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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Excitation-Dependent Emission in Sb³⁺-Doped All-Inorganic Rare-Earth Double Perovskites for Anticounterfeiting Applications

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(23), P. 10481 - 10489

Published: May 24, 2024

Achieving high-efficiency tunable emission in a single phosphor remains significant challenge. Herein, we report series of Sb3+-doped all-inorganic double perovskites, Sb3+:Cs2NaScCl6, with efficient excitation-dependent emission. In 0.5%Sb3+:Cs2NaScCl6, strong blue high photoluminescence quantum yield (PLQY) 85% is obtained under 265 nm light irradiation, which turns into bright neutral white PLQY 56% when excited at 303 nm. Spectroscopic and computational investigations were performed to reveal the mechanism this Sb3+ doping induces two different excitation channels: internal transition Sb3+: 5s2 → 5s5p electron transfer 5s Sc3+ 3d. The former one generates ions, can undergo energy populate host self-trapped exciton (STE) state, yielding enhanced latter leads formation new STE state hole localized on delocalized nearest Sc3+, accounts for newly exhibited low-energy difference pathways emitting states results highly emission, making doped systems promising anticounterfeiting materials.

Language: Английский

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Dynamic Phosphorescence/Fluorescence Switching in Hybrid Metal Halides Toward Time‐Resolved Multi‐Level Anti‐Counterfeiting

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 18, 2024

Abstract Hybrid metal halides (HMHs) with time‐resolved luminescence behavior promise to be a breakthrough in multi‐level anti‐counterfeiting, but controlling the dynamic switching between phosphorescence and fluorescence is extremely challenging. Herein, an array of 0D HMHs constructed by screening π ‐conjugated ligand room‐temperature (RTP). Compared organic chromophore, (ETPP) 2 ZrCl 6 possesses misaligned stacking rigid structure, contributing improved quantum yield (Φ P = 27.50%) extended lifetime ( τ 0.6234 s), as intervening inorganic unit [ZrCl ] 2− suppresses energy losses caused nonradiative relaxation prompts intersystem crossover (ISC) process. Not only that, interplay phosphorescence‐fluorescence dual‐mode emission can intelligently controlled doping active Te 4+ , resulting RTP self‐trapped exciton (STE) fluorescence. DFT calculations reveal governing origins RTP‐STE from intermolecular ISC channels spin‐orbit coupling (SOC) coefficients. These precise images into periodic pixelated arrays enable anti‐counterfeiting information encryption. This work proposes fluorescence‐phosphorescence co‐modulating strategy under premise dissecting structural for optimizing phosphorescence, which paves way designing high‐security‐level materials.

Language: Английский

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Advances and Challenges in X-ray-Excited Scintillators and Their Biomedical Applications: Current Insights and Future Directions

ACS Applied Materials & Interfaces, Journal Year: 2025, Volume and Issue: unknown

Published: April 7, 2025

This review explores the pivotal role of scintillators in biomedical applications, with a particular emphasis on their utilization context X-ray excitation. It commences an in-depth analysis two predominant categories scintillators: inorganic and organic, meticulously delineating distinctive properties respective applications. The discourse subsequently advances to explore critical applications X-ray-excited (XESs), underscoring significant advancements medical imaging, radiation detection, dosimetry. Moreover, identifies prevailing challenges limitations deployment these for purposes, thereby establishing robust foundation ongoing research endeavors. outlines potential directions, advocating interdisciplinary collaborations overcome existing barriers. By synthesizing current knowledge identifying areas future investigation, this aims guide researchers enhancing efficacy application science.

Language: Английский

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Tuning Covalent Bonding in Znic-Based Hybrid Halides towards Tunable Room-Temperature Phosphorescence

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This work investigates organic–inorganic metal halides with room-temperature phosphorescence, showing that tuning the organic components and their interactions improves RTP performance for anti-counterfeiting applications.

Language: Английский

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Advances of Low-Dimensional Organic-Inorganic Hybrid Metal Halide Luminescent Materials: A Review

Crystals, Journal Year: 2025, Volume and Issue: 15(4), P. 364 - 364

Published: April 16, 2025

Low-dimensional organic–inorganic hybrid metal halides (OIMHs) have garnered significant research attention due to their remarkable optical, electrical, and mechanical properties. These materials feature tunable optoelectronic characteristics, high photovoltaic efficiency, exceptional scalability processability ease of fabrication. By selecting appropriate organic inorganic components, it is possible achieve molecular-level dimensional control the halides. Here, this review provides an in-depth analysis structure synthesis methods OIMHs materials, explores optical properties, summarizes current applications in areas such as white-light LEDs, X-ray detectors, sensors, solar cells. Finally, we also discuss challenges faced by these offer a perspective on future development, aiming serve reference for advancing OIMHs.

Language: Английский

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N₂H₄Zn(HC₃N₃O₃): exceptionally strong second harmonic generation and ultra-long phosphorescence

Chemical Science, Journal Year: 2024, Volume and Issue: 15(38), P. 15725 - 15730

Published: Jan. 1, 2024

A novel hydro-isocyanurate, N 2 H 4 Zn(HC 3 O ), possessing an asymmetric topological diamond-like 3D network exhibits the strongest second harmonic generation among cyanurates (13 × KDP) and ultra-long room-temperature phosphorescence (448 ms).

Language: Английский

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Zero-dimensional organic–inorganic hybrid zinc halide with stable broadband blue light emissions

CrystEngComm, Journal Year: 2024, Volume and Issue: 26(46), P. 6585 - 6590

Published: Jan. 1, 2024

A series of zero-dimensional zinc halide materials based on [ZnX 4 ] 2− tetrahedra are prepared, which exhibit intense broadband blue light emission.

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, Journal Year: 2024, Volume and Issue: 136(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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Unique Organic Crystal Skeleton Based on N‐Phenyl‐Carbazole Derivatives with Adjustable Room Temperature Phosphorescence and Highly Stable Inclusion Ability to Dichloromethane

Small, Journal Year: 2024, Volume and Issue: 20(47)

Published: Aug. 20, 2024

Monosubstituted 9-(2-bromophenyl)-carbazole (1Br1CZ) and disubstituted 9,9'-(2,4-dibromo-1,3-phenylene) bis(9H-carbazole) (2Br2CZ) are synthesized by introducing bromine into ortho-phenyl position of 9-phenyl-carbazole (PhCZ). The decomposition temperature with 5% mass loss melting point 2Br2CZ crystal 360 230 °C. highest occupied molecular orbital energy level PhCZ is the highest, that lowest. crystals PhCZ, 1Br1CZ, monoclinic, orthorhombic, triclinic system, which exhibit room phosphorescence lifetimes 171.81, 37.15, 28.77 ms, their corresponding quantum yields 0.83%, 0.16%, 4.58%. It theoretically reveals six triplet levels (T

Language: Английский

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