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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Circularly Polarized Luminescence Induced by Hydrogen‐Bonding Networks in a One‐Dimensional Hybrid Manganese(II) Chloride

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

Published: April 12, 2024

Chiral hybrid metal halides hold great potential as circularly polarized luminescence light sources. Herein, we have obtained two enantiomeric pairs of one-dimensional chiral manganese(II) chloride single crystals, R/S-(3-methyl piperidine)MnCl

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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Ionothermal synthesis of a hybrid cuprous(I) iodide scintillator with efficient cyan emission and high antiwater stability

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 159971 - 159971

Published: Jan. 1, 2025

Language: Английский

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Isomeric Zero-Dimensional Hybrid Copper(I) Iodides as Highly Efficient Multicolor Phosphors

ACS Materials Letters, Journal Year: 2024, Volume and Issue: 6(3), P. 865 - 876

Published: Feb. 7, 2024

The design and construction of new phosphors with significantly different emission colors are key areas in solid-state lighting technologies. Hybrid copper(I) iodides excellent candidates multicolor luminescence due to their remarkable structural diversity, superior performance, highly tunable optical characteristics. Here, we synthesize characterize a series 0D isomeric copper iodides, namely, Cu4I4(3-trifluoromethylpyridine)4. center [Cu4I4] cubane coordinates sterically hindered 3-trifluoromethylpyridine ligand form four isolated iodide clusters, which show ligand-configuration-dependent photoluminescence. polymorphs emit blue, green, yellow, pure white-light, respectively, high photoluminescence quantum yields (PLQYs) the range 80–95%. Time-resolved spectra all compounds long averaged decay lifetime up 10 μs. Density functional theory calculations reveal electronic structures characteristics at excited states, illustrating structure–emission relations. Our results demonstrate that configurations orientations have strong impact on distortion state, leading energy transitions colors. This work provides strategy for luminescent presents first example white-light system near-unity PLQY.

Language: Английский

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Copper(I)‐Arsine Clusters with a Near‐Unity Phosphorescence Quantum Yield for X‐Ray Scintillation and LED Applications

Advanced Optical Materials, Journal Year: 2024, Volume and Issue: 12(14)

Published: March 4, 2024

Abstract Rare‐earth element‐free materials that exhibit strong room temperature phosphorescence (RTP) and X‐ray scintillation properties are gaining global interest incessantly in the recent years. This work reports a series of easily synthesizable cubane Cu 4 I ‐triarsenic clusters [Cu (R 3 As) L] (L = none or nitrile), yellow‐green RTP with quantum efficiencies up to 100% short decay times (4.4–4.9 µs). The title cluster complexes display record ultralow detection limit (18.1 nGy s −1 ) perfectly linear dose rate response within remarkably wide window (0–640 µGy air ). (Ph ] is highlighted as an efficient phosphor for UV‐pumped white yellow LED devices, demonstrating excellent spectrum CIE index (0.32,0.33) bright emission, respectively. These results may stimulate future efforts designing highly arsenic‐based enriching family.

Language: Английский

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Dual-Emissive γ-[Cu₄I₈]^4– Enables Luminescent Thermochromism in an Organic–Inorganic Hybrid Copper(I) Halide

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(13), P. 5821 - 5830

Published: March 21, 2024

A highly luminescent (C13H28N2)2Cu4I8 single crystal containing isolated γ-[Cu4I8]4– anionic cluster was synthesized without the use of unsaturated cations. To best our knowledge, compounds bearing such like anions are not dual-emitting under UV excitation. However, dual emission does occur in (C13H28N2)2Cu4I8. Moreover, bands were found to be temperature-sensitive, allowing tuning colors from blue (0.19, 0.20) green (0.33, 0.47) Commission International de L' Eclairage (CIE) chromaticity coordinates. Remarkably, color could restored on returning initial temperature, confirming an efficient and reversible thermochromic effect The origin this excellent optical performance is discussed, difference mechanism with dual-emissive Cu(I) halide complexes also elucidated. Overall, work provides a promising way achieve thermochromism. developed represents one viable alternatives for eco-friendly materials.

Language: Английский

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Mono‐ and Bi‐Dentate Chiral Ligands Lead to Efficient Circularly Polarized Luminescence in 0D and 3D Semiconducting Copper(I) Iodides

Advanced Optical Materials, Journal Year: 2023, Volume and Issue: 11(19)

Published: May 13, 2023

Abstract Chiral hybrid Cu(I)‐based iodides with d 10 closed shell demonstrate great potential for circularly polarized luminescence (CPL) because of high photoluminescence quantum yield (PLQY). Herein, by incorporating mono‐ or bi‐dentate coordination mode ligands as chiral source, the self‐assembly four pairs iodides, namely, ( R / S )‐Cu 4 I (Hmpy) ·H 2 O ‐1), (3Hpy) ‐2), (2MePI) ‐3), and (3AD) ‐4) (where ‐Hmpy = ‐2‐pyrrolidinemethanol, ‐3Hpy ‐3‐hydroxypyrrolidine, ‐2MePI ‐2‐methylpiperazine, ‐3AD ‐3‐aminopiperidine), are reported. With monodentate bidentate ligands, these materials belong to two different structural types: 0D molecular clusters ‐1, ‐2) 3D porous metal–organic frameworks ‐3, ‐4). These all crystallize in non‐centrosymmetric space groups containing similar basic Cu cubane tetramer building units but modes. They also semiconductors, optical bandgaps ranging from 2.70 2.94 eV. The (PL) emissions further characterized, where highest PLQY ≈95% CPL dissymmetry factor g lum ) ≈7 × −3 achieved ‐1. This work offers a systematic comparison between types blocks, bridging flexible shows that copper highly promising candidates next‐generation optoelectronics chiroptics.

Language: Английский

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Controllable Circularly Polarized Luminescence with High Dissymmetry Factor via Co‐Assembly of Achiral Dyes in Liquid Crystal Polymer Films

Small Methods, Journal Year: 2024, Volume and Issue: 8(9)

Published: Jan. 14, 2024

Abstract Circularly polarized luminescence (CPL) materials are highly demanded due to their great potential in optoelectronic and chiroptical elements. However, the preparation of CPL films with high dissymmetry factors (g lum ) remains a formidable task, which impedes practical application film‐based devices. Herein, facile strategy prepare solid film g through exogenous chiral induction amplification liquid crystal polymers is proposed. Amplification reversion appear when annealed at nematic crystalline temperature maximal up 0.30 enhancement selective reflection. Thermal annealing treatment different states facilitates formation phase adjusts circularly emission. This work not only provides straightforward versatile platform construct organic capable exhibiting strong emission but also helpful understanding exact mechanism for performance.

Language: Английский

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Confined Self-Assembly of Anionic [Cu₈I₁₄]^6–-Type Supramolecular Cluster and Performance Enhancement of Photo-Oxidation and Photo-Click Reaction

Chemistry of Materials, Journal Year: 2024, Volume and Issue: 36(4), P. 2027 - 2038

Published: Feb. 14, 2024

The self-assembly of cuprous iodide supramolecular clusters with novel molecular structures and excellent photocatalytic performance through weak noncovalent interactions remains a major challenge. In this work, we fabricate dimeric anionic cluster [(Cu8I14)6–(L13+)2] (HUBU-1) using multicomponent confined strategy via host–guest encapsulation associated multicharge electrostatic interaction. Furthermore, HUBU-1 exhibits exceptional visible light absorption capability surmountable energy bandgap (Eg = 2.73 eV), which is crucial for the generation reactive oxygen species other radicals in photocatalysis process. Excellent photoelectric endows highly activity toward both oxidative coupling reaction benzylamine cycloaddition azide–alkynes (CuAAC) acetonitrile. Specifically, yields imine products reach 60–76% nine amine substrates under illumination. Likewise, photoinduced catalytic efficiency CuAAC reactions involving alkyne derivatives ranges from 56 to 90%. Consequently, by utilizing density functional theory calculations electron paramagnetic resonance experiments, propose mechanism superoxide radical-triggered photo-oxidation phenylacetylene radical-initiated cycloaddition.

Language: Английский

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