Achieving Near‐unity Photoluminescence Quantum Yields in Organic‐Inorganic Hybrid Antimony (III) Chlorides with the [SbCl₅] Geometry

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(10)

Published: Jan. 9, 2023

Hybrid organic-inorganic antimony halides have attracted increasing attention due to the non-toxicity, stability, and high photoluminescence quantum yield (PLQY). To shed light on structural factors that contribute PLQY, five pairs of with general formula A2 SbCl5 Sb2 Cl8 are synthesized via two distinct methods characterized. The type adopts square pyramidal [SbCl5 ] geometry near-unity while seesaw dimmer [Sb2 PLQY≈0 %. Through combined data analysis literature, we found series generally has much longer Sb⋅⋅⋅Sb distances, leading more expressed lone SbIII . Additional including Sb-Cl distance stability chlorides may also affect PLQY. Our targeted synthesis correlated insights provide efficient tools precisely form highly emissive materials for optoelectronic applications.

Language: Английский

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Multi‐Stimuli Responsive Luminescence and Domino Phase Transition of Hybrid Copper Halides with Nonlinear Optical Switching Behavior

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(18)

Published: March 2, 2023

Although phase transition materials (PTMs) under external stimuli are of great research interest duo to their rich potential applications, it is still challenging explore multi-responsive PTMs. Herein, two different phases organic-inorganic hybrid copper-based halides, α- and β-Gua3 Cu2 I5 (Gua+ =CN3 H6+ ), were synthesized by solvent evaporation method, which they crystalize in the noncentrosymmetric space group Fdd2 with zero-dimensional structure centrosymmetric C2/c one-dimensional metal-halogen framework, respectively. Interestingly, firstly demonstrated that Gua3 simultaneously possesses reversible PL conversion NLO switching properties response thermal stimulus. Strikingly, apart from heat, its structural can also be triggered crystalline-phase-recognition (CPR) mechanical force. These new findings may pave a path for future exploration PTMs multiple physical properties.

Language: Английский

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Reversible Triple-Mode Photo- and Radioluminescence and Nonlinear Optical Switching in Highly Efficient 0D Hybrid Cuprous Halides

Chemistry of Materials, Journal Year: 2023, Volume and Issue: 35(17), P. 6598 - 6611

Published: Aug. 17, 2023

Multifunctional stimuli-responsive luminescent and optical switching is extremely crucial for wide advanced photonic applications, but it remains a challenging objective halide perovskites. Herein, by performing single-crystal to (SC–SC) transformation as dynamic molecular strategy, we realized reversible triple-mode photoluminescence, radioluminescence (PL RL), nonlinear (NLO) in pair of zero-dimensional (0D) hybrid cuprous halides [ETPP]2Cu4Br6 [ETPP]CuBr2. Specifically, [ETPP]CuBr2 display highly efficient yellow green light emissions under UV excitation with the highest quantum yield up near unity. Simultaneously, identical can also be activated using X-ray RL 57,974 photons MeV–1, surpassing most previously reported halides. Most remarkably, SC–SC between them an ethanol impregnation-heating process, which provides PL/RL transitions two light-emitting states. Additionally, this process accompanied transition centrosymmetric NLO-inactive noncentrosymmetric NLO-active through second harmonic generation (SHG) "silent-active" switching. To best our knowledge, first PL, RL, SHG perovskite chemistry, realize applications data storage, information security, logic gates, etc.

Language: Английский

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Multiple Stimuli‐Responsive Luminescent Chiral Hybrid Antimony Chlorides for Anti‐Counterfeiting and Encryption Applications

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(36)

Published: July 18, 2023

Stimuli-responsive circularly polarized luminescence (CPL) materials are ideal for information anti-countering applications, but the best-performing have not yet been identified. This work presents enantiomorphic hybrid antimony halides R-(C5 H12 NO)2 SbCl5 (1) and S-(C5 (2) showing mirror-imaged CPL activity with a dissymmetry factor of 1.2×10-3 . Interestingly, DMF-induced structural transformation is realized to obtain non-emissive ⋅ DMF (3) (4) upon exposure vapor. The process reversed heating. DFT calculations showed that DMF-induced-quenched-luminescence attributed intersection ground excited state curves on configuration coordinates. Unexpectedly, nanocrystals chiral 1 2 were prepared indicate excellent solution performance. reversible PL switching gives system applications in technology, anti-counterfeiting, encryption-decryption, logic gates.

Language: Английский

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High‐Temperature, Reversible, and Robust Thermochromic Fluorescence Based on Rb₂MnBr₄(H₂O)₂ for Anti‐Counterfeiting

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(35)

Published: May 12, 2023

Thermochromic fluorescent materials (TFMs) characterized by noticeable emission color variation with temperature have attracted pervasive attention for their frontier application in stimulus-response and optical encryption technologies. However, existing TFMs typically suffer from weak PL reversibility as well limited mild operating severe quenching. switching under extreme conditions such high will undoubtedly improve security, while it is still challenging present TFMs. In this work, high-temperature thermochromic fluorescence up to 473 K robust structural of 80 cycles are observed Rb2 MnBr4 (H2 O)2 related crystals, which seldom reported changes at a temperature. Temperature-driven nonluminous, red green light states can be achieved specific temperatures the modulation mechanism verified situ measurements single particle transition. By virtue unique feature, multicolor anti-counterfeiting label based on broad gradient multidimensional information applications demonstrated. This work opens window design inorganic multi-PL change development advanced strategies stimuli source.

Language: Английский

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Multisite Fine‐Tuning in Hybrid Cadmium Halides Enables Wide Range Emissions for Anti‐Counterfeiting

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Feb. 13, 2024

Abstract Achieving tunable emissions spanning the spectrum, from blue to near‐infrared (NIR) light, within a single component is formidable challenge with significant implication, particularly in tailoring multicolor luminescence for anti‐counterfeiting purposes. In this study, we demonstrate broad spectrum of emissions, covering red and extending into NIR light [BPy] 2 Cd X 4 : x Sb 3+ (BPy=Butylpyridinium; =Cl, Br; =0 0.08) through precise multisite structural fine‐tuning. Notably, CdBr manifest distinctive pattern, transitioning yellow tandem host further its homologous CdCl , resulting simultaneous presence intersecting independent emission colors. Detailed modulation chemical composition enables partial switching, facilitating creation diverse patterns by employing as phosphors. This study first time successfully implements several groups colors matrix via Such an effective strategy not only develops specific relationships between adjustable compositions, but also introduces cost‐effective straightforward approach achieving unique, high‐level, plentiful‐color multiple‐information‐storage labels advanced applications.

Language: Английский

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Stimuli‐Responsive Emission from Hybrid Metal Halides

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(17)

Published: Jan. 7, 2024

Abstract Stimuli‐responsive photoluminescent (PL) materials have attracted considerable attention in recent years owing to their potential applications anti‐counterfeiting, information encryption, and sensing. Further investigations of the transformation mechanism stimulus‐responsive PL are considerably important. In current study, an organic–inorganic metal halide, C 9 H 15 N 3 SbCl 5 ([C 13 ] 2+ is a 1‐(2‐pyridyl) piperazine cation) obtained, which exhibits 0D structure with P‐ 1 space group. At room temperature, when excited by UV light, single crystals exhibit unimodal blue light emission at 405 nm, grinding or hydrostatic pressure induces double‐peak emissions 650 nm. Interestingly, double‐emission samples can be restored single‐emission short annealing storage air for 2 weeks, this process reversible. Luminescence response mechanical stimuli also achieved presence hydrochloric acid water. Spectral analysis microstructural changes revealed that structural modifications inorganic group play pivotal role stimulus. Finally, composite film device based on prepared demonstrate these smart anti‐counterfeiting sensing applications.

Language: Английский

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Achieving Near‐Unity Red Light Photoluminescence in Antimony Halide Crystals via Polyhedron Regulation

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: April 15, 2024

Exploration of efficient red emitting antimony hybrid halide with large Stokes shift and zero self-absorption is highly desirable due to its enormous potential for applications in solid light emitting, active optical waveguides. However, it still challenging rarely reported. Herein, a series (TMS)

Language: Английский

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Zero-Dimensional Hybrid Cuprous Halide of [BAPMA]Cu₂Br₅ as a Highly Efficient Light Emitter and an X-Ray Scintillator

ACS Applied Materials & Interfaces, Journal Year: 2023, Volume and Issue: 15(16), P. 20219 - 20227

Published: April 17, 2023

Lead halide perovskites have been explored as a new kind of promising X-ray with wide applications in radiation-associated fields, but low light yield and serious toxicity extremely restrict further applications. To address these issues, we herein demonstrated one zero-dimensional (0D) organic-inorganic hybrid cuprous [BAPMA]Cu2Br5 (BAPMA = N,N-Bis(3-aminopropyl) methylamine) containing discrete [Cu4Br10]6- tetramers excellent lead-free scintillators. Upon UV excitation, displays highly efficient broadband yellowish-green emission dominant peak at 526 nm, large Stokes shift 244 high photoluminescent quantum 53.40%. Significantly, this can also be excited by higher-energy radioluminescence scintillation 43,744 photons/MeV. The detection limit 0.074 μGyair/s is far less than the required value for regular medical diagnostics 5.5 μGyair/s. solution-assembled structure facilely enables [BAPMA]Cu2Br5-based screen to display high-performance imaging spatial resolution 15.79 lp/mm showcasing potential application radiography. In brief, combined merits cost, negligible self-absorption, limit, considerable yield, highlight performance 0D halide.

Language: Английский

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Origin of singlet self-trapped exciton and enhancement of photoluminescence quantum yield of organic–inorganic hybrid antimony(III) chlorides with the [SbCl5]2− units

Nano Research, Journal Year: 2023, Volume and Issue: 16(11), P. 12680 - 12688

Published: Aug. 29, 2023

Language: Английский

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