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RESEARCH PAPER · Chemistry of Materials · 2024

Metal Methanesulfonates with Mixed Anionic Groups with Large Band Gaps and Enhanced Birefringence

Mingli Liang, Yujie Zhang, Eugene Izvarin, Michael J. Waters, James M. Rondinelli, P. Shiv Halasyamani

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Metal Methanesulfonates with Mixed Anionic Groups with Large Band Gaps and Enhanced BirefringenceOriginalCrystal clear: unveiling giant birefringence in organic–inorganic cocrystals33Strategically designed metal-free deep-ultraviolet birefringent crystals with superior optical properties18Hg16O12(NO3)6F2(H2O): A Mercury-Rich Nitrate Oxyfluoride with Diverse Triple-Coordinated Mercury-Based Units That Exhibits an Unparalleled [(Hg16O12F2(H2O))6+]∞ Cationic Framework and a Large Birefringence12Remarkable Second Harmonic Generation Response in (C 5 H 6 NO) + (CH 3 SO 3 ) − : Unraveling the Role of Hydrogen Bond in Thermal Driven Nonlinear Optical Switch50Remarkable Second Harmonic Generation Response in (C5H6NO)+(CH3SO3)−: Unraveling the Role of Hydrogen Bond in Thermal Driven Nonlinear Optical Switch10Old tree blossoms anew: Research progress on the structures and optical properties of ultraviolet selenites56Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension‐Reduced Zn‐Based Crystals66Breaking Boundaries: Giant Ultraviolet Birefringence in Dimension‐Reduced Zn‐Based Crystals8The preparation and investigation of ionic functional resins for deep dehydration of toluene2Sulfate 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 Ordering4Synthesis and Large Crystal Growth of a Noncentrosymmetric Sodium Methylsulfanetriol Borate Lewis-Adduct: Na(S(OH)3CH3)(BO3)10MgPO2F3: An Ultraviolet Nonlinear Optical System with an Extremely Short Phase-Matching Wavelength Achieved by Introducing Dual-Type Fluorine via Structure Prediction1The New Paradigm of Ligand Substitution-Driven Enhancement of Anisotropy from SO4 Units in Short-Wavelength Region14Exploring ultra-high optical anisotropy in polyiodides7Hg 2 (HTe 2 O 5 )(PO 4 ): a novel phosphate crystal with enhanced birefringence enabled by the synergistic modification of multiple functional groups12Hg 2 (SeO 3 )(TeO 3 ): a novel tellurite–selenite birefringent crystal achieved by assembling multiple functional groups11Hg[CS(NH 2 ) 2 ] 4 (SiF 6 ): a fluorosilicate crystal with large birefringence achieved via multi-functional group modification6NaCaGa 3 S 6 : a mixed alkali metal and alkaline earth metal sulfide with a distinctive [Ga 5 S 10 ] ∞ layered framework0Synthesis and large crystal growth of a family of mixed-anionic methanesulfonate salts by anionic site-substitution: Na 5 (SO 3 CH 3 ) 4 (X) (X = BF 4 − , ClO 4 − , PF 6 − , I − )9(NH 4 ) 2 Cd 2 Cl 3 F 3 and (NH 4 ) 2 Cd 2 Br 3 F 3 : The First Fluoride‐Containing d 10 Metal Mixed Halides Exhibiting Superior Ultraviolet Nonlinear Optical Properties28From Holodirected to Hemidirected Coordination Activated by Oxygenation Strategy: A Facile Route to Long Wave Infrared Birefringent Crystal4From Holodirected to Hemidirected Coordination Activated by Oxygenation Strategy: A Facile Route to Long Wave Infrared Birefringent Crystal28Regulation of Refractive Index by Halogens in Two-Dimensional Layered Methylsulfonate Halides7Designed Metal‐Free Quasi‐1D Crystals with Giant Birefringence8Metal Cation Engineered UV Birefringent Crystals in π‐Conjugated Sulfonates with Record‐High Optical Anisotropy17Na[B3IO7(OH)] and Na2[B4IO9](IO3): Explorations of Boroiodates with Strong Second Harmonic Generation Response and Large Birefringence54La2Zn3(SeO3)6: A UV Selenite Crystal with Second-Harmonic Generation and Large Birefringence13Recent progress in structural design strategies of high-birefringence optical crystals54Crystal growth of an unusual salt derived from methanesulfonic acid: Rb(CH 3 SO 3 )(CH 3 SO 3 H)2Designing Hybrid Sb-Based Nonlinear Optical Crystals with Large Birefringence by Combining the Lone Pair and π-Conjugated Genes10Achieving Dual-Color Luminescence via Halogen Regulation in Copper-Based Halides for Anticounterfeiting3Synthesis and Optical Properties of Trivalent Metal Methanesulfonates Containing Y(III), Bi(III), In(III), and Sb(III)6Anhydrous Methane Sulfonates of Group 13 Metals: Synthesis and Characterization of Ga(CH 3 SO 3 ) 3 , In(CH 3 SO 3 ) 3 , and Tl(CH 3 SO 3 ) 32(C7H10N)3Bi2I9·I2: Synergistic Cooperation of π-Conjugated Cations and Distorted [BiI6] Octahedra Enabling a Large Infrared Birefringence4Ag3In3(SeO3)3(SO4)F4: A Sulfate Selenite Nonlinear Optical Material with a Wide Bandgap3Metal Chloride‐Iodate Nonlinear Optical Materials via Direct Chlorination of Centrosymmetric Metal Iodate Crystals0Brominated Methanesulfonates: Characterization of K[Br 3 CSO 3 ] ⋅ H 2 O, K 2 [Br 2 C(SO 3 ) 2 ] ⋅ H 2 O and K 3 [BrC(SO 3 ) 3 ] ⋅ H 2 O2Between the Sheets: CH 3 SO 3 H Molecules Intercalating B 2 O 3 Layers3Selective Crystal Growth and Optical Properties of Magnesium Methanesulfonate Hydrates Mg(SO 3 CH 3 ) 2 (H 2 O) n ( n = 4 and 12)2Sb 2 (SeO 3 ) 2 SeO 4 : A Selenite–Selenate Crystal with Balanced Band Gap and Birefringence3A mercury-based selenite with wide bandgap and moderate birefringence via cation substitution and partial fluorination1KTeOPO 4 and NH 4 SnClSO 4 : two new KTiOPO 4 derivatives as birefringent crystals featuring enhanced optical anisotropy0Syntheses and characterization of nonmolecular lead organosulfonates, Pb(O 3 SCH 3 ) 2 , Pb(O 3 SC 6 H 5 ) 2 ·H 2 O, Pb(O 3 SC 6 H 4 CH 3 ) 2 , and Pb(O 3 S(CH 2 ) 2 SO 3 )0Confinement-assembled ultraviolet nonlinear optical crystal from pyridine-expanded π-systems with exhibiting strong SHG and birefringence18Dual‐Functional Ultraviolet Nonlinear Optics and Bright Luminescence Achieved in the First Fluorine‐Containing Hybrid Lone‐Pair Metal Mixed Halides8Recent Progress in Hg-Based Oxysalt Crystals for Nonlinear Optics and Birefringence Applications5Cation-sulfur-driven dimensional reduction engineering for tailoring sulfonate birefringent crystals with enhanced anisotropy2A novel tetrafluoroborate with giant birefringence assembled from biocompatible adenine0Assembly of dual π-conjugated units toward enhanced birefringence in a 2D organic sulfonate crystal0

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