Exploring New Horizons in Mid-to-Far Infrared Nonlinear Optical Crystals: The Significant Potential of Trigonal Pyramidal [TeS₃]²⁻ Functional Units

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

The [TeS 3 ] 2− unit with a SCALP disrupts tetrahedral symmetry, leading to the synthesis of Cu 10 Te 4 S 13 for first time. This material exhibits strong SHG (3.75 × AgGaS 2 ) and widest MFIR transparency (2.5–25 μm) reported NLO chalcogenides.

Язык: Английский

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Discovering Pseudo-Supertetrahedral Functional Units in Salt-Inclusion Nonlinear Optical Material [Ba₂₂(SO₄)₅][Zn₁₄Ga₁₈S₅₈]

ACS Materials Letters, Год журнала: 2025, Номер unknown, С. 1512 - 1519

Опубликована: Март 21, 2025

Язык: Английский

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(NH₄)₂Cd₂Cl₃F₃ and (NH₄)₂Cd₂Br₃F₃: The First Fluoride‐Containing d¹⁰ Metal Mixed Halides Exhibiting Superior Ultraviolet Nonlinear Optical Properties

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 28, 2025

Abstract In the search for new ultraviolet (UV) nonlinear optical (NLO) materials, two novel cadmium mixed halide compounds, (NH 4 ) 2 Cd Cl 3 F and Br , are successfully synthesized via hydrothermal methods. These compounds crystallize in noncentrosymmetric (NCS) space group, R 32, composed of distorted octahedral [CdX ] (X═Cl or Br) units, which extend into a 3D framework. Remarkably, both demonstrate strong second‐harmonic generation (SHG) efficiencies—3.0 8.0 times that KH PO Cl‐ Br‐containing analogs, respectively—with phase‐matching behavior observed. The SHG efficiency is attributed to highly coordination environment polarizable d 10 2+ ions, with benefiting further from Br's greater polarizability. Furthermore, these exhibit wide bandgaps exceeding 4.2 eV, making them first metal systems incorporating fluoride suitable UV NLO applications. With absorption cut‐off edges as short 203 nm 243 materials represent significant advancement development UV‐transparent materials. This study introduces synthetic strategy design enhanced properties, offering promising candidates future technologies.

Язык: Английский

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Tuning Birefringence in Supramolecular Mg-PDA Frameworks: Modulating Bonding and Layer Connectivity

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Март 21, 2025

Herein, we prepared two novel hydrogen-bonded supramolecular frameworks within the Mg-pyridine dicarboxylic acid (Mg-PDA) system: [Mg(H2O)6][(C7H4NO4)·H2O]2 (1) and Mg(C7H3NO4)(H2O)2 (2). In compound 1, 2D [(C7H4NO4)·H2O]∞– anionic layer is formed by O/N–H···O hydrogen bonding connecting (C7H4NO4)− anions with free water molecules. contrast, [Mg(C7H3NO4)(H2O)2]∞ neutral in 2 connected Mg–O/N coordination bonds, which promote coplanar arrangement of π-conjugated six-membered pyridine rings. This structural enhances disparity between in-plane out-of-plane interactions [Mg(C7H3NO4)(H2O)2] layer. Consequently, both experimental data theoretical calculations indicate that shows strong optical anisotropy, giant birefringence (Δn = 0.44 @ 546 nm) surpassing 1 0.34 exceeding commercially available α-BaB2O4 0.122 nm). More importantly, combination their short-wave UV cutoff edges (279 nm for 273 2), features most promising birefringent properties among all Mg-containing crystals.

Язык: Английский

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Na[B₃IO₇(OH)] and Na₂[B₄IO₉](IO₃): Explorations of Boroiodates with Strong Second Harmonic Generation Response and Large Birefringence

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 7, 2025

In the exploration of nonlinear optical (NLO) materials, developing new functional groups for high performance is essential. Achieving a balance among band gap, second harmonic generation (SHG), and birefringence within compound quite challenging. By directly connecting iodates borates by B-O-I bridges, two boroiodates with novel [B3IO8(OH)]3- [B4IO11]5- anionic groups, namely, Na[B3IO7(OH)] (NBIO-I) Na2[B4IO9](IO3) (NBIO-II), were successfully synthesized first time through boric acid melting method under different molar ratios H3BO3/NaIO3. NBIO-I (Pbca) features unique 1D ∞1[B3IO7(OH)]- chain composed corner-sharing [B3O6(OH)]4- [IO3]- hanging on both sides chain. contrast, NBIO-II (Cc) displays 2D layer ∞2[B4IO9]-, in which all are same side ∞2[B4O7]2- formed [B3O7]5- [BO3]3- groups. Remarkably, exhibits wide gap (4.3 eV), large (0.298@546 nm), strongest SHG response (7.8 × KDP) borate-iodates reported previously. This work not only discovered as promising NLO crystals but also provided an effective synthetic route excellent properties.

Язык: Английский

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Nonbonding Electron Inversion‐Driven Structural Engineering: Synergistic Enhancement of Linear and Nonlinear Optical Properties

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Апрель 29, 2025

Abstract The simultaneous optimization of large birefringence (Δn, a linear optical property) and strong second‐harmonic generation (SHG, nonlinear (NLO) in single crystal remains significant challenge due to the inherently distinct structural requirements for these properties. Although nonbonding electrons have been extensively studied oxides chalcogenides, research has predominantly focused on their role along polar axes, leaving influence axes tetrahedral stacking largely unexplored. Herein, we propose electron‐inversion strategy overcome phase‐matching limitations defect diamond‐like structures. By incorporating T2‐[Ga 4 S 10 ] supertetrahedral motifs, successfully synthesized [Ba Cl 2 ][CdGa (space group: I ), which exhibits 219% enhancement Δn compared nonphase‐matching parent structure Cd GaS . weakly bound electrons, governed by atomic potentials, demonstrate SHG responses under fields. compound not only achieves broad transmission range (0.28–18.6 µm) high laser‐induced damage threshold (40.1 × AgGaS ) but also optimally balances wide bandgap ( E g = 3.58 eV) response (1.4 representing one best‐performing Cd‐based materials date. This work introduces first design based electron‐driven structure–property relationships, providing critical insights rational high‐performance NLO materials.

Язык: Английский

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Hydrogen‐Bonded Assembly of Functional Units for Constructing Linear and Nonlinear Optical Crystals

Advanced Optical Materials, Год журнала: 2025, Номер unknown

Опубликована: Апрель 29, 2025

Abstract The ideal foundation for constructing nonlinear optical (NLO) and birefringent materials is provided by planar π‐conjugated units with high hyperpolarizability anisotropy. However, the bandgap diminishes number of functional joined covalent bonds, making their employment challenging in short‐wavelength spectral region. To overcome this limitation, a strategy devised that assembles different via hydrogen bonding. By using [C 3 H x O 4 ] ( = 2–4), [CN 7 ], 6 as fundamental building blocks omitting metal cations, six compounds are effectively synthesized. ][C exhibits moderate second harmonic generation (SHG) response (1.2 × KDP) along shortest phase‐matching wavelength 255 nm. Additionally, 2 display significant birefringence 0.209 0.182 at 1064 nm, respectively, possess short cutoff edges 233 200 indicating potential ultraviolet NLO materials. This study confirms role bonding structural rearrangement, which thereby reinforces properties.

Язык: Английский

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Controllable Synthesis of a Strong Ultraviolet Nonlinear Optical Crystal by Tailoring the Lead Oxychloride Polyhedron

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 28, 2025

The exploration of ultraviolet (UV) nonlinear optical (NLO) crystals owning a strong second-harmonic generation (SHG) response has consistently been difficult task. Herein, we have controllably tailored the lead-oxychloride polyhedron by tuning amount KCl under mixed-solvothermal conditions to afford new UV NLO crystal, K3[Pb2Cl5(HCOO)2]·H2O. Interestingly, benefiting from oriented arrangement large [Pb6Cl24O12] rings, microscopic second-order susceptibilities distorted [PbCl5O2] polyhedrons are effectively superimposed. Remarkably, K3[Pb2Cl5(HCOO)2]·H2O owns unique 3D polar framework, phase-matchable SHG that is 3.1 times as KDP, suitable birefringence 0.108@1064 nm, broad high transparent window extending 340 nm in region, and feasible crystal growth. Dipole moment theoretical calculations elucidate originates polyhedron. This study will shed light on development subsequent crystals.

Язык: Английский

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Deep‐Ultraviolet Transparent Nonlinear Optical Phosphates: A New Alternative to Conventional Borates

Chemistry - A European Journal, Год журнала: 2024, Номер 31(8)

Опубликована: Ноя. 21, 2024

Abstract Deep ultraviolet (DUV) nonlinear optical (NLO) crystals with balanced performance are crucial for extending laser wavelengths into the DUV region, essential various applications. However, developing ideal is challenging due to stringent requirements: strong second‐harmonic generation (SHG) response, short cut‐off wavelength, and effective phase‐matching behavior. NLO borates, which feature π‐conjugated groups, have garnered attention their higher SHG coefficients compared phosphates. phosphates typically show UV edges large HOMO‐LUMO gap (approximately 9.6 eV) of [PO₄] units. To enhance effect while maintaining transparency in phosphates, several strategies been proposed: 1) using distorted polymerized P−O groups like isolated C₁‐[P₃O₁₀]⁵ − [P₂O₇]⁴ ; 2) aligning 3− tetrahedra along polar screw axis; 3) introducing additional NLO‐active units; 4) exploring new units derived from , such as [PO₃F] 2− tetrahedra. These led successful development non‐centrosymmetric highlighting potential candidates. This review explores relationship between crystal structures performance, proposes future directions materials.

Язык: Английский

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Achieving the Birefringence Optimization by Methyl Modulation in Organic Nonlinear Optical Crystals

Advanced Optical Materials, Год журнала: 2024, Номер unknown

Опубликована: Сен. 19, 2024

Abstract Non‐centrosymmetric organics are promising nonlinear optical (NLO) candidates, which always exhibit a short UV absorption cutoff edge, and strong second harmonic generation (SHG) response, but an overlarge birefringence. Here, in order to optimize the birefringence, methyl modulation of π‐conjugated organic planar units is proposed implemented with urea structure as template. Thus, N ‐methylurea N,N' ‐dimethylurea crystals obtained by partially replacing hydrogen atoms groups. This replacement reduces donors weakens interchain bonds, facilitates decreasing density parallel arrangement units. Hence, both not only optimized birefringence ( ≈0.099 ≈0.072 at 546 nm) also enhanced SHG response ≈1.2 × β ‐BaB 2 O 4 ≈1.9 ), while maintaining edge. Therefore, this work provides novel strategy for structural design performance NLO crystals.

Язык: Английский

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