The Journal of Physical Chemistry Letters最新文献_第7页

Unveiling the Intrinsic Energy Barrier in Single-Photon Upconversion of Perovskite Quantum Dots for Optical Refrigeration 揭示用于光学制冷的钙钛矿量子点单光子上转换的本征能垒

IF 6.475 2区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry Letters

Pub Date : 2026-01-28 DOI: 10.1021/acs.jpclett.5c03718

Hongzhe Du, Jie Gao, Dongxu Zhao, Dandan Cao, Xiao Huang, Hao-Yi Wang, Yi Wang, Xi-Cheng Ai, Jian-Ping Zhang

Perovskite quantum dots (PQDs) feature exceptional single-photon upconversion (SPUC) photoluminescence, rendering them promising candidates for use in optical refrigeration. Despite significant advancements in recent fundamental studies, the specific scenario of uphill carrier activation involved in the SPUC process has not been fully elucidated. Herein, the mechanism of SPUC in PQDs, with particular attention paid to the underlying carrier-transition kinetics, is systematically investigated through time- and energy-resolved spectroscopic techniques. Quantitative analysis results indicate a significant deviation of the upconversion behavior from that predicted by the two-level direct-transition model, a simplified theoretical framework commonly applied to PQDs. Conversely, an additional energy barrier ΔE*, superposed on the SPUC energy gap, plays a pivotal role in determining the carrier activation kinetics. We further verify that ΔE* is associated with the intrinsic properties of the perovskite lattice and is barely influenced by the nanocrystal surface chemistry. The presented findings provide a valuable framework for improving the SPUC performance of PQDs from the perspective of lattice regulation, in addition to the widely used ligand engineering approach, paving the way for the rational design of next-generation optical refrigeration materials.

钙钛矿量子点（PQDs）具有特殊的单光子上转换（SPUC）光致发光特性，使其成为光学制冷中有前途的候选者。尽管最近的基础研究取得了重大进展，但SPUC过程中上坡载流子活化的具体情况尚未完全阐明。本文通过时间分辨和能量分辨光谱技术，系统地研究了pqd中SPUC的机理，特别关注了潜在的载流子转变动力学。定量分析结果表明，上转换行为与两级直接跃迁模型（一种简化的pqd理论框架）预测的上转换行为存在显著偏差。相反，一个附加的能垒ΔE*，叠加在SPUC能隙上，在决定载体活化动力学中起关键作用。我们进一步验证了ΔE*与钙钛矿晶格的内在性质有关，并且几乎不受纳米晶体表面化学的影响。本研究结果为从晶格调控的角度改善pqd的SPUC性能提供了一个有价值的框架，以及广泛使用的配体工程方法，为下一代光学制冷材料的合理设计铺平了道路。

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引用次数: 0

In-situ Crystallization of Ag Clusters in Polymer Matrices for X-ray Imaging 用于x射线成像的银团簇在聚合物基体中的原位结晶

IF 6.475 2区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry Letters

Pub Date : 2026-01-28 DOI: 10.1021/acs.jpclett.5c03653

Wei Tang, Guansheng Xing, Xiaomei Wu, Bing Chen

We report the preparation of flexible scintillation films based on Ag₆N₆S₁₂C₅₄H₄₈ (Ag-R-4PTT) clusters formed by in-situ crystallization within a polymer matrix. The Ag-R-4PTT clusters exhibit thermally activated delayed fluorescence with a high photoluminescence quantum yield of 93.1%. Controlled crystallization yields microcrystalline clusters in poly(vinylpyrrolidone)/thermoplastic polyurethane matrices with excellent radioluminescence performance and high structural stability, leading to a light yield of 33 400 photons MeV^–1 and an X-ray detection limit down to 231 nGy_air s^–1. The scintillation films retain high mechanical flexibility, optical transmittance, and water-resistance, achieving a spatial resolution of 21 lp mm^–1 for X-ray imaging. This study introduces a general strategy to stabilize Ag clusters via coordination engineering as well as in-situ crystallization, offering a promising platform for flexible radiation detection and high-resolution imaging.

我们报道了基于Ag6N6S12C54H48 （Ag-R-4PTT）簇的柔性闪烁薄膜的制备，该簇是在聚合物基体内通过原位结晶形成的。Ag-R-4PTT簇表现出热激活的延迟荧光，光致发光量子产率高达93.1%。在聚乙烯醇吡啶酮/热塑性聚氨酯基体中控制结晶生成微晶簇，具有优异的放射发光性能和高结构稳定性，产光率为33 400光子MeV-1， x射线检测限降至231 nGyair s-1。该闪烁膜保持了较高的机械灵活性、透光率和耐水性，实现了21 lp mm-1的x射线成像空间分辨率。本研究介绍了一种通过配位工程和原位结晶来稳定银团簇的一般策略，为柔性辐射检测和高分辨率成像提供了一个有前途的平台。

引用次数: 0

Improving the Stability and Efficiency of Blue Organic Light-Emitting Diodes via Remote tert-Butyl Modification on a Pt(II) complex. Pt（II）配合物远端叔丁基修饰提高蓝色有机发光二极管的稳定性和效率。

IF 6.475 2区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry Letters

Pub Date : 2026-01-28 DOI: 10.1021/acs.jpclett.5c03924

Yaqi Dai,Jiajun Pan,Yihan Chu,Qingyuan Qian,Xiang Li,Yueqi Wang,Wenhuan Wang,Qinghua Xia,Cong Zhang,Xiao-Chun Hang

High-quality phosphors are pivotal in achieving high-performance deep-blue organic light-emitting diodes (OLEDs) confronting the critical challenge of high efficiency and long lifespan. Here, we report a new Pt(II) emitter, PtON-H, by introducing a tert-butyl (t-Bu) moiety on the carbene site of the ligand based on the imminent emitter PtON-TBBI. The t-Bu group in PtON-H minimally affects the central conformation but increases the molecular volume by 10% and enhances vibration decoupling for the phosphorescent emission compared to PtON-TBBI. Thus, PtON-H has almost the same emission spectrum as PtON-TBBI but demonstrates higher photoluminescence quantum yield and radiative decay rate in both dichloromethane solution and a solid host. The corresponding phosphorescent OLED incorporating PtON-H achieved a 10.4% higher external quantum efficiency (EQE) of 17% and a 2-fold life-span improvement of LT90 = 69 h at 1000 cd/m2 over the PhOLED device based on PtON-TBBI. The corresponding deep-blue phosphor-sensitized OLED using PtON-H realized a high maximum EQE of 18.9%, an LT90 of 37 h, and a CIE coordinate of (0.14, 0.15). These findings provide insights into a dynamically driven strategy for improving the electroluminescent performance of phosphors.

高质量的荧光粉是实现高性能深蓝有机发光二极管（oled）的关键，它面临着高效率和长寿命的严峻挑战。在这里，我们报道了一个新的Pt（II）发射器，PtON-H，通过在配体的碳位点上引入叔丁基（t-Bu）部分，基于临近的发射器PtON-TBBI。与PtON-TBBI相比，PtON-H中的t-Bu基团对中心构象的影响最小，但使分子体积增加了10%，并增强了磷光发射的振动解耦性。因此，PtON-H具有与PtON-TBBI几乎相同的发射光谱，但在二氯甲烷溶液和固体基质中均表现出更高的光致发光量子产率和辐射衰减率。与基于PtON-TBBI的PhOLED器件相比，采用PtON-TBBI的磷光OLED器件的外量子效率（EQE）提高了10.4%，达到17%，寿命提高了2倍，在1000 cd/m2下LT90 = 69 h。使用PtON-H的相应深蓝磷敏化OLED实现了高达18.9%的最大EQE， 37 h的LT90和（0.14,0.15）的CIE坐标。这些发现为提高荧光粉电致发光性能的动态驱动策略提供了见解。

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引用次数: 0

Stress-Regulated Crystallization on Mesoporous Nickel Oxide Enables High-Efficiency and Stable Inverted Perovskite Solar Cells 介孔氧化镍的应力调控结晶可实现高效稳定的倒钙钛矿太阳能电池。

IF 4.6 2区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry Letters

Pub Date : 2026-01-27 DOI: 10.1021/acs.jpclett.5c03815

Jiaqi Wang, , , Zhirui Chen, , , Haojie You, , , Linshan Li, , , Junyu Nie, , , Ziyue Jiao, , , Caixuan Wang, , , Zhihai Cheng, , , Yi Wang, , , Qi Li, , and , Cheng Mu*,

Nickel oxide (NiO_x) is one of the most widely employed hole transport layers (HTLs) in inverted perovskite solar cells (PSCs) due to its low-temperature processability, compatibility with scalable fabrication, and favorable energy-level alignment. Since 2015, extensive efforts have been devoted to enhancing the optoelectronic properties of NiO_x; however, most studies have predominantly focused on planar NiO_x (pNiO_x) films. In this study, we fabricate a mesoporous nickel oxide (mNiO_x) HTL via high-temperature calcination, using nickel nitrate hexahydrate (Ni(NO₃)₂·6H₂O) as the nickel precursor, Pluronic P123 and a small amount of polyvinylpyrrolidone (PVP) as structure-directing templates. The resulting mesoporous framework modulates the perovskite crystallization kinetics, enhances the buried interface, improves the crystallization quality, reduces the defect density, and shifts the interfacial stress state from tensile to compressive. Consequently, both the open-circuit voltage (V_OC) and fill factor (FF) of the devices are significantly enhanced. The PSCs based on the mNiO_x HTL achieve a power conversion efficiency (PCE) of 23.19%, along with markedly improved operation and storage stability.

氧化镍（NiOx）是倒置钙钛矿太阳能电池（PSCs）中应用最广泛的空穴传输层（HTLs）之一，因为它具有低温可加工性、可扩展制造兼容性和良好的能级排列。自2015年以来，在提高NiOx的光电性能方面做了大量的工作；然而，大多数研究主要集中在平面NiOx （pNiOx）薄膜上。本研究以六水硝酸镍（Ni(NO3)2·6H2O）为镍前驱体，Pluronic P123和少量聚乙烯吡咯烷酮（PVP）为结构导向模板，通过高温煅烧法制备了介孔氧化镍（mNiOx） HTL。由此产生的介孔框架调节了钙钛矿结晶动力学，增强了埋藏界面，提高了结晶质量，降低了缺陷密度，并将界面应力状态从拉伸状态转变为压缩状态。因此，器件的开路电压（VOC）和填充因子（FF）都得到了显著提高。基于mNiOx html的PSCs的功率转换效率（PCE）可达23.19%，同时显著提高了运行和存储稳定性。

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引用次数: 0

Exploring the Role of Four-Phonon Scattering in the Lattice Thermal Transport of LaMoN3 探索四声子散射在LaMoN3晶格热输运中的作用

IF 4.6 2区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry Letters

Pub Date : 2026-01-27 DOI: 10.1021/acs.jpclett.5c03911

Manjari Jain*, , , Sanchi Monga, , and , Saswata Bhattacharya*,

In this work, we systematically investigate the lattice thermal conductivity (κ_L) of LaMoN₃ in the C2/c and R3c phases using first-principles calculations combined with the Boltzmann transport equation. In the C2/c phase, κ_L exhibits strong anisotropy, with values of 0.75 W/mK, 1.89 W/mK, and 0.82 W/mK along the a, b, and c axes, respectively, at 300 K. In contrast, the R3c phase shows nearly isotropic thermal conductivity, with values of 6.28 W/mK, 7.05 W/mK, and 7.31 W/mK along the a, b, and c directions. In both phases, acoustic and low-frequency optical phonons dominate the thermal transport. However, the C2/c phase exhibits increased three-phonon scattering leading to smaller values of κ_L. Additionally, four-phonon scattering plays a dominant role in the C2/c phase, reducing κ_L by approximately 96%, whereas in the R3c phase, it leads to a smaller but still significant reduction of ∼50%. These results highlight the critical role of four-phonon interactions in determining the thermal transport properties of LaMoN₃ and reveal the stark contrast in thermal conductivity between its two structural phases.

在这项工作中，我们系统地研究了LaMoN3在C2/c和R3c相的晶格导热系数（κL），采用第一性原理计算结合玻尔兹曼输运方程。在C2/c相，κL表现出较强的各向异性，在300 K时沿a、b和c轴分别为0.75 W/mK、1.89 W/mK和0.82 W/mK。R3c相在a、b、c三个方向的导热系数分别为6.28 W/mK、7.05 W/mK和7.31 W/mK。在这两个阶段，声子和低频光声子主导热输运。而C2/c相的三声子散射增加，导致κL值减小。此外，四声子散射在C2/c相中起主导作用，使κL降低了约96%，而在R3c相中，它导致了较小但仍然显著的约50%的降低。这些结果强调了四声子相互作用在决定LaMoN3的热输运性质中的关键作用，并揭示了其两个结构相之间导热性的鲜明对比。

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引用次数: 0

Spin-Polarized Electron Transport and Catalytic Enhancement in Chiral Supramolecular Polymer Assemblies. 手性超分子聚合物组件中的自旋极化电子输运和催化增强。

IF 6.475 2区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry Letters

Pub Date : 2026-01-27 DOI: 10.1021/acs.jpclett.5c03824

Mive Yasmin,Rabia Garg,Anujit Balo,Amit Kumar Mondal,Koyel Banerjee Ghosh

Chirality is recognized as a vital factor in generating strong spin selectivity in organic π-conjugated systems. In recent years, chiral polymers and supramolecular assemblies have attracted interest as potential spin-filtering materials because of the chirality-induced spin-selectivity (CISS) effect. However, despite their potential applications in spintronics, the CISS effect in metal-free supramolecular architectures remains relatively less explored. In this work, we have investigated metal-free supramolecular materials based on chiral naphthalenediimide (NDI) moieties for potential applications of the CISS effect. Our results highlight the crucial role of electron spin in governing spin-selective charge transport, as well as in boosting oxygen reduction and evolution reactions. Notably, the CISS effect enables chiral analogues to exhibit superior catalytic behavior, reflected in higher current densities and more positive onset potentials, clear evidence of spin-dependent processes. Overall, this work demonstrates the substantial promise of metal-free chiral organic materials for spintronics applications, opening new avenues for device design and advanced functionalities.

手性被认为是有机π共轭体系产生强自旋选择性的重要因素。近年来，由于手性诱导的自旋选择性（CISS）效应，手性聚合物和超分子组装体作为潜在的自旋过滤材料引起了人们的关注。然而，尽管它们在自旋电子学中有潜在的应用，但CISS效应在无金属超分子结构中的探索仍然相对较少。在这项工作中，我们研究了基于手性萘二酰亚胺（NDI）基团的无金属超分子材料，用于CISS效应的潜在应用。我们的研究结果强调了电子自旋在控制自旋选择性电荷输运以及促进氧还原和进化反应中的关键作用。值得注意的是，CISS效应使手性类似物表现出优越的催化行为，反映在更高的电流密度和更多的正起始电位上，这是自旋依赖过程的明确证据。总的来说，这项工作展示了无金属手性有机材料在自旋电子学应用中的巨大前景，为器件设计和先进功能开辟了新的途径。

{"title":"Spin-Polarized Electron Transport and Catalytic Enhancement in Chiral Supramolecular Polymer Assemblies.","authors":"Mive Yasmin,Rabia Garg,Anujit Balo,Amit Kumar Mondal,Koyel Banerjee Ghosh","doi":"10.1021/acs.jpclett.5c03824","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03824","url":null,"abstract":"Chirality is recognized as a vital factor in generating strong spin selectivity in organic π-conjugated systems. In recent years, chiral polymers and supramolecular assemblies have attracted interest as potential spin-filtering materials because of the chirality-induced spin-selectivity (CISS) effect. However, despite their potential applications in spintronics, the CISS effect in metal-free supramolecular architectures remains relatively less explored. In this work, we have investigated metal-free supramolecular materials based on chiral naphthalenediimide (NDI) moieties for potential applications of the CISS effect. Our results highlight the crucial role of electron spin in governing spin-selective charge transport, as well as in boosting oxygen reduction and evolution reactions. Notably, the CISS effect enables chiral analogues to exhibit superior catalytic behavior, reflected in higher current densities and more positive onset potentials, clear evidence of spin-dependent processes. Overall, this work demonstrates the substantial promise of metal-free chiral organic materials for spintronics applications, opening new avenues for device design and advanced functionalities.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"293 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056767","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Topological Advantage for Adsorbate Chemisorption on Conjugated Chains 共轭链上吸附物化学吸附的拓扑优势

IF 6.475 2区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry Letters

Pub Date : 2026-01-27 DOI: 10.1021/acs.jpclett.5c03500

Luis Martinez-Gomez, Raphael F. Ribeiro

Topological matter offers opportunities for control of charge and energy flow with implications for chemistry still incompletely understood. In this work, we study an ensemble of adsorbates with an empty frontier level (LUMO) coupled to the edges, domain walls (solitons), and bulk of a Su–Schrieffer–Heeger polyacetylene chain across its trivial insulator, metallic, and topological insulator phases. We find that two experimentally relevant observables, charge donation into the LUMO and the magnitude of adsorbate electronic friction, are significantly impacted by the electronic phase of the SSH chain and show clear signatures of the topological phase transition. Localized, symmetry-protected midgap states at edges and solitons strongly enhance electron donation relative to both the metallic and trivial phases, whereas, by contrast, the metal’s extended states, despite larger total DOS near the Fermi energy, hybridize more weakly with a molecular adsorbate near a particular site. Electronic friction is largest in the metal, strongly suppressed in gapped regions, and intermediate at topological edges, where hybridization splits the midgap resonance. These trends persist with disorder, highlighting their robustness, and suggest engineering domain walls and topological boundaries as pathways for employing topological matter in molecular catalysis and sensing.

拓扑物质为控制电荷和能量流动提供了机会，其对化学的影响仍未完全理解。在这项工作中，我们研究了一个具有空边界能级（LUMO）耦合到边缘、畴壁（孤子）和Su-Schrieffer-Heeger聚乙炔链主体的吸附物集合，该吸附物横跨其普通绝缘体、金属和拓扑绝缘体相。我们发现两个实验相关的观测值，即LUMO的电荷捐赠和吸附质电子摩擦的大小，受到SSH链电子相的显著影响，并显示出清晰的拓扑相变特征。相对于金属相和普通相，边缘和孤子的局域化、对称保护的中隙态强烈地增强了电子赋能，然而，相比之下，金属的扩展态，尽管在费米能量附近有较大的总DOS，但在特定位置附近与分子吸附质的杂化更弱。电子摩擦在金属中最大，在间隙区域被强烈抑制，在拓扑边缘处处于中间位置，杂化分裂了间隙共振。这些趋势在无序中持续存在，突出了它们的稳健性，并表明工程结构域壁和拓扑边界是在分子催化和传感中使用拓扑物质的途径。

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引用次数: 0

Rotationally Resolved Predissociation Spectrum of the 15Φ ← X5Δ Rovibronic Band of FeH. FeH旋分辨预解谱15Φ←X5Δ振动带。

IF 6.475 2区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry Letters

Pub Date : 2026-01-27 DOI: 10.1021/acs.jpclett.5c03818

Shan Jin,Marc Reimann,Christian van der Linde,Milan Ončák,Martin K Beyer

The elusive diatomic molecule FeH+ has long been hypothesized to exist in cool interstellar environments, yet its spectral signature has remained unidentified due to the lack of laboratory data. Its neutral counterpart FeH, on the other hand, is a well-known feature in the atmospheres of M-dwarfs, Sunspots, and hot Jupiter. Here we present the first rotationally resolved photodissociation spectrum of gas-phase FeH+, covering the energy range of 18550-18830 cm-1 (5390.8-5310.7 Å). The rotational structure of the 15Φ ← X5Δ electronic transition is resolved and conclusively assigned using state-of-the-art multireference and coupled cluster calculations and rovibrational spectra simulations. FeH+ spectral peaks in this specific band are broadened by predissociation, which arises from curve crossings of the bound 15Φ potential curve with those of repulsive 7Π, 7Δ states. The photodissociation cross-section does not exceed 5 × 10-20 cm2, and comparison of the laboratory spectrum with observation data from HD 183143 does not reveal a match for this relatively weak band. Due to the uncertainty of the spin-rotation coupling constant, it is not possible to predict the precise positions of the rotational line spectrum. However, the high spin and orbital angular momentum quantum numbers of the electronic ground state place the onset of the spectrum above 1300 GHz, a frequency region that cannot be observed with ground-based telescopes.

长期以来，人们一直假设难以捉摸的双原子分子FeH+存在于凉爽的星际环境中，但由于缺乏实验室数据，其光谱特征仍未确定。另一方面，它的中性对偶FeH在m矮星、太阳黑子和热木星的大气中是一个众所周知的特征。本文首次获得了气相FeH+的旋转分辨光解光谱，其能量范围为18550-18830 cm-1 （5390.8-5310.7 Å）。利用最先进的多参考和耦合簇计算和旋转振动谱模拟，解决并最终分配了15Φ←X5Δ电子跃迁的旋转结构。这一特定波段的FeH+光谱峰由于预解离而展宽，这是由于束缚态15Φ电位曲线与排斥态7Π、7Δ电位曲线相交。光解截面不超过5 × 10-20 cm2，实验室光谱与HD 183143观测数据的比较没有发现这个相对较弱的波段的匹配。由于自旋-旋转耦合常数的不确定性，无法准确预测旋转谱线的位置。然而，电子基态的高自旋和轨道角动量量子数使光谱的起始点超过1300千兆赫，这是地面望远镜无法观测到的频率区域。

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引用次数: 0

White Light Excited Two-Dimensional Fluorescence Excitation Spectroscopy: Picosecond Time-Resolved Excitation Emission Matrix 白光激发二维荧光激发光谱学：皮秒时间分辨激发发射矩阵

IF 6.475 2区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry Letters

Pub Date : 2026-01-27 DOI: 10.1021/acs.jpclett.5c03373

Tatsuya Yoshida, Kiyoshi Miyata, Ken Onda

Two-dimensional electronic spectroscopy (2DES) has been widely employed to probe the dynamics of electronic excitations. However, conventional 2DES often encounters challenges in spectral assignment due to the intrinsic limitations of transient absorption detection. To overcome these issues, fluorescence-detected 2DES has been anticipated, and broadband excitation sources can enhance its performance. In this study, we have developed a two-dimensional fluorescence excitation (2DFLEX) spectroscopy by combining white-light excitation with Kerr-gate detection. This approach exploits the white light generated from a high-repetition-rate Yb-amplifier laser, providing both broad spectral coverage and excellent stability. Importantly, 2DFLEX exhibits intrinsic selectivity for stimulated emission, enabling the isolation of excited-state dynamics. This technique represents a significant advancement in fluorescence-detected 2DES and opens new opportunities for elucidating complex electronic processes. 2DFLEX is a spectroscopic technique that integrates excitation-spectrum measurements with time-resolved photoluminescence and has the potential to become a novel standard analytical method for photofunctional materials.

二维电子能谱（2DES）已被广泛用于探测电子激发动力学。然而，由于瞬态吸收检测的固有局限性，传统的2DES在光谱分配方面经常遇到挑战。为了克服这些问题，预计荧光检测2DES，宽带激发源可以提高其性能。在这项研究中，我们将白光激发与克尔门检测相结合，建立了二维荧光激发（2DFLEX）光谱。这种方法利用了高重复率镱放大器激光器产生的白光，提供了广泛的光谱覆盖和出色的稳定性。重要的是，2DFLEX对受激发射表现出固有的选择性，从而能够隔离激发态动力学。这项技术代表了荧光检测2DES的重大进步，并为阐明复杂的电子过程开辟了新的机会。2DFLEX是一种将激发光谱测量与时间分辨光致发光相结合的光谱技术，有可能成为光功能材料的一种新的标准分析方法。

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引用次数: 0

Excited-State Sudden Polarization Dynamics of Sulfone-Functionalized Symmetric Stable Diradicaloids. 砜功能化对称稳定二根类化合物的激发态突变极化动力学。

IF 6.475 2区化学 Q2 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry Letters

Pub Date : 2026-01-27 DOI: 10.1021/acs.jpclett.5c03807

Zixi Liu,Junji Zhao,Zhibiao Zhou,Yuhang Yang,Siping Du,Yang Li,Gang-Hua Deng,Hongwei Song,Yan Wan,Zebing Zeng,Andong Xia,Zhuoran Kuang

The sudden polarization (SP) effect converts a resonant zwitterionic state into a polarized charge-separated (CS) state, yet its dynamics in stable diradicaloids remain insufficiently understood. Here we investigate a pair of C2-symmetric sulfone-functionalized Chichibabin's hydrocarbons with nearly degenerate zwitterionic states but differing in symmetric electron-withdrawing groups (EWGs). Femtosecond transient absorption spectroscopy directly captures subpicosecond SP processes in both systems and, together with quantum-chemical calculations, reveals the thermodynamic accessibility of the CS state governed by solvent polarity and excitonic coupling. Increasing solvent polarity facilitates the SP effect, which leads to full charge separation via the relaxation of polarized zwitterionic states. Additionally, weakening excitonic coupling through the substituent effect allows the CS state to be accessible across all polar media. These results establish the SP effect as the trigger for symmetry breaking and establish tunable substituents and dielectric environments as effective handles for directing SP relaxation dynamics in symmetric diradicaloids.

突然极化（SP）效应将共振两性离子状态转变为极化电荷分离（CS）状态，但其在稳定的二根碱中的动力学仍未得到充分的了解。本文研究了一对具有近似简并两性离子状态但在对称吸电子基团（EWGs）上不同的c2对称磺基化奇奇巴宾碳氢化合物。飞秒瞬态吸收光谱直接捕获了两种体系中的亚皮秒SP过程，并与量子化学计算一起揭示了溶剂极性和激子耦合控制下CS态的热力学可及性。溶剂极性的增加有利于SP效应，SP效应通过极化两性离子态的弛豫导致电荷完全分离。此外，通过取代基效应减弱激子耦合，使得CS态可以在所有极性介质中获得。这些结果确立了SP效应是对称破缺的触发因素，并确立了可调取代基和介电环境作为指导对称二根碱中SP弛豫动力学的有效手柄。

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引用次数: 0