Temperature/Component‐Dependent Luminescence in Lead‐Free Hybrid Metal Halides for Temperature Sensor and Anti‐Counterfeiting

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(34)

Published: June 6, 2024

Abstract Hybrid metal halides (HMHs) have emerged as a promising platform for optically functional crystalline materials, but it is extremely challenging to thoroughly elucidate the electron transition coupled additional ligand emission. Herein, discover sequences of lead‐free HMHs with distinct active cations are aimed, that is, Sb 3+ (5s 2 ) lone‐pair configuration and In (4d 10 fully‐filled configuration. (Me NH 4 M Cl 6 ·Cl = −CH 3 , Sb, In) exhibits superior temperature/component‐dependent luminescence behaviors resulting from competition between triplet‐states (T n ‐S 0 self‐trapped excitons (STEs) inorganic units singlet‐state (S 1 organic cations, which manipulated by optical activity levels [SbCl ] 3− [InCl . The bonding differences /In − in terms electronic excitation hybridization emphasized, different electron‐transition mechanisms established according PL spectra at extreme temperature 5 305 K theoretical calculations. By fine‐tuning B‐site alloying, photoluminescence quantum yield (PLQY 81.5%) stability optimized 20% alloying This research sheds light on rules governing HMHs, well exploring optical‐functional application aviation sensors access‐control systems.

Language: 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, Journal Year: 2024, Volume and Issue: 63(19)

Published: March 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.

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 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.

Language: Английский

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Achieving Strong Circularly Polarized Luminescence through Cascade Cationic Insertion in Lead‐free Hybrid Metal Halides

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 28, 2024

Abstract Generating circularly polarized luminescence (CPL) with simultaneous high photoluminescence quantum yield (PLQY) and dissymmetry factor ( g lum ) is difficult due to usually unmatched electric transition dipole moment μ magnetic m of materials. Herein we tackle this issue by playing a “cascade cationic insertion” trick achieve strong CPL (with PLQY ~100 %) in lead‐free metal halides values reaching −2.3×10 −2 without using any chiral inducers. Achiral solvents hydrochloric acid (HCl) N, N ‐dimethylformamide (DMF) infiltrate the crystal lattice via asymmetric hydrogen bonding, distorting perovskite structure induce “intrinsic” chirality. Surprisingly, additional insertion Cs + cation substitute partial (CH 3 2 NH transforms space group achiral but maintains chiroptical activity. Further doping Sb 3+ stimulates as result self‐trapped excitons (STEs) formation disturbing framework. The perovskites indium‐antimony chlorides embedded on LEDs chips demonstrate promising potential emitters. Our work presents rare cases activity highly luminescent from only building blocks spontaneous resolution symmetry breaking.

Language: Английский

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Reversible Local Protonation‐Deprotonation: Tuning Stimuli‐Responsive Circularly Polarized Luminescence in Chiral Hybrid Zinc Halides for Anti‐Counterfeiting and Encryption

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(46)

Published: Aug. 13, 2024

Abstract Precise control over the organic composition is crucial for tailoring distinctive structures and properties of hybrid metal halides. However, this approach seldom utilized to develop materials that exhibit stimuli‐responsive circularly polarized luminescence (CPL). Herein, we present synthesis characterization enantiomeric zinc bromides: biprotonated (( R/S )‐C 12 H 16 N 2 )ZnBr 4 ‐LH2)ZnBr ) monoprotonated 15 ZnBr ‐LH1) ), derived from chiral amine ( )‐2,3,4,9‐Tetrahydro‐1H‐carbazol‐3‐amine 14 ). These compounds showcase luminescent properties; zero‐dimensional form emits green light at 505 nm, while form, with a pseudo‐layered structure, displays red 599 649 nm. Remarkably, reversible local protonation‐deprotonation behavior cations allows exposure polar solvents heating induce structural transformations between two forms. Theoretical calculations reveal lower energy barrier associated deprotonation process within pyrrole ring responsible observed. enantiomorphic bromides also switchable circular dichroism (CD) CPL properties. Furthermore, their chloride counterparts were successfully obtained by adjusting halogen ions. Importantly, unique characteristics position these halides as promising candidates applications in information storage, anti‐counterfeiting, encryption.

Language: Английский

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Mechanical Twisting-Induced Enhancement of Second-Order Optical Nonlinearity in a Flexible Molecular Crystal

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

Flexible molecular crystals are essential for advancing smart materials, providing unique functionality and adaptability applications in next-generation electronics, pharmaceuticals, energy storage. However, the optical of flexible have been largely restricted to linear optics, with nonlinear (NLO) properties rarely explored. Herein, we report on application mechanical twisting second-order optics. The crystal formed through self-assembly model compound 9-anthraldehyde (AA) features an intrinsic chiral noncentrosymmetric structure, demonstrating high efficiency second harmonic generation (SHG) NLO circular dichroism, which could be greatly enhanced by macroscopic twisting. anisotropic stacking imparts AA flexibility combined elastic bending plastic isochiral enhance SHG intensities order magnitude depending their M- or P-configuration. Meanwhile, dichroism factor gSHG-CD twisted is increased, achieving highest reported anisotropy among organic materials. These boosted performances intensity chiroptical response expected expand photonic crystals.

Language: Английский

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Achieving strong second harmonic generation effects induced via dimensional increase of PbX₆ octahedra and halogen substitutes in (C₁₀H₁₁N₃)PbX₄ (X = Cl or Br)

Inorganic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(12), P. 3618 - 3625

Published: Jan. 1, 2024

The second harmonic generation effect and birefringence of (C 10 H 11 N 3 )BX 4 perovskites are considerably enhanced via structural evolution halogen substitution strategies.

Language: Английский

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Solvent-induced structural regulation and luminescence switch of hybrid copper(I) halides for encryption and anti-counterfeiting applications

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(68), P. 9034 - 9037

Published: Jan. 1, 2024

Copper( i ) halides with different polyhedron units were obtained via solvent volatilization, showing consecutive structural evolution and photoluminescence tuning.

Language: Английский

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Macroscopic Twisting of Chiral Metal Halide Single Crystals Driven by Thermo-Induced Topochemical Dehydration

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(38), P. 26534 - 26542

Published: Sept. 10, 2024

Dynamic twisting crystals, combining the features of dynamic crystals and promise advanced applications in targeted drug delivery, biosensors, microrobots, spiral optoelectronics. However, determination with specific directions remains a formidable challenge practical applications. Herein, based on organic-inorganic hybrid metal halide (OIHMH) single we have realized chirality-induced macroscopic driven by thermo-induced topochemical dehydration reaction. These exhibit molecular-chirality-induced upon heating, along reversals their linear chiroptical circular dichroism nonlinear second harmonic generation dichroism. Such an induced has been attributed to alteration helical arrangement chiral cation post-topochemical dehydration. The feasibility tuning OIHMH switching properties might open up new avenues for developing microactuating optoelectronic

Language: Английский

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Near‐Complete Suppression of NIR‐II Luminescence Quenching in Halide Double Perovskites for Surface Functionalization Through Facet Engineering

Advanced Science, Journal Year: 2024, Volume and Issue: 11(32)

Published: June 26, 2024

Abstract Lanthanide‐based NIR‐II‐emitting materials (1000–1700 nm) show promise for optoelectronic devices, phototherapy, and bioimaging. However, one major bottleneck to prevent their widespread use lies in low quantum efficiencies, which are significantly constrained by various quenching effects. Here, a highly oriented (222) facet is achieved via engineering Cs 2 NaErCl 6 double perovskites, enabling near‐complete suppression of NIR‐II luminescence quenching. The optimally (222)‐oriented Ag 0.10 Na 0.90 ErCl microcrystals emit Er 3+ 1540 nm light with unprecedented high efficiencies 90 ± 6% under 379 UV excitation (ultralarge Stokes shift >1000 nm), record near‐unity yield 98.6% also obtained (222)‐based NaYb 0.40 0.60 Cl microcrystallites 980 excitation. With combined experimental theoretical studies, the underlying mechanism facet‐dependent emissions revealed, can contribute surface asymmetry‐induced breakdown parity‐forbidden transition undesired non‐radiative processes. Further, role reexamined molecular dynamics based on two facets, highlighting drastic two‐phonon coupling effect hydroxyl group 4 I 13/2 level . Surface‐functionalized facets will provide new insights tunable open up avenue developing efficient emitters toward broad applications.

Language: Английский

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