerium Iodates with Good Nonlinear Optical and Birefringent Properties14K2Sr4(PO3)10: A Polyphosphate with Deep-UV Cutoff Edge and Enlarged Birefringence6A Two‐Dimensional Hybrid Perovskite With Heat Switching Birefringence47A Two‐Dimensional Hybrid Perovskite With Heat Switching Birefringence7Stereochemically Active Lone-Pair Containing Metal Substitution in Polar Axis toward a Giant Phase-Matchable Optical Nonlinear Silicate Crystal Li 3 (OH)PbSiO 463YSO4F·H2O: A Deep-Ultraviolet Birefringent Rare-Earth Sulfate Fluoride with Enhanced Birefringence Induced by Fluorinated Y-Centered Polyhedra19Designing a Hybrid Perovskite with Enlarged Birefringence and Bandgap for Modulation of Light Polarization32Ln 2 F 2 (OH 2 )(MoO 3 ) 2 (SeO 3 ) 2 : Promising Multifunctional Nonlinear Optical Materials Created by Partial Fluorination Strategy under Corrosion Resistant Supercritical Reactions25Highly Birefringent d 0 Transition Metal Fluoroantimonite in the Mid Infrared Band: Order–Disorder Regulation by Cationic Size83Designing Sulfate Crystals with Strong Optical Anisotropy through π‐Conjugated Tailoring51Designing Sulfate Crystals with Strong Optical Anisotropy through π‐Conjugated Tailoring11Hydroxyl-Driven Enhanced Birefringence in Borophosphates3PbTeB 4 O 9 : a lead tellurium borate with unprecedented fundamental building block [B 4 O 10 ] and large birefringence12Positive and Negative Contribution from Lead–Oxygen Groups and Halogen Atoms to Birefringence: A First Principles Investigation4CsSn2(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 pairs12A highly birefringent metal-free crystal assembled by cooperative non-covalent interactions30Computer-aided screening of bismuth molybdates nonlinear optical crystals γ -Bi 2 MoO 63Designing promising ultraviolet (UV) birefringent crystals with different hydrogen-bonded phosphate frameworks18Exploration of antimony( iii ) oxyhalides via single-site substitution in quest of large birefringence10Greatly enhanced optical anisotropy in thiophosphates inspired by rational coupling of tetrahedra and ethane-like [P 2 S 6 ] 4− groups7K 2 MgMoP 2 O 10 and K 3 Mg 2 MoP 3 O 14 : two new molybdophosphates exhibiting different optical anisotropies induced by variable dimensionality of the anion framework4K, Rb-hydroxyborates series with deep-ultraviolet KRbB 5 O 8 (OH) possessing moderate second harmonic generation response0Na 4 Sn 4 (C 2 O 4 ) 3 F 6 and NaSnC 2 O 4 F·H 2 O: two tin( ii ) fluoride oxalates display large birefringence11New antimony fluorooxoborates with strong birefringence and unprecedented structural characterisation19Novel antimony phosphates with enlarged birefringence induced by lone pair cations4Optimized arrangement of non-π-conjugated PO 3 NH 3 units leads to enhanced ultraviolet optical nonlinearity in NaPO 3 NH 328Partial substitution with a significant effect: coexistence of a wide band gap and large birefringence in the oxychalcogenide AEGe 2 O 4 Se (AE = Sr and Ba)17Pb 2 (SeO 3 )(SiF 6 ): the first selenite fluorosilicate with a wide bandgap and large birefringence achieved through perfluorinated group modification45RbSb(SO 4 )(H 2 PO 2 )F: a short-wave UV antimony( iii ) oxysalt with mixed-anions demonstrating enhanced birefringence11Structural characterisation and optical properties of new alkaline earth phosphate CaMg(P 4 O 12 ) and alkaline alumophosphate Cs 3 Al 4 (PO 4 ) 51Sb4O5I2: 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 Halides23AX·(H2SeO3)n (A = K, Cs; X = Cl, Br; n = 1, 2): A Series of Ionic Cocrystals as Promising UV Birefringent Materials with Large Birefringence and Wide Band Gap20Designing Optical Anisotropy: Silver-Aminoalkylpyridine Nitrate Complexes with Tunable Structures3Two Short-Wave UV Antimony(III) Sulfates Exhibiting Large Birefringence18Design of deep-ultraviolet zero-order waveplate materials using LiB3O5 as the template8Stereochemically Active Lone Pair Leads to Birefringence in the Vacancy Ordered Cs3Sb2Cl9 Perovskite Single Crystals13Enhancement of Birefringence in π-Conjugated Oxyfluorides Achieved via van der Waals Layered Structural Optimization10The Spin–Orbit Effect on the Electronic Structures, Refractive Indices, and Birefringence of X2PO4I (X = Pb, Sn, Ba and Sr): A First-Principles Investigation6Layered (C5H6ON)2[Sb2O(C2O4)3] with a large birefringence derived from the uniform arrangement of π-conjugated units11Two Hydroxyfluorooxoborates Achieving Deep‐Ultraviolet Cutoff Edges and Moderate Birefringence by Assembling Multi‐Anionic Groups6Sb2O2SeO3 and Sb2O(SeO3)2: Two-Layered Antimony(III) Selenites with Enhanced Birefringence10Enhanced 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 Construction116Theoretical insight on structure, electronic, and optical properties of two d 0–d 10 electron transition-metal oxyhalides SHG materials2Halogen Bond Unlocks Ultra‐High Birefringence73Halogen Bond Unlocks Ultra‐High Birefringence14Gradual Increase in Birefringence of Antimony Oxalates through Precise Tuning of the Sb3+/[C2O4]2– Ratio7β-Pb3P2S8: A new optical crystal with exceptional birefringence effect11Optimization of Functional Building Blocks Generates a Substantial Improvement in Birefringence from Sn2OSO4 to Sn3O2(OH)(HSO4)6C6N7(NH2)3·H3PO4: Strong Second Harmonic Generation and Giant Birefringence Benefiting from Amino Substitution Strategy24Photoluminescence and Refractive Index Dispersion Properties of Zn3−xMx(PO4)2 (M=Co, Ni; x = 1) Nanoparticles0A Robust Phosphonate‐Based Hydrogen‐Bonded Organic Framework Birefringent Crystal39Tetrahedra Modification of Phosphates for Optical Anisotropy Enhancement13A2Cd(PO3)4 (A = K, Rb, Cs): Series of cadmium polyphosphates with infinite 1[(PO3)4]ꝏ chains and deep ultraviolet transparency windows2Unusual Triple-State Switching of Thermally Induced Birefringence in a Two-Dimensional Perovskite Ferroelectric45Pb2TeV2O10: A Lead Vanadate Tellurate with Wide Mid-IR Transparency and Large Birefringence Induced by Multiple Birefringence-Active Groups11A Giant Optically Anisotropic Phosphate Driven by Mixed Valence Mercury Units22First-principles study of three isomers of the large birefringent crystal Sb4O4F4: electronic structure and optical properties0From Ba2Bi2Zn(PO4)4 to Ba2Bi2Cu(PO4)4: Rational design of an ultraviolet phosphate with enhanced birefringence2Functional assembly and modification of nonlinear optical fundamental motifs in phosphates27Birefringence Disparity Induced by Synergistic Effects of Stereochemically Active Lone Pairs19Novel antimony-based mixed halides exhibiting an excellent SHG response and a broad transmission range20Tin chalcohalide Sn 11 (PS 4 ) 4 I 10 obtained from structural-template-oriented synthesis: exhibiting balanced infrared nonlinear optical performance6“All-four-in-one”: a novel mercury tellurite–nitrate Hg 3 (TeO 3 )(Te 3 O 7 )(NO 3 ) 2 exhibiting exceptional optical anisotropy29(C 5 N 2 H 7 )IO 2 F 2 and (C 3 N 6 H 8 )(IO 2 F 2 ) 2 : two new organic–inorganic hybrid fluoroiodate birefringent crystals7A π-conjugated organic molecule-modified strategy to achieve high-performance metal nitrate birefringent crystals9Cation tuning in anionic framework hydroborates: tailored deep-ultraviolet optical crystals with large birefringence1Four noncentrosymmetric molybdophosphates discovered by a chemical substitution strategy4Harnessing the dual role of DMSO in the synthesis of SbOCl·DMSO: an excellent nonlinear optical crystal with unique 1D spiral chain10Hg 2 (HTe 2 O 5 )(PO 4 ): a novel phosphate crystal with enhanced birefringence enabled by the synergistic modification of multiple functional groups12Li 2 CeRbB 18 O 30 and Li 2 Cs 2 SrB 18 O 30 : promising low-birefringence materials for UV and deep UV zero-order waveplates4M 2 Al 2 Ti(PO 4 ) 4 (M = Rb, Cs): synthesis and optical property investigation of two titanium phosphates with a dissimilar structural configuration2Structural chemistry of antimony( iii ) oxalates with lone pairs: polyhedral distortion [SbO 4 F 2 ], π-conjugation [C 2 O 4 ], and birefringence tuning1新型非线性光学晶体和双折射晶体的研究进展(特邀)4Can Low Structural Anisotropy Produce High Optical Anisotropy? Anomalous Giant Optical Birefringent Effect in PI4AlI4 in Focus11

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  3. [C(NH 2 ) 3 ]BiCl 2 SO 4 : an excellent birefringent material obtained by multifunctional group synergy

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  4. Ba 2 Zn 2 B 6 O 13 : coplanar [B 2 O 5 ] in unnoted U-shaped [B 6 O 13 ] groups achieving large birefringence

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  5. Halogen regulation triggers structural transformation from centrosymmetric to noncentrosymmetric switches in tin phosphate halides Sn 2 PO 4 X (X = F, Cl)

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  7. Large optical anisotropy-oriented construction of a carbonate-nitrate chloride compound as a potential ultraviolet birefringent material

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