Hg₄(Te₂O₅)(SO₄): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(11), С. 7868 - 7874

Опубликована: Март 8, 2024

Sulfate crystals are often criticized for their low birefringence. The small anisotropic SO4 group is becoming the biggest bottleneck hindering application of sulfates in optical functional materials. In this study, we report a new method to significantly enhance birefringence sulfates. title compound increases recording 0.542@546 nm, which larger than that commercial birefringent crystal TiO2 ([email protected] nm). At infrared wavelength, Hg4(Te2O5)(SO4) can be up 0.400@1064 also much YVO4 (0.209@1064 addition, it has wide transparency range, high thermal stability, and excellent environmental making potential material. features novel two-dimensional layered structure composed [Hg4(Te2O5)]2+ layers separated by isolated (SO4)2– tetrahedra. This was designed introducing highly selective cation tellurite sulfate system. valence coordination cations connect with groups only, structure. steric repulsive action tetrahedra may regulate linear lone pair arranged way favors large proven theoretical calculations. PAWED studies showed originated from synergistic effect (Hg2O2)2–, (Te2O5)2–, units, contribution ratio 42.17, 37.92, 19.88%, respectively. Our work breaks limitation opens possibilities as crystals.

Язык: Английский

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Record Second-Harmonic Generation and Birefringence in an Ultraviolet Antimonate by Bond Engineering

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(14), С. 9975 - 9983

Опубликована: Март 11, 2024

Oxides have attracted considerable attention owing to their potential for nonlinear optical (NLO) applications. Although significant progress has been achieved in optimizing the structural characteristics of primitives (corresponding simplest constituent groups, namely, cations/anions/neutral molecules) comprising crystalline oxides, role primitives' interaction determining resultant functional structure and properties long underappreciated remains unclear. In this study, we employ a π-conjugated organic primitive confinement strategy manipulate interactions between antimonates thereby significantly enhance nonlinearity. Chemical bonds relatively weak H-bonding promote formation cis- trans-Sb(III)-based dimer configurations (C5H5NO)(Sb2OF4) (4-HPYSOF) (C5H7N2)(Sb2F7) (4-APSF), respectively, resulting very different second-harmonic generation (SHG) efficiencies birefringences. particular, 4-HPYSOF displays an exceptionally strong SHG response (12 × KH2PO4 at 1064 nm) large birefringence (0.513 546 Sb(III)-based NLO oxide as well UV cutoff edge. Structural analyses theoretical studies indicate that polarized ionic bond facilitate favorable arrangement both inorganic primitives, enhancing nonlinearity 4-HPYSOF. Our findings shed new light on intricate correlations configuration, properties, and, more broadly, our approach provides perspective development advanced materials through interatomic engineering oxides.

Язык: Английский

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A UV non-hydrogen pure selenite nonlinear optical material for achieving balanced properties through framework-optimized structural transformation

Materials Horizons, Год журнала: 2024, Номер 11(7), С. 1704 - 1709

Опубликована: Янв. 1, 2024

For non-centrosymmetric (NCS) oxides intended for ultraviolet (UV) nonlinear optical (NLO) applications, achieving a wide band gap, large second harmonic generation (SHG) intensity, and sufficient birefringence to satisfy phase matching is significant challenge due their inherent incompatibility. To address this issue, study proposes strategy called framework-optimized structural transformation. Building upon centrosymmetric (CS) NaGa(SeO

Язык: Английский

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Old tree blossoms anew: Research progress on the structures and optical properties of ultraviolet selenites

Coordination Chemistry Reviews, Год журнала: 2024, Номер 517, С. 216000 - 216000

Опубликована: Июнь 15, 2024

Язык: Английский

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Hg₃Se(SeO₃)(SO₄): A Mixed-Valent Selenium Compound with Mid-Infrared Transmittance Obtained by In Situ Reaction

Inorganic Chemistry, Год журнала: 2024, Номер 63(9), С. 4011 - 4016

Опубликована: Фев. 16, 2024

Exploring new material systems is a highly significant task in the field of inorganic chemistry. A mixed-valent selenium compound, Hg3Se(SeO3)(SO4), was successfully synthesized through situ reactions. This compound exhibits novel three-dimensional structure composed Hg3Se(SO4) layers bridged by SeO3 trigonal pyramids. It first containing (SeO3)2–, (SO4)2–, and Se2– simultaneously. In addition, Hg3Se(SeO3)(SO4) possesses wide bandgap (3.5 eV), moderate birefringence (Cal:0.064@546 nm, Exp:0.069@546 nm), high laser-induced damage threshold (23.35 MW cm–2), transmittance window (0.28–6.6 μm). Our work demonstrates that (+4, −2) selenite selenide can be potential optical materials for mid-infrared region.

Язык: Английский

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[(C₅H₆N₂)₂H](Sb₄F₁₃): A polyfluoroantimonite with strong second harmonic generation effect

Chemical Science, Год журнала: 2024, Номер 15(21), С. 8071 - 8079

Опубликована: Янв. 1, 2024

A universal synthesis method for polyfluoroantimonites has been developed. Polar [(C 5 H 6 N 2 ) H](Sb 4 F 13 was achieved by polyfluoroantimonite strategy. It features a strong SHG effect, large birefringence and high LIDT value.

Язык: Английский

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HgBr₂: an easily growing wide-spectrum birefringent crystal

Chemical Science, Год журнала: 2024, Номер 15(18), С. 6891 - 6896

Опубликована: Янв. 1, 2024

The present work fully investigated the potential of mercury bromide as an excellent birefringent crystal.

Язык: Английский

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From (NH₄)₃[Zr(PO₄)₂F] to (NH₄)₃[Sn₂(PO₄)₂]Cl: the rational design of a tin-based short-wave ultraviolet phosphate with large optical anisotropy

Inorganic Chemistry Frontiers, Год журнала: 2024, Номер 11(6), С. 1775 - 1780

Опубликована: Янв. 1, 2024

(NH 4 ) 3 [Sn 2 (PO ]Cl: the rational design of a tin-based phosphate with coexistence large optical anisotropy and short-wave ultraviolet transparency.

Язык: Английский

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Highly Stable MOF‐Type Lead Halide Luminescent Ferroelectrics

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(29)

Опубликована: Май 15, 2024

Abstract Lead halide molecular ferroelectrics represent an important class of luminescent ferroelectrics, distinguished by their high chemical and structural tunability, excellent processability distinctive characteristics. However, inherent instability, prone to decomposition upon exposure moisture light, hinders broader ferroelectric applications. Herein, for the first time, we present a series isoreticular metal–organic framework (MOF)‐type lead demonstrating exceptional robustness under ambient conditions at least 15 months even when subjected aqueous boiling conditions. Unlike conventional metal‐oxo secondary building units (SBUs) in MOFs adopting highly centrosymmetric structure with limited distortion, our halide‐based occupy structurally deformable [Pb 2 X] + (X=Cl − /Br /I ) SBUs that facilitate c ‐axis‐biased displacement Pb 2+ centers substantially contribute thermoinducible transformation. Importantly, this MOF‐type undergo ferroelectric‐to‐paraelectric phase transitions remarkably Curie temperature up 505 K, superior most ferroelectrics. Moreover, covalent bonding between phosphorescent organic component light‐harvesting inorganic achieves efficient spin‐orbit coupling intersystem crossing, resulting long‐lived afterglow emission. The compelling combination stability, ferroelectricity emission exhibited opens many potential opportunities energy‐conversion

Язык: Английский

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Halide-driven polarity tuning and optimized SHG-bandgap balance in (C₄H₁₁N₂)ZnX₃ (X = Cl, Br, I)

Inorganic Chemistry Frontiers, Год журнала: 2024, Номер 11(17), С. 5587 - 5597

Опубликована: Янв. 1, 2024

The halide substitutions in (C 4 H 11 N 2 )ZnX 3 (X = Cl, Br, I) induce polarity tuning and then optimized SHG-bandgap balance.

Язык: Английский

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