Hafnium-Based Chiral 2D Organic–Inorganic Hybrid Metal Halides: Engineering Polarity and Nonlinear Optical Properties via Para-Substituent Effects

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 8, 2025

Two-dimensional (2D) organic–inorganic hybrid metal halides (OIMHs), characterized by noncentrosymmetric structures arising from the incorporation of chiral organic molecules that break inversion symmetry, have attracted significant attention. Particularly, chiral-polar 2D OIMHs offer a unique platform for multifunctional applications, as coexistence chirality and polarity enables simultaneous manifestation distinct properties such nonlinear optical (NLO) effects, circular dichroism (CD), ferroelectricity. In this study, we report first synthesis hafnium (Hf)-based OIMHs, achieved through strategic para-substituents on benzene ring components. By tuning substituents, successfully modulate crystal structures, resulting in both chiral-nonpolar systems. Our analysis structural properties, supported density functional theory calculations, demonstrates these materials can be systematically tuned, enabling adjustable band gaps CD UV range (200–280 nm). Notably, halogen substitution at para-position layer produces tunable ranging 4.33 to 4.48 eV, widest reported date OIMHs. Furthermore, exhibit enhanced NLO including remarkable 3.3-fold increase second-harmonic generation intensity compounds compared their counterparts. These findings position Hf-based promising candidates UV-region devices self-driven circularly polarized light detectors, offering new opportunities designing optoelectronic harnessing interplay between polarity.

Язык: Английский

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Chiral europium halides with high-performance magnetic field tunable red circularly polarized luminescence at room temperature

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Март 14, 2025

Chiral organic-inorganic hybrid metal halides as promising circularly polarized luminescence (CPL) emitter candidates hold great potential for high-definition displays and future spin-optoelectronics. The recent challenge lies primarily in developing high-performance red CPL emitters. Here, coupling the f-f transition characteristics of trivalent europium ions (Eu3+) with chirality, we construct chiral Eu-based halides, (R/S-3BrMBA)3EuCl6, which exhibit strong predictable emission large photoluminescence quantum yield (59.8%), narrow bandwidth (≈2 nm), long lifetime ms), together dissymmetry factor |glum| 1.84 × 10−2. Compared previously reported these show highest brightness. Furthermore, degree polarization (R/S-3BrMBA)3EuCl6 can be manipulated by external magnetic field. Particularly, benefiting from field-generated Zeeman splitting spin mixing at exciton states, an anomalously positive magneto-photoluminescence was observed room temperature. This work provides efficient strategy constructing both pure-red It also opens door rare-earth toward optoelectronic spintronic applications. perovskites are materials luminescence. Here authors present leading to magneto-chiroptical properties.

Язык: Английский

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Chiral Inorganic Nanomaterial‐Based Diagnosis and Treatments for Neurodegenerative Diseases

Advanced Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 9, 2025

Chiral nanomaterials are widely investigated over recent decades due to their biocompatibility and unique chiral effects. These key properties have significantly promoted the rapid development of in bioengineering medicine. In this review, basic principles constructing along with latest progress research comprehensively summarized. Then, application for diagnosis neurodegenerative diseases (NDDs) is systematically described. addition, significant potential broad prospects treatment NDDs highlighted from several aspects, including disaggregation neurofibrils, scavenging reactive oxygen species, regulation microbial-gut-brain axis, elimination senescent cells, promotion directed differentiation neural stem cells. Finally, a perspective challenges future provided.

Язык: Английский

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Singlet Carbenes Are Stereoinductive Main Group Ambiphiles

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 21, 2025

Stereogenic units are a critical source of molecular complexity, but their stereoselective formation via main group ambiphiles─which suitable for derivatizing wide scope functionalities─is largely unexplored. Herein, using chiral cyclic (alkyl)(amino)carbenes (ChiCAACs), we study stereoinduction during the oxidative addition E-H σ-bonds (E = C, N, O, Si, P). Through computational modeling, relationship between stereochemical outcome and mechanism is elucidated, providing insight into when why ChiCAACs exhibit excellent stereoselectivities. Altogether, these results demonstrate potential ambiphiles to generate stereogenic in highly controlled manner opening avenues applying "metal-like" reactivity metal-free asymmetric syntheses.

Язык: Английский

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Chiroptical Activities of Low‐Dimensional Lead‐Free Chiral Halide Perovskites with White‐Light Emission

Small Science, Год журнала: 2025, Номер unknown

Опубликована: Май 15, 2025

Chiral halide perovskites have attracted considerable attention due to their intrinsic chirality‐induced circular dichroism (CD), circularly polarized luminescence (CPL), and spin selectivity. However, chiroptical activities of low‐dimensional lead‐free chiral are hardly observed, especially for those with white‐light emission. Herein, different ratios 0D Cs 3 Cu 2 I 5 1D CsCu realized. Chiroptical introduced into these films by post‐treatment r‐/s‐methylbenzylammonium iodide realize perovskites. The absorption, photoluminescence, photoluminescence excitation, CD, CPL spectra investigated. Commission Internationale de L’Eclairage chromaticity coordinates (0.33, 0.33) obtained when the excitation wavelength is 300 nm. Large Stokes shifts broadband emission observed attributed presence self‐trapped excitons. At room temperature, CD signals without application an external magnetic field, indicating chirality in Room‐temperature also from perovskites, but only component. This fact that does not produce spin‐polarized excitons do transfer .

Язык: Английский

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Spin‐Orbital Ordering Effects of Light Emission in Organic–Inorganic Hybrid Metal Halide Perovskites

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Дек. 10, 2024

Organic-inorganic hybrid metal halide perovskites carrying strong spin-orbital coupling (SOC) have demonstrated remarkable light-emitting properties in spontaneous emission, amplified emission (ASE), and circularly-polarized luminescence (CPL). Experimental studies shown that SOC plays an important role controlling the such perovskites. Here, consists of both orbital (L) spin (S) momentum, leading to formation J (= L + S) excitons intrinsically involving momentum. In general, there are three issues determining effects on excitons. First, when function as individual quasi-particles, configurations momentum directly decide bright dark Second, mutually interacting collective exciton-exciton interactions can occur through The give rise different properties, presenting ordering effects. Third, develop ASE coherent interaction CPL exciton-helical effect. This review article discusses ASE, organic-inorganic

Язык: Английский

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Exploring π-extended chiral ligands for the direct detection of circularly polarized light in 2D chiral perovskites

Journal of Materials Chemistry C, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

In this work, we synthesized π-extended phenyl based chiral organic ligands and successfully constructed larger-sized perovskites, enabling the detection of circularly polarized light.

Язык: Английский

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