Anomalous Charge Transfer from Organic Ligands to Metal Halides in Zero‐Dimensional [(C₆H₅)₄P]₂SbCl₅ Enabled by Pressure‐Induced Lone Pair‐π Interaction

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(37)

Published: July 19, 2023

Low-dimensional (low-D) organic metal halide hybrids (OMHHs) have emerged as fascinating candidates for optoelectronics due to their integrated properties from both and inorganic components. However, most of low-D OMHHs, especially the zero-D (0D) compounds, inferior electronic coupling between ligands halides prevents efficient charge transfer at hybrid interfaces thus limits further tunability optical properties. Here, using pressure regulate interfacial interactions, is achieved, which leads a near-unity photoluminescence quantum yield (PLQY) around 6.0 GPa in 0D OMHH, [(C6 H5 )4 P]2 SbCl5 . In situ experimental characterizations theoretical simulations reveal that pressure-induced lone-pair electrons Sb3+ π benzene ring (lp-π interaction) serves an unexpected "bridge" transfer. Our work opens versatile strategy new materials design by manipulating lp-π interactions organic-inorganic systems.

Language: Английский

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A Luminescent Hybrid Bimetallic Halide Family with Solvent‐Coordinated Rare Earth and Alkaline Earth Metals

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: May 6, 2024

Abstract Hybrid metal halides are an extraordinary class of optoelectronic materials with extensive applications. To further diversify and study the in‐depth structure‐property relations, we report here a new family 21 zero‐dimensional hybrid bimetallic chlorides general formula A ( L ) n [ B Cl m ] =rare earth RE ), alkaline metals Mn; =solvent ligand; =Sb, Bi Te). The (DMSO) 8 6 =La, Ce, Sm, Eu, Tb, Dy; DMSO=dimethyl sulfoxide) series shows broadband emission attributed to triplet radiative recombination from Sb Bi, incorporating characteristic metals, where Eu(DMSO) [BiCl staggering PL quantum yield 94 %. pseudo‐octahedral [SbCl 5 vacancy in II =Mg, Ca Mn) square pyramidal (TMSO) (TMSO=tetramethylene enhance stereoactive expression s 2 lone pairs 3+ , giving rise observation dual‐band singlet emission, respectively. Te(IV) analogues have been characterized, showing blue‐light‐excitable single‐band emission. This work expands space for emphasis on harnessing elements, provides important insights into designing emitters regulating their properties.

Language: Английский

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Blue Long Afterglow and Ultra Broadband Vis‐NIR Emission from All‐Inorganic Copper‐Doped Silver Halide Single Crystals

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(25)

Published: April 18, 2024

Abstract All‐inorganic metal halides with afterglow emission have attracted increasing attention due to their significantly longer duration and higher stability compared organic–inorganic hybrid counterparts. However, colors not yet reached the blue spectral region. Here, we report all‐inorganic copper‐doped Rb 2 AgBr 3 single crystals ultralong (>300 s) by modulating defect states through doping engineering. The introduction of copper(I) ions into facilitates formation bromine vacancies, thus density trap available for charge storage enabling bright, persistent after ceasing excitation. Moreover, cascade energy transfer between distinct emissive centers in results ultra‐broadband photoluminescence, only covering whole white light near‐unity quantum yield but also extending near‐infrared This ‘cocktail’ exotic light‐emission properties, conjunction excellent crystals, allowed us demonstrate implementation solid‐state lighting, night vision, intelligent anti‐counterfeiting.

Language: Английский

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Near-unity photoluminescence quantum yield in zero-dimensional lead-free indium-based hybrid perovskites by antimony doping

Journal of Materials Chemistry C, Journal Year: 2024, Volume and Issue: 12(7), P. 2571 - 2577

Published: Jan. 1, 2024

High-performance broadband emission with a near-unity photoluminescence quantum yield of ∼99.3% was observed in (C 4 H 12 N) 2 InC 5 ·DMF:Sb 3+ hybrid perovskites, which can be attributed to the self-trapped excitons [SbCl ·DMF] 2− polyhedron.

Language: Английский

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Multi-stimuli-responsive luminescence enabled by crown ether anchored chiral antimony halide phosphors

Chemical Science, Journal Year: 2024, Volume and Issue: 15(10), P. 3530 - 3538

Published: Jan. 1, 2024

The chirality-dependent lattice distortion assisted by a crown ether leads to an intense STEs emission along with CPL. distinct endows the Sb halides multi-stimuli-responsive PL behaviours towards excitation wavelength and temperature.

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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Optoelectronic insights of lead-free layered halide perovskites

Chemical Science, Journal Year: 2024, Volume and Issue: 15(20), P. 7374 - 7393

Published: Jan. 1, 2024

Two-dimensional organic-inorganic halide perovskites have emerged as promising candidates for a multitude of optoelectronic technologies, owing to their versatile structure and electronic properties. The optical properties are harmoniously integrated with both the inorganic metal octahedral slab, organic spacer layer. layers can also assemble into periodically stacked nanoplatelets, which interconnected by ammonium cation, resulting in formation superlattice or superstructure. In this perspective, we explore structural, electronic, lead-free hybrid halides, layered perovskite single crystals nanostructures, expanding our understanding diverse applications enabled these structures. superlattices function layer thickness, center either divalent combination monovalent trivalent cations, composition. distinct absorption emission features guided structural deformation, electron-phonon coupling, polaronic effect. Among possibilities, focused on photodetection capability crystals, elucidated descriptors such excitonic band gap, effective mass, carrier mobility, Rashba splitting, spin texture that decides direct component transitions.

Language: Английский

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Chiral Copper(I) Iodide Cluster Hybrids Enabling Highly Efficient Circularly Polarized Electroluminescence

Advanced Functional Materials, Journal Year: 2025, Volume and Issue: unknown

Published: March 16, 2025

Abstract While the emergence of copper(I)‐iodide cluster hybrid materials as potential substitutes for toxic lead halides in electroluminescence applications represents a major advancement, efficiency still needs improvement and fact circularly polarized (CPEL) remains largely unexplored. In this work, design chiral phosphine ligands is dedicated to attaining strongly luminescent materials, thus achieving high‐efficiency CPEL through host‐guest doping strategy. The hybrids exhibit intense yellow emission peaked at 567 nm with notable luminescence (CPL). Doping films comprising 30% 1,3‐bis(N‐carbazolyl)benzene (mCP), 2,6‐bis(3‐(9H‐carbazol‐9‐yl)phenyl)pyridine (2,6‐DCZPPY), 40% Cu 2 I demonstrated excellent CPL quantum yield (PLQY) exceeding 80% low surface roughness 0.358 nm. Based on this, electrically driven light‐emitting diodes (LEDs) dissymmetry factor ( g EL ) 1.36×10 −3 peak external (EQE) 20.5% are successfully developed. Notably, work not only first demonstration Cu(I) halide clusters but also provides one top device efficiencies non‐lead metal materials.

Language: Английский

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Environment-Friendly and Highly Efficiency Organic Antimony Halide Scintillator for Light Emitting Diode and X-ray Imaging

Journal of Alloys and Compounds, Journal Year: 2025, Volume and Issue: unknown, P. 180205 - 180205

Published: April 1, 2025

Language: Английский

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Antimony -doped indium-based halide single crystals enabling white-light emission

Inorganic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(19), P. 5008 - 5015

Published: Jan. 1, 2022

Metal halides (TMPL) 3 InCl 6 ·EtOH:xSb 3+ with tunable colors were obtained by gradient Sb doping. Interestingly, white emission was achieved when 0.1% of employed, due to a combination the cyan organic moiety and orange from metal halides.

Language: Английский

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