Correlating π–π Stacking of Aromatic Diammoniums with Stability and Dimensional Reduction of Dion–Jacobson 2D Perovskites

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(12), С. 8198 - 8205

Опубликована: Март 13, 2024

Dion–Jacobson (DJ) phase 2D perovskites with various aromatic diammonium cations, potentially possessing high stability, have been developed for optoelectronics. However, their stability does not meet initial expectations, and some of them even easily degrade into lower-dimensional structures. Underlying the mechanism dimensional reduction these DJ remains elusive. Herein, we report that π–π stacking intensity between cations determines structural variation by investigating nine benzene diammoniums (BDAs)-derived low-dimensional perovskites. The BDAs without intermolecular form stable perovskites, while those showing strong tend to generate 1D 0D architectures. Furthermore, highly relies on molecular symmetry electrostatic potential BDAs; namely, asymmetry small dipole moment facilitate alleviating stacking, leading formation vice versa. Our findings establish relationship structure−π–π interaction–perovskite dimensionality, which can guide design manipulation perovskite dimensionality optoelectronic applications.

Язык: Английский

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Robust Single-Supermolecule Switches Operating in Response to Two Different Noncovalent Interactions

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(34), С. 18800 - 18811

Опубликована: Авг. 17, 2023

Supramolecular electronics provide an opportunity to introduce molecular assemblies into electronic devices through a combination of noncovalent interactions such as [π···π] and hydrogen-bonding interactions. The fidelity dynamics hold considerable promise when it comes building with controllable reproducible switching functions. Here, we demonstrate strategy for electronically robust switches by harnessing two different between couple pyridine derivatives. single-supermolecule switch is turned ON compressing the junction enabling dominate transport, while OFF stretching form hydrogen-bonded dimers, leading dramatic decrease in conductance. robustness reproducibility these were achieved modulating Ångström precision at frequencies up 190 Hz obtaining high ON/OFF ratios ∼600. research presented herein opens avenue designing bistable mechanoresponsive which will find applications integrated circuits microelectromechanical systems.

Язык: Английский

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A Carbonyl and Azo-Based Polymer Cathode for Low-Temperature Na-Ion Batteries

ACS Nano, Год журнала: 2024, Номер 18(5), С. 4159 - 4169

Опубликована: Янв. 24, 2024

Due to flexible structure tunability and abundant diversity, redox-active polymers are promising cathode materials for developing affordable sustainable Na-ion batteries (NIBs). However, polymer cathodes still suffer from low capacity, poor cycle life, sluggish reaction kinetics. Herein, we designed synthesized a material bearing carbonyl azo groups as well extended conjugation structures in the repeating units. The exhibited exceptional electrochemical performance NIBs terms of high long lifetime, fast When coupled with low-concentration electrolyte, it shows superior at temperatures down −50 °C, demonstrating great promise low-temperature battery applications. Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) were employed study mechanism, interphase structure, morphological evolution, confirming reversible redox reactions between azo/carbonyl Na+/electrons, NaF-rich interphase, stability upon cycling. This work provides an effective approach high-performance affordable, sustainable, NIBs.

Язык: Английский

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Polymerization-Induced Sulfone-Bond-Driven Self-Assembly

Macromolecules, Год журнала: 2025, Номер 58(3), С. 1621 - 1629

Опубликована: Янв. 31, 2025

Sulfone bonding refers to dipole–dipole interactions between sulfone groups, which have been long overlooked. Herein, was employed for the first time as driving force self-assembly of block copolymers via a polymerization-induced sulfone-bond-driven (PI-SDSA) strategy. The presence in sulfone-functionalized monomer confirmed by scanning tunneling microscopy break junction measurements at single-molecule level. Successful PI-SDSA achieved toluene, and polymerization kinetics polymerization-enhanced force. demonstrated possess peculiar monomer/solvent library successful series sulfone-containing monomers solvents with varying dipole moments. as-prepared polymer assemblies manifested unique salt-responsiveness because competitive ion–dipole ions enabling salt-responsive payload release. use has provided new perspective both will inspire design stimuli-responsive supramolecular materials.

Язык: Английский

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Intermolecular and Electrode-Molecule Bonding in a Single Dimer Junction of Naphthalenethiol as Revealed by Surface-Enhanced Raman Scattering Combined with Transport Measurements

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(29), С. 15788 - 15795

Опубликована: Июль 12, 2023

Electron transport through noncovalent interaction is of fundamental and practical importance in nanomaterials nanodevices. Recent single-molecule studies employing junctions have revealed unique electron properties interactions, especially those a π-π interaction. However, the relationship between junction structure remains elusive due to insufficient knowledge geometric structures. In this article, we employ surface-enhanced Raman scattering (SERS) synchronized with current-voltage (I-V) measurements characterize structure, together properties, single dimer monomer naphthalenethiol, former which was formed by intermolecular The correlation analysis vibrational energy electrical conductance enables identifying molecule-electrode interactions these molecular and, consequently, addressing exclusively associated addition, achieved discrimination NT molecule Au electrode junction, i.e., Au-π through-π coupling though-space coupling. power density spectra support character at interfaces junctions. These results demonstrate that simultaneous SERS I-V technique provides means for structural investigation interactions.

Язык: Английский

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Delocalizing Excitation for Highly‐Active Organic Photovoltaic Catalysts

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(26)

Опубликована: Апрель 19, 2024

Localized excitation in traditional organic photocatalysts typically prevents the generation and extraction of photo-induced free charge carriers, limiting their activity enhancement under illumination. Here, we enhance delocalized photoexcitation small molecular photovoltaic catalysts by weakening electron-phonon coupling via rational fluoro-substitution. The optimized 2FBP-4F catalyst develop here exhibits a minimized Huang-Rhys factor 0.35 solution, high dielectric constant strong crystallization solid state. As result, energy barrier for exciton dissociation is decreased, more importantly, polarons are unusually observed nanoparticles (NPs). With increased hole transfer efficiency prolonged carrier lifetime highly related to enhanced delocalization, PM6 : heterojunction NPs at varied concentration exhibit much higher photocatalytic (207.6-561.8 mmol h

Язык: Английский

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Color‐Tunable White Circularly Polarized Electroluminescence Triggered Using Chiral Co‐Assembly‐Sensitized Strategy

Laser & Photonics Review, Год журнала: 2024, Номер 18(11)

Опубликована: Июнь 26, 2024

Abstract White circularly polarized organic light‐emitting diodes (CP‐WOLEDs) are central to prospective 3D displays and lighting sources. However, owing the unwanted charge trapping effect inefficient chirality transfer, development of CP‐WOLEDs with a high color rendering index (CRI) large dissymmetry factor ( g EL ) is challenging. Herein, pioneering strategy chiral co‐assembly‐sensitized luminescence (CCS‐CPL) proposed for improving performance white electroluminescence (CP‐EL). Chiral co‐assembled sensitizers (( S ‐/ R ‐Cz) 0.2 ‐( I ‐P) 0.8 smartly developed using π – stacking interactions between binaphthyl derivatives achiral conjugated pyrene‐based polymer in molar ratio 1:4. Using on aggregation‐induced emission (AIE) dyes emitting layers (EMLs) OLEDs, full‐color AIE‐active can be sensitized by co‐assembly . The color‐tunable CP‐EL achieved at CIE coordinates (0.33, 0.33) an ultrahigh CRI 93 value up 0.071. This study thus provides valuable guidance CCS‐type CP‐WOLEDs.

Язык: Английский

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Tracking Noncovalent Interactions of π, π-Hole, and Ion in Molecular Complexes at the Single-Molecule Level

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(36), С. 25290 - 25298

Опубликована: Авг. 28, 2024

Noncovalent interactions involving aromatic rings, such as π-stacking and π-ion interactions, play an essential role in molecular recognition, assembly, catalysis, electronics. However, the inherently weak complex nature of these has made it challenging to study them experimentally, especially with regard elucidating their properties solution. Herein, noncovalent between π π-hole, cation, π-hole anion complexes nonpolar solution are investigated situ through single-molecule electrical measurements combination theoretical calculations. Specifically, phenyl pentafluorobenzyl groups serve sites, respectively, while Li+ Cl– employed cation anion. Our findings reveal that, comparison homogeneous π···π heterogeneous π···π-hole π···cation exhibit greater binding energies, resulting a longer lifetime junctions. Meanwhile, π···Li+ π-hole···Cl– present significantly distinct characteristics, former being stronger but more flexible than latter. Furthermore, by changing components, similar conductivity can be achieved both dimers or sandwich complexes. These results provide new insights into π- π-hole-involved offering novel strategies for precise manipulation device.

Язык: Английский

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Perfluoroaryl⋯aryl interaction: The most important subset of π -hole⋯ π bonding

Chemical Physics Reviews, Год журнала: 2024, Номер 5(3)

Опубликована: Июль 9, 2024

The perfluoroaryl⋯aryl interaction, the most important subset of π-hole⋯π bonding, refers to attractive stacking interaction between a perfluoroaryl group and an aryl group. In contrast aryl⋯aryl with same size, much stronger has its own characteristics applications. A brief history development was given first in this review, followed by overview state-of-the-art nature interaction. Much attention paid application both traditional research fields such as crystal engineering organic luminescent materials hot photovoltaics biological engineering. It is believed that timely comprehensive review provides foundation guide for future

Язык: Английский

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Molecular-Potential and Redox Coregulated Cathodic Electrosynthesis toward Ionic Azulene-Based Thin Films for Organic Memristors

ACS Applied Materials & Interfaces, Год журнала: 2024, Номер 16(17), С. 22217 - 22228

Опубликована: Апрель 19, 2024

Organic memristors as promising electronic units are attracting significant attention owing to their simplicity of molecular structure design. However, fabricating high-quality organic films via novel synthetic technologies and exploring unprecedented chemical structures achieve excellent memory performance in memristor devices highly challenging. In this work, we report a cathodic electropolymerization synthesize an ionic azulene-based memristive film (PPMAz-Py+Br–) under the molecular-potential redox coregulation. During process, electropositive pyridinium salts migrate cathode electric field, undergo reduction-coupling deprotonation reaction, polymerize into uniform with controllable thickness on electrode surface. The prepared Al/PPMAz-Py+Br–/ITO not only exhibit high ON/OFF ratio 1.8 × 103, stability, long retention, endurance wide range voltage scans, but also multilevel storage history-dependent performance. addition, can mimic important biosynaptic functions, such learning/forgetting function, synaptic enhancement/inhibition, paired-pulse facilitation/depression, spiking-rate-dependent plasticity. tunable performances attributed capture free electrons cations, migration aluminum ions (Al3+), form Al conductive filaments scans.

Язык: Английский

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