Chirality-Dependent Structural Transformation in Chiral 2D Perovskites under High Pressure

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(16), С. 8908 - 8916

Опубликована: Апрель 14, 2023

Chiral perovskites have attracted considerable attention owing to their potential applications in spintronic- and polarization-based optoelectronic devices. However, the structural chirality/asymmetry transfer mechanism between chiral organic ammoniums achiral inorganic frameworks is still equivocal, especially under extreme conditions, as systematic differences been rarely explored. Herein, we successfully synthesized a pair of new enantiomeric perovskite (S/R-3PYEA)PbI4 (3PYEA2+ = C5NH5C2H4NH32+) an (rac-3PYEA)PbI4. Hydrostatic pressure was used, for first time, systematically investigate evolution optical behavior At approximately 7.0 GPa, exhibits chirality-dependent transformation with bandgap "red jump" dramatic piezochromism from translucent red opaque black. Upon further compression, previously unreported chirality-induced negative linear compressibility (NLC) achieved (S/R-3PYEA)PbI4. High-pressure characterizations first-principles calculations demonstrate that pressure-driven homodirectional tilting homochiral ammonium cations strengthens interactions S/R-3PYEA2+ Pb–I frameworks, inducing formation asymmetric hydrogen bonds N–H···I–Pb The enhanced H-bonding break symmetry trigger greater degree in-plane out-of-plane distortion [PbI6]4– octahedra, which are responsible phase transition NLC, respectively. Nevertheless, balanced H-bonds incurred by equal proportions S-3PYEA2+ R-3PYEA2+ counteract force, leading absence transition, spectral jump", NLC

Язык: Английский

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Resonant Second Harmonic Generation in Proline Hybrid Lead Halide Perovskites

Advanced Optical Materials, Год журнала: 2023, Номер 11(8)

Опубликована: Фев. 8, 2023

Abstract Chiral hybrid organic−inorganic perovskites (HOIPs) with intrinsic noncentrosymmetry have shown great potentials for chiroptoelectronic applications including second‐order nonlinear optics (NLO). Ideal NLO materials should simultaneously feature a large coefficient, wide optical transparency, high laser damage threshold, and physicochemical stability. However, the development of applicable has been largely restricted due to their strict requirement on structural noncentrosymmetry. Here, chiral amino acids abundant in nature adopted synthesize lead halide ( D ‐/ L ‐Pro)PbI 3 ·H 2 O (Pro = Proline) resonance enhanced second‐harmonic generation (SHG). Their crystals balanced performances transparent region, polarization ratio. This work demonstrates promise naturally construction metal next optoelectronic materials.

Язык: Английский

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Boosted Second Harmonic Generation of a Chiral Hybrid Lead Halide Resonant to Charge Transfer Exciton from Metal Halide Octahedra to Ligand

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(19)

Опубликована: Март 12, 2024

Abstract Chiral hybrid organic–inorganic metal halides (HOMHs) offer an ideal platform for the advancement of second‐order nonlinear optical (NLO) materials owing to their inherent noncentrosymmetric structures. The enhancement nonlinearity chiral HOMHs could be achieved by matching free exciton and/or self‐trapped energy levels with desired NLO frequencies. However, current scarcity resonance modes and low ratio hamper further improvements performance. Herein, we propose a new resonant channel charge transfer (CT) excited states from halide polyhedra organic ligand boost HOMHs. model lead (C 7 H 10 N)PbBr 3 N=1‐ethylpyridinium) exhibits drastically enhanced second harmonic generation in deep CT energy, intensity up 111.0 times that KDP 10.9 urea. effective coefficient has been determined as high ~40.2 pm V −1 , balanced large polarization laser damage threshold. This work highlights contribution ligands construction enhancing coefficients halides, thus provides guidelines designing advanced photonic applications.

Язык: Английский

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Near Ultraviolet‐Excitable Cyan‐Emissive Hybrid Copper(I) Halides Nonlinear Optical Crystals with Near‐Unity Photoluminescence Quantum Yield and High‐Efficiency X‐ray Scintillation

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Авг. 23, 2024

Designing and synthesizing multifunctional hybrid copper halides with near ultraviolet (NUV) light-excited high-energy emission (<500 nm) remains challenging. Here, a pair of broadband-excited emitting isomers, namely, α-/β-(MePh

Язык: Английский

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1D Tin(II)‐Based Chiral Hybrid Perovskite Single Crystals with Extremely Distorted Inorganic Chains for Second Harmonic Generation

Advanced Optical Materials, Год журнала: 2024, Номер 12(17)

Опубликована: Фев. 17, 2024

Abstract The organic–inorganic hybrid metal halides with chiral structures have attracted great attentions in the field of optoelectronic functional materials, especially for nonlinear optics. To date, second harmonic generation (SHG) properties several classes different ions been reported. However, SHG‐active tin(II)‐based materials are rarely explored, hindering deep understandings relationship between their and SHG properties. Herein, Sn 2+ successfully introduced into perovskites, four new species perovskites ( R / S ‐α‐PEA)SnX 3 (X = Cl Br, PEA phenylethylammonium) obtained. as‐grown crystals P 2 1 space group, highly distorted [SnX 6 ] octahedral units forming 1D chain lattice, due to effect stereochemically active lone pair 5s electrons . Such an response ≈1.4× Y‐cut α‐quartz ‐α‐PEA)SnBr ≈0.9× ‐α‐PEA)SnCl at 1020 nm excitation, high polarization ratio signals as well wide bandgaps transparency windows meanwhile. This work opens up a platform discovering more novel superior optical future.

Язык: Английский

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Supramolecular Metal Halide Complexes for High-Temperature Nonlinear Optical Switches

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 8971 - 8980

Опубликована: Фев. 23, 2024

Nonlinear optical (NLO) switching materials, which exhibit reversible intensity modulation in response to thermal stimuli, have found extensive applications across diverse fields including sensing, photoelectronics, and photonic applications. While significant progress has been made solid-state NLO these materials typically showcase their highest performance near room temperature. However, this drastically deteriorates upon heating, primarily due the phase transition undergone by from noncentrosymmetric centrosymmetric phase. Here, we introduce a new class of supramolecular compounds 18-Crown-6 ether@Cu2Cl4·4H2O (1·4H2O), exhibiting stable when subjected near-infrared (NIR) photoexcitation and/or stimuli. The crystal structure external stimuli is attributed presence weakly coordinated bridging water molecule facilitated hydrogen bonding/chelation interactions between metal halide crown-ether supramolecules. We observed an exceptionally high second-harmonic generation (SHG) signal under continuous photoexcitation, even at temperatures exceeding 110 °C. In addition, molecules within complex can be released recaptured fully manner, all without requiring excessive energy input. This feature allows for precise control SHG activation deactivation through structural transformations, resulting high-contrast off/on ratio, reaching values million-fold range.

Язык: Английский

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Magneto‐chiral Nonlinear Optical Effect with Large Anisotropic Response in Two‐Dimensional Halide Perovskite

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(21)

Опубликована: Март 28, 2024

Abstract The chiral organic–inorganic halide perovskites (OIHPs) are vital candidates for superior nonlinear optical (NLO) effects associated with circularly polarized (CP) light. NLO in materials often couples magnetic dipole (MD) transition, as well the conventional electric (ED) transition. However, importance of MD transition process OIHPs has not yet been recognized. Here, circular probe analysis second harmonic generation dichroism (SHG‐CD) provides direct evidence that contribution leads to a large anisotropic response CP lights OIHPs, (R‐/S‐MBACl) 2 PbI 4 . thin films exhibit great sensitivity over wide wavelength range, and g‐value reaches up 1.57 at where is maximized. Furthermore, it also effective light generator, outputting CP‐SHG maximum g‐factor 1.76 upon stimulation linearly This study deepens understanding relation between chirality magneto‐optical effect, such an efficient discrimination signal highly applicable chirality‐based sensor communication devices.

Язык: Английский

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Enhancements of the first and second hyperpolarizability of a GMP coordination polymer: crystal structure and computational studies

Dalton Transactions, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

A chiral cobalt coordination complex {[Co(GMP)(BPE)(H 2 O) 3 ]·9H O} n (1) has been studied and characterized by X-ray single crystal powder diffraction.

Язык: Английский

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Cooperative Enhancement of Second Harmonic Generation in an Organic–Inorganic Hybrid Antimony Halide

Crystal Growth & Design, Год журнала: 2022, Номер 22(6), С. 3875 - 3881

Опубликована: Май 5, 2022

Exploration of nonlinear optical (NLO) crystalline materials is a hot and continuing research topic in modern optoelectronics laser technology. Within this portfolio, the emerging organic–inorganic hybrid metal halides provide infinite opportunities due to their fascinating advantages inorganic frameworks organic molecules. Herein, by cooperatively combining second-order Jahn–Teller distorted octahedron [SbCl6] π-conjugated aromatic amine (N,N,4-trimethylaniline, C9H13N), non-centrosymmetric (NCS) antimony halide, (C9H14N)SbCl4, has been developed. Meanwhile, bulky colorless single crystals (C9H14N)SbCl4 with dimensions 10 × 3 0.5 mm3 are grown temperature-lowering crystallization process. Further property investigations reveal that possess remarkable second harmonic generation (SHG) response (2.1 KDP, KH2PO4) moderate birefringence (0.095@546 nm) achieve phase-matching behavior, they demonstrate promising prospects for application NLO field. Furthermore, crystal structure analysis theoretical calculations large SHG primarily originates from cooperative coupling between highly asymmetric (3.649 10–3) amine. This work points out an efficient route future exploration new quadratic excellent performance halides.

Язык: Английский

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A chiral lead-free tin(IV)-based halide organic-inorganic semiconductor with dielectric switching and phase transition

Chinese Chemical Letters, Год журнала: 2022, Номер 34(8), С. 107980 - 107980

Опубликована: Ноя. 4, 2022

Язык: Английский

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