Dyes and Pigments最新文献_第6页

Multicolor exciplex-based solution-processed organic light emitting diodes tuned by an identical blue TADF acceptor 由相同的蓝色TADF受体调谐的多色激光基溶液处理有机发光二极管

IF 4.2 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments

Pub Date : 2025-11-19 DOI: 10.1016/j.dyepig.2025.113433

Yixuan Pu , Zhongxin Zhou , Shijing Jin , Weihao Du , Zhonglian Wu , Changheng Guan , Weiguo Zhu , Yu Liu

In recent years, exciplex systems composed of donor-acceptor pairs exhibiting thermally activated delayed fluorescence (TADF) have gained increasing attention in organic light-emitting diodes (OLEDs). Reported herein is a novel blue TADF emitter, BO-QAD, which contains 2,12-di-tert-butyl-5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene (BO) as donor with quinolino[3,2,1-de]acridine-5,9-dione (QAD) as acceptor. BO-QAD emits an intense blue emission at 455 nm and 465 nm in its toluene and film, characterized by a narrow full width at half maximum (FWHM) of 27 nm. A high photoluminescence quantum yield (Φ_PL) of 84.2 % was obtained in mCP:(2.0 wt%) BO-QAD blend film. Quantum calculations and photophysical experiments confirmed its TADF properties. Employed it as an identical exciplex acceptor and matching it with various electron-donating emitters (DMAC-DPS, TCTA, TAPC, or m-MTDATA), yellow-green, yellow, orange-red, and near-infrared (NIR) exciplex-based solution-processed OLEDs have been demonstrated for the first time, and exhibiting emission peaks at 559, 579, 600, and 718 nm with FWHM values of 94, 100, 102, and 188 nm, respectively. A white OLED employing a CBP host matrix and a BO-QAD:m-MTDATA exciplex guest system, achieving a color rendering index (CRI) of 76 at CIE coordinates of (0.33, 0.34), values close to D65 white light standard. Furthermore, three near-white OLEDs were fabricated by the same BO-QAD:m-MTDATA exciplex guest but different host matrices, mCP, mCBP, and 26-DCzPPy. This work highlights the promising potential of using NIR and white OLEDs in display applications.

近年来，由热激活延迟荧光（TADF）的供体-受体对组成的异构体系统在有机发光二极管（oled）中越来越受到关注。本文报道了一种新型的蓝色TADF发射器BO-QAD，它以2,12-二叔丁基-5,9-二氧杂甲-13b-硼萘环[3,2,1-de]蒽（BO）为供体，喹啉[3,2,1-de]吖啶-5,9-二酮（QAD）为受体。BO-QAD在甲苯和薄膜中分别在455 nm和465 nm处发出强烈的蓝色辐射，其特点是半峰全宽（FWHM）为27 nm。mCP:(2.0 wt%) BO-QAD共混膜的光致发光量子产率（ΦPL）高达84.2%。量子计算和光物理实验证实了它的TADF性质。将其作为相同的激复受体，并与各种给电子发射器（DMAC-DPS， TCTA， TAPC或m-MTDATA）匹配，首次证明了黄绿色，黄色，橙红色和近红外（NIR）激复基溶液处理的oled，其发射峰分别为559,579,600和718 nm， FWHM值分别为94,100,102和188 nm。采用CBP主矩阵和BO-QAD:m-MTDATA混合guest系统的白色OLED，在CIE坐标（0.33,0.34）下实现了76的显色指数（CRI），接近D65白光标准值。此外，用相同的BO-QAD制备了3个近白色oled:m-MTDATA外复客体，但不同的主基质，mCP， mCBP和26-DCzPPy。这项工作强调了在显示应用中使用近红外和白光oled的巨大潜力。

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引用次数: 0

A cationic lanthanide-based fluorescent sensor for highly selective and on-site detection of chromium oxyanions 一种用于高选择性和现场检测铬氧离子的阳离子镧系荧光传感器

IF 4.2 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments

Pub Date : 2025-11-19 DOI: 10.1016/j.dyepig.2025.113414

Huangjie Lu , Yanrui Wang , Jingqi Ma , Huiliang Hou , Ming-Yang He , Qun Chen , Zhi-Hui Zhang , Jian Lin , Junfeng Qian

The detection of Cr(VI) oxyanions in aquatic environments has garnered significant attention due to their biotoxicity, environmental risks, and pivotal role in the nuclear fuel cycle, particularly in environmental and industrial applications. However, existing fluorescent probes for CrO₄²⁻ and Cr₂O₇²⁻ are often constrained by low sensitivity, poor selectivity, and complex detection procedures. In this study, we report the development of a hydrolytically stable cationic lanthanide-based cluster, Tb-bppCOO, which exhibits excellent chemical and photoluminescence stability across a broad pH range (4–10). The intrinsic luminescence of Tb³⁺ facilitates the detection of CrO₄²⁻ and Cr₂O₇²⁻ through a luminescence quenching mechanism, exhibiting a good linear Stern–Volmer relationship (I₀/I = 1 + Ksv [Q]) in the concentration range of 0–80 μM. The quenching effect is attributed to the partial overlap of the absorption peak of Tb-bppCOO with the absorption of Cr(VI) at 365 nm, allowing chromium oxyanions to compete for excitation light upon adsorption, thereby achieving selective detection of CrO₄²⁻ and Cr₂O₇²⁻ with detection limits of 148 nM and 58 nM, respectively. Moreover, integration of Tb-bppCOO into PVDF films demonstrates its potential as a promising material for on-site and semi-quantitative analysis of Cr(VI) oxyanions in aqueous solutions.

由于其生物毒性、环境风险以及在核燃料循环，特别是在环境和工业应用中的关键作用，水生环境中Cr（VI）氧离子的检测受到了广泛关注。然而，现有的CrO42 -和Cr2O72 -荧光探针往往受到灵敏度低、选择性差和检测程序复杂的限制。在这项研究中，我们报道了一种水解稳定的阳离子镧系簇，Tb-bppCOO，它在很宽的pH范围内表现出优异的化学和光致发光稳定性（4-10）。在0 ~ 80 μM的浓度范围内，Tb3+的本然发光通过发光猝灭机制促进了对CrO42−和Cr2O72−的检测，表现出良好的线性Stern-Volmer关系（I0/I = 1 + Ksv [Q]）。这种猝灭效应是由于Tb-bppCOO在365 nm处的吸收峰与Cr（VI）的吸收峰部分重叠，使得铬氧离子在吸附时竞争激发光，从而实现了对CrO42−和Cr2O72−的选择性检测，检测限分别为148 nm和58 nm。此外，将Tb-bppCOO整合到PVDF薄膜中，显示了其作为水溶液中Cr（VI）氧阴离子的现场和半定量分析材料的潜力。

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引用次数: 0

σ-Bond unit strategy: Constructing deep-blue triplet-triplet annihilation emitters based on anthracene core for efficient non-doped OLEDs σ-键单元策略：构建高效非掺杂oled中基于蒽核的深蓝色三重-三重湮灭发射体

IF 4.2 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments

Pub Date : 2025-11-19 DOI: 10.1016/j.dyepig.2025.113436

Rong Zhang , Xiliang Chen , Xilin Yang , Xue-Wei Duan , Shi-Jian Su , Jian-Yong Hu

The triplet-triplet annihilation (TTA) mechanism, which converts low-energy triplet excitons into singlet excitons, has been successfully applied to manufacture high-performance organic light-emitting diodes (OLEDs). TTA-type materials usually exhibited weak intramolecular charge transfer (ICT) effect, which are advantageous for designing deep-blue emitters. Herein, we reported two newly developed TTA molecules, An-σ-Ph and An-σ-DA, based on anthracene core by a σ-bond unit strategy to weak the intramolecular conjugation degree. Their molecular structures, and thermochemical/photophysical/electrochemical properties have been systematically studied in both experimental and theoretical aspects. These molecules achieved deep-blue emission with high PLQYs in solution and thin films. As a result, non-doped OLEDs based on An-σ-Ph and An-σ-DA achieved a maximum external quantum efficiency (EQE_max) and a maximum luminance (L_max) of 3.26 %/4398 cd m⁻² and 3.43 %/12870 cd m⁻², respectively, displaying a deep-blue emission with a peak electroluminescence at 447/438 nm. Furthermore, the EQE roll-off of An-σ-DA-based device can be ignored at 1000 cd m⁻² and maintain good device performances at 10000 cd m⁻². This study provides a new avenue for designing novel deep-blue TTA emitters for efficient non-doped OLEDs.

将低能三重态激子转化为单重态激子的三重态-三重态湮灭机制已成功应用于高性能有机发光二极管（oled）的制造中。ta型材料通常表现出较弱的分子内电荷转移（ICT）效应，这有利于设计深蓝色发射体。本文报道了两种基于蒽核的TTA分子An-σ-Ph和An-σ-DA，通过σ键单元策略来减弱分子内的共轭度。它们的分子结构、热化学/光物理/电化学性质在实验和理论方面都得到了系统的研究。这些分子在溶液和薄膜中获得了高PLQYs的深蓝色发射。结果表明，基于An-σ-Ph和An-σ-DA的非掺杂oled的最大外量子效率（EQEmax）和最大亮度（Lmax）分别为3.26% /4398 cd m−2和3.43% /12870 cd m−2，发光深度为深蓝，电致发光峰位于447/438 nm。此外，基于An-σ- da的器件在1000 cd m−2时可以忽略EQE滚降，并在10000 cd m−2时保持良好的器件性能。该研究为设计高效无掺杂oled的新型深蓝TTA发射体提供了新的途径。

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引用次数: 0

Dark blue β-phthalocyanines with high near-infrared reflectance and strong solar Attenuation 深蓝色β-酞菁具有高的近红外反射率和强的太阳衰减

IF 4.2 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments

Pub Date : 2025-11-19 DOI: 10.1016/j.dyepig.2025.113417

Xiangbin Zou , Shuo Yang , Sizhe Tang , Hao Zeng , Xueyu Yuan , Zihao Zhou , Yujie Song , Bing Li , Ming Liu

Radiative cooling offers an energy-efficient solution for passive thermal management, particularly amid escalating global warming. However, conventional cooling materials typically rely on white or light-colored surfaces to maximize solar reflectance, limiting their aesthetic appeal and contributing to light pollution. Phthalocyanines, with their vivid coloration, stability, and low cost, present an attractive alternative. In this study, metal-free phthalocyanine (H₂Pc) and copper phthalocyanine (CuPc) were thermally converted from their α-phase to β-phase as confirmed by XRD, FT–IR, and UV–VIS spectroscopy. The β-phase exhibited markedly improved near-infrared (NIR) reflectance relative to the α-phase. Outdoor testing demonstrated that β-CuPc outperformed Prussian blue, and commonly used blue pigment, in cooling performance. EnergyPlus simulations further indicated that β-CuPc coated roofs reduced cooling energy consumption by 4.9–10.9 % compared to conventional roofs. These findings position β-CuPc as a promising NIR-reflective pigment for colored radiative cooling applications balancing energy efficiency, deep coloration, and reduced light pollution, ideal for buildings, vehicles, and urban infrastructure.

辐射冷却为被动热管理提供了一种节能的解决方案，特别是在全球变暖加剧的情况下。然而，传统的冷却材料通常依靠白色或浅色表面来最大化太阳反射率，限制了它们的美学吸引力并导致光污染。酞菁具有鲜艳的颜色、稳定性和低成本，是一种有吸引力的替代品。通过XRD、FT-IR、UV-VIS等光谱分析，证实了无金属酞菁（H2Pc）和铜酞菁（CuPc）从α相热转化为β相。相对于α相，β相的近红外（NIR）反射率明显提高。室外测试表明，β-CuPc在冷却性能上优于普鲁士蓝和常用的蓝色颜料。EnergyPlus模拟进一步表明，与传统屋顶相比，β-CuPc涂层屋顶减少了4.9 - 10.9%的冷却能耗。这些发现将β-CuPc定位为一种有前途的nir反射色素，用于彩色辐射冷却应用，平衡能源效率，深着色和减少光污染，是建筑物，车辆和城市基础设施的理想选择。

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引用次数: 0

A tetradentate Pt(II) complex bearing a sterically hindered (triphenylsilyl)phenyl group for efficient green phosphorescent organic light-emitting diodes 一种具有位阻（三苯基硅基）苯基的四齿铂（II）配合物，用于高效的绿色磷光有机发光二极管

IF 4.2 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments

Pub Date : 2025-11-19 DOI: 10.1016/j.dyepig.2025.113439

Yi-Jin Ryu , Seung Chan Kim , Jihun Han , Jun Yeob Lee , Hea Jung Park , Do-Hoon Hwang

We designed and synthesized a novel green phosphorescent Pt(II) complex, PtON7-TPS, by incorporating an electron-rich phenyl substituent at the 4-position of the phenyl unit within the central carbon skeleton of a tetradentate ligand. To further suppress intermolecular interaction, a sterically hindered triphenylsilyl group was incorporated at the para-position of this substituent. This bulky group not only increases the intermolecular Pt–Pt distance but also effectively prevents excimer formation in the solid state. Single-crystal X-ray crystallography confirmed that the complex exists as a racemic mixture with helical molecular geometry, and photophysical characterization revealed identical emission maxima (494 nm) in both the solution and film states, with a broad emission profile due to increased vibronic transitions. PtON7-TPS exhibited high thermal stability (T_d = 441 °C), a relative photoluminescence quantum yield of 0.57, and more stabilized HOMO/LUMO energy levels compared to other NHC-containing Pt(II) analogues. As a result, organic light-emitting diode (OLED) devices using PtON7-TPS as a dopant achieved excellent device performance: a maximum external quantum efficiency of 19.6 %, high current and power efficiencies of 48.8 cd/A and 42.8 lm/W, respectively, a luminance of 19,446 cd/m², and Commission Internationale de l'Éclairage coordinates of (0.18, 0.44) at a 5 % doping ratio. These findings highlight the potential of the sterically engineered PtON7-TPS for efficient and stable green-emitting OLEDs.

我们设计并合成了一种新型的绿色磷光Pt（II）配合物PtON7-TPS，该配合物在四齿配体的中心碳骨架中苯基单元的4位上加入了富电子的苯基取代基。为了进一步抑制分子间的相互作用，在取代基的对位上加入了一个位阻三苯基硅基。这个庞大的基团不仅增加了分子间Pt-Pt的距离，而且有效地防止了固体状态下准分子的形成。单晶x射线晶体学证实了该配合物以螺旋分子结构的外消旋混合物的形式存在，光物理表征显示溶液态和薄膜态的发射最大值相同（494 nm），由于增加了振动跃迁，发射谱线较宽。PtON7-TPS具有较高的热稳定性（Td = 441°C），相对光致发光量子产率为0.57，与其他含nhc的Pt（II）类似物相比，具有更稳定的HOMO/LUMO能级。结果表明，使用PtON7-TPS作为掺杂剂的有机发光二极管（OLED）器件获得了优异的器件性能：在掺杂率为5%时，最大外量子效率为19.6%，电流效率和功率效率分别为48.8 cd/ a和42.8 lm/W，亮度为19,446 cd/m2，国际委员会de l'Éclairage坐标为（0.18,0.44）。这些发现突出了立体工程PtON7-TPS在高效稳定的绿色发光oled方面的潜力。

{"title":"A tetradentate Pt(II) complex bearing a sterically hindered (triphenylsilyl)phenyl group for efficient green phosphorescent organic light-emitting diodes","authors":"Yi-Jin Ryu , Seung Chan Kim , Jihun Han , Jun Yeob Lee , Hea Jung Park , Do-Hoon Hwang","doi":"10.1016/j.dyepig.2025.113439","DOIUrl":"10.1016/j.dyepig.2025.113439","url":null,"abstract":"<div><div>We designed and synthesized a novel green phosphorescent Pt(II) complex, PtON7-TPS, by incorporating an electron-rich phenyl substituent at the 4-position of the phenyl unit within the central carbon skeleton of a tetradentate ligand. To further suppress intermolecular interaction, a sterically hindered triphenylsilyl group was incorporated at the para-position of this substituent. This bulky group not only increases the intermolecular Pt–Pt distance but also effectively prevents excimer formation in the solid state. Single-crystal X-ray crystallography confirmed that the complex exists as a racemic mixture with helical molecular geometry, and photophysical characterization revealed identical emission maxima (494 nm) in both the solution and film states, with a broad emission profile due to increased vibronic transitions. PtON7-TPS exhibited high thermal stability (T<sub>d</sub> = 441 °C), a relative photoluminescence quantum yield of 0.57, and more stabilized HOMO/LUMO energy levels compared to other NHC-containing Pt(II) analogues. As a result, organic light-emitting diode (OLED) devices using PtON7-TPS as a dopant achieved excellent device performance: a maximum external quantum efficiency of 19.6 %, high current and power efficiencies of 48.8 cd/A and 42.8 lm/W, respectively, a luminance of 19,446 cd/m<sup>2</sup>, and Commission Internationale de l'Éclairage coordinates of (0.18, 0.44) at a 5 % doping ratio. These findings highlight the potential of the sterically engineered PtON7-TPS for efficient and stable green-emitting OLEDs.</div></div>","PeriodicalId":302,"journal":{"name":"Dyes and Pigments","volume":"246 ","pages":"Article 113439"},"PeriodicalIF":4.2,"publicationDate":"2025-11-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145576375","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A high-throughput screening frame of polymer donor for efficient organic solar cell constructed by machine learning with encoded frequency molecular fingerprint 基于编码频率分子指纹的机器学习构建了高效有机太阳能电池聚合物供体高通量筛选框架

IF 4.2 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments

Pub Date : 2025-11-17 DOI: 10.1016/j.dyepig.2025.113428

Zhiyan Peng , Kuo Wang , Ziye Chen , Yu Ding , Yuxuan Wang , Dan Li , Jiahao Deng , Kang Zhang , Zhiming Feng , Jiaojiao Liang , Min Lei , Di Huang

The improvement in the performance of organic solar cells (OSCs) is constrained by the challenges of traditional trial-and-error methods in a vast and high-cost chemical space for the novel donor molecule design. In this work, a high-throughput screening frame with machine learning (ML) based on the frequency molecular fingerprint (FreMFp) is proposed to address the limitation of insufficient expression of polymer donor structures via traditional molecular fingerprints. The constructed CatBoost model with FreMFp of substructure function classification and frequency quantization exhibits excellent prediction performance on power conversion efficiency (PCE), which is significantly superior to the traditional molecular fingerprints as the descriptor. Interpretability analysis revealed the positive effects of key sub-units, liking 4-fluoro-2-methylthiophene (Sub-unit 45), dithieno[3′,2':3,4; 2″,3'':5,6]benzo[1,2-c][1,2,5]thiadiazole (Sub-unit 178), 2-ethylhexyl (Sub-unit 196) in fused-ring skeleton, monocyclic-ring linker, and side-chain modification group on PCE. Further approximately six million virtual structures are generated by the screened key sub-units, and finally the D-π-A-π type and D-A type candidate donors that matched both acceptors of Y6 and L8-BO are screened out. More importantly, the typical representatives of D-π-A-π type (D18-D2Cl) and D-A type (PTQ10-EH) with L8-BO can obtain the predicted PCE of binary OSCs of 19.59 % and 17.79 %, respectively. And density functional theory (DFT) further demonstrates the regulation of energy level arrangement and charge transfer characteristics by the electron-induced effect and steric hindrance caused by halogen substitution in the efficient candidate molecule of D18-D2Cl. The built ML frame in this work provides an efficient and low-cost solution to design the donor materials for accelerating the development process of high-performance OSCs.

有机太阳能电池（OSCs）性能的提高受到传统试错方法的挑战，这种方法在巨大且高成本的化学空间中用于新型供体分子设计。本文提出了一种基于频率分子指纹（FreMFp）的机器学习高通量筛选框架，以解决传统分子指纹对聚合物供体结构表达不足的局限性。利用子结构函数分类和频率量化的FreMFp构建的CatBoost模型对功率转换效率（PCE）的预测性能优异，明显优于传统的分子指纹作为描述符。可解释性分析显示了关键亚基的积极作用，如4-氟-2-甲基噻吩（亚基45），二噻吩[3 ',2':3,4；2″，3'':5,6]苯并[1,2-c][1,2,5]噻二唑（亚基178），2-乙基己基（亚基196）在融合环骨架，单环连接器和PCE侧链修饰基团上。进一步筛选的关键亚基产生了大约600万个虚拟结构，最终筛选出匹配Y6和L8-BO受体的D-π- a -π型和D- a型候选供体。更重要的是，具有L8-BO的D-π- a -π型（D18-D2Cl）和D- a型（PTQ10-EH）的典型代表二元osc的预测PCE分别为19.59%和17.79%。密度泛函理论（DFT）进一步证明了D18-D2Cl高效候选分子中卤素取代引起的电子诱导效应和空间位阻对能级排列和电荷转移特性的调控。本文构建的ML框架为加速高性能osc的开发提供了一种高效、低成本的供体材料设计解决方案。

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引用次数: 0

Thiosemicarbazones as ion chelators: Unveiling their coordination and multifaceted applications 硫代氨基脲作为离子螯合剂：揭示它们的配位和多方面的应用

IF 4.2 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments

Pub Date : 2025-11-17 DOI: 10.1016/j.dyepig.2025.113419

Arup Tarai , Bhaskar Nath , Swarup Kumar Tarai , Sankar Ch Moi

Thiosemicarbazones (TSCs) are distinctive class of Schiff base ligands widely recognized for their potential in ions recognition. Their ability to coordinate selectively with cations by forming stable metal complexes, along with anion through hydrogen bonding and electrostatic interactions involving the thiourea (–N–CS) moiety, makes them highly effective in molecular recognition. Certain TSC derivatives further demonstrate dual recognition of both cations and anions, offering improved selectivity and sensitivity for sensing applications. Beyond their sensing capability, the versatile coordination chemistry of TSCs enables the formation of stable complexes with transition and main-group metal ions, contributing to structural diversity and tunable electronic properties. These features not only expand their role in supramolecular chemistry and functional material design but also open avenues for biomedical applications. In particular, TSC-based complexes have emerged as promising candidates for bioimaging, where their coordination-driven properties enhance both activity and specificity. While previous reviews have focused on individual aspects, a comprehensive account integrating ions sensing, coordination chemistry, and bioimaging is lacking. This review aims to provide such a perspective, highlighting the multifaceted role of TSCs as ion chelators and functional potential for advanced applications.

硫代氨基脲（tsc）是一类独特的席夫碱配体，因其在离子识别方面的潜力而被广泛认可。它们通过形成稳定的金属配合物选择性地与阳离子配合，通过氢键和涉及硫脲（-N-CS）部分的静电相互作用与阴离子配合，使它们在分子识别中非常有效。某些TSC衍生物进一步证明了阳离子和阴离子的双重识别，为传感应用提供了更好的选择性和灵敏度。除了它们的传感能力外，tsc的多功能配位化学使其能够与过渡和主基团金属离子形成稳定的配合物，有助于结构多样性和可调谐的电子性质。这些特点不仅扩大了它们在超分子化学和功能材料设计中的作用，而且为生物医学应用开辟了道路。特别是，基于tsc的复合物已经成为生物成像的有希望的候选者，其中它们的配位驱动特性增强了活性和特异性。虽然以前的评论集中在单个方面，但缺乏综合离子传感，配位化学和生物成像的综合说明。这篇综述旨在提供这样的观点，强调tsc作为离子螯合剂的多方面作用和先进应用的功能潜力。

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引用次数: 0

Reversible mechanochromism and sunlight-induced photoisomerization in a multi-stimuli responsive phenothiazine-oxadiazoborole system 多刺激反应性吩噻嗪-恶二唑啉体系的可逆机械变色和阳光诱导的光异构化

IF 4.2 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments

Pub Date : 2025-11-17 DOI: 10.1016/j.dyepig.2025.113418

Sachin Philip , Athira Kokkadan Subhash , Dhanya Plavidayil Jacob , Aldrin Antony , Luc Van Meervelt , Wim Dehaen , Santhini Pulikkal Veetil , Shandev Pookkandam Parambil

Combining mechanochromic and photoisomerization properties within a single, synthetically accessible molecular framework represents a compelling strategy for advancing the design of multifunctional stimuli-responsive materials. Herein, we present a D-A molecule (PTZ-BOAHY), integrating a phenothiazine (PTZ) donor and an oxadiazoborole (BOAHY) acceptor unit. The E/Z isomeric forms of PTZ-BOAHY were separated using column chromatography and were characterized using NMR, HRMS, single crystal XRD and various spectroscopic techniques. The E and Z isomers were fluorescent in both solid and solution states and exhibit a large Stokes shift, pronounced solvatochromism and aggregation-induced quenching. The Z isomer shows reversible chromic responses to grinding with a distinct red-shift of 52 nm in emission wavelength. Photoisomerization of the Z to the E isomer occurs in solution upon sunlight exposure with a visible colour change from red to green. Cyclic voltammetry measurements and density functional theory (DFT) calculations were employed to probe the electronic properties of the molecules. Additionally, thermal measurements showed that the isomers exhibit good thermal stability up to 250 °C.

将机械变色和光异构特性结合在一个单一的、可合成的分子框架内，代表了推进多功能刺激响应材料设计的一个引人注目的策略。在这里，我们提出了一个D-A分子（PTZ-BOAHY），整合了一个吩噻嗪（PTZ）供体和一个恶二唑啉（BOAHY）受体单元。采用柱层析法分离了PTZ-BOAHY的E/Z异构体，并用NMR、HRMS、单晶XRD和各种光谱技术对其进行了表征。E和Z异构体在固体和溶液状态下都具有荧光，表现出较大的斯托克斯位移，明显的溶剂变色和聚集诱导猝灭。Z异构体在磨削过程中表现出可逆的色响应，发射波长红移明显，达到52 nm。Z到E异构体的光异构发生在阳光照射下的溶液中，颜色由红色变为绿色。采用循环伏安法测量和密度泛函理论（DFT）计算来探测分子的电子性质。此外，热测量表明，该异构体在高达250°C的温度下具有良好的热稳定性。

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引用次数: 0

Staphylococcus aureus and Escherichia coli inactivation through mercaptophenylboronic acid-functionalized fluorinated porphyrin 巯基苯硼酸功能化氟化卟啉灭活金黄色葡萄球菌和大肠杆菌

IF 4.2 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments

Pub Date : 2025-11-17 DOI: 10.1016/j.dyepig.2025.113429

Daiane N. Maronde , Cátia Vieira , José E. Rodríguez-Borges , Adelaide Almeida , Leandro M.O. Lourenço

Photodynamic inactivation (PDI) represents an effective strategy to combat resistant pathogens, emerging as a potential approach against Gram-positive and Gram-negative bacteria. Here, we report for the first time the synthesis, characterization, and photophysical properties of novel free-base fluorinated porphyrin tetra-substituted with 4-mercaptophenylboronic acid units (H₂Por 1). The PDI of H₂Por 1 was assessed against methicillin resistant Staphylococcus aureus (MRSA) and Escherichia coli using two photosensitizer (PS) concentrations (5.0 and 10.0 μM) under white light irradiation at 100 mW cm⁻², with exposure times of up to 60 min (total light dose of 360 J cm⁻²). For MRSA, H₂Por 1 alone at 5–10 μM promoted bacterial inactivation in 45–60 min (270–360 J cm⁻²) of irradiation, highlighting the PS concentration and irradiation time dependence. When combined with KI, H₂Por 1 exhibited pronounced synergistic effects, leading to a viability reduction >8 Log CFU/mL in MRSA in ≤5 min (30 J cm⁻²). For E. coli, H₂Por 1 alone, even at 10 μM, did not inactivate the bacterium under the tested conditions. The addition of KI enabled effective inactivation of E. coli within ≤5 min of irradiation, demonstrating a strong combined effect between the PS and KI > 8 Log CFU/mL. These findings reinforce the potential of H₂Por 1 as a versatile antimicrobial agent, particularly when combined with KI, for the photodynamic treatment of infections caused by Gram-positive and Gram-negative bacteria. The H₂Por 1 effective performance even with low PS concentrations and low irradiation levels represents a significant advantage for future clinical applications in antimicrobial photodynamic therapy.

光动力失活（PDI）是对抗耐药病原体的有效策略，是对抗革兰氏阳性和革兰氏阴性细菌的潜在方法。本文首次报道了4-巯基苯基硼酸取代的新型游离基四氟化卟啉（H2Por 1）的合成、表征和光物理性质。采用两种光敏剂（PS）浓度（5.0和10.0 μM），在100mw cm−2的白光照射下（总光剂量为360 J cm−2），检测H2Por 1对耐甲氧西林金黄色葡萄球菌（MRSA）和大肠杆菌的PDI。对于MRSA， 5-10 μM的H2Por 1在45-60 min （270-360 jcm−2）的照射下促进细菌灭活，突出了PS浓度和照射时间的依赖性。当与KI联合时，H2Por 1表现出明显的协同效应，导致MRSA在≤5分钟（30 J cm−2）内活力降低>；8 Log CFU/mL。对于大肠杆菌，即使在10 μM的浓度下，单独使用H2Por 1也不能灭活细菌。KI的加入使大肠杆菌在辐照≤5分钟内有效失活，表明PS和KI具有8 Log CFU/mL的强联合效应。这些发现加强了H2Por 1作为一种多功能抗菌剂的潜力，特别是当与KI联合使用时，用于革兰氏阳性和革兰氏阴性细菌引起的感染的光动力治疗。即使在低PS浓度和低照射水平下，H2Por 1的有效性能也为未来抗菌光动力治疗的临床应用提供了显著优势。

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引用次数: 0

Deep blue donor-bridge-acceptor type thermally activated delayed fluorescence emitters with the sulfur bridge 具有硫桥的深蓝色给体-桥体-受体型热激活延迟荧光发射器

IF 4.2 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments

Pub Date : 2025-11-15 DOI: 10.1016/j.dyepig.2025.113408

Yuanyuan Zheng , Changsheng Shi , Bo Ma , Ning Sun , Qiang Wang

The development of deep blue thermally activated delayed fluorescence (TADF) emitters still remains a big challenge. In this work, four donor-bridge-acceptor type sulfur-containing TADF emitters are developed with carbazole (Cz) derivatives as the donor unit and triphenyltriazine (Trz) as the acceptor moiety. The sulfur atom was used as the bridge to construct Trz-S-Cz and Trz-S-tBuCz, and the sulfone group was employed to construct Trz–SO₂–Cz and Trz–SO₂–tBuCz. The sp³ sulfur bridge interrupts the conjugation between Cz and Trz groups, leading to totally separated orbital distribution. The electron-deficient sulfone group deepens the LUMO level and produces the redshifted emitting wavelength compared to the sulfur atom containing emitters. The four emitters show blue emission, excellent thermal stability and small ΔE_ST values. The optimized OLEDs based on TrZ-S-Cz and Trz-S-tBuCz realize the highest external quantum efficiencies (EQEs) of 22.0 % and 18.2 %, respectively. The sulfone group containing emitters TrZ–SO₂–Cz and TrZ–SO₂–tBuCz achieve the maximum EQEs of 20.1 % and 19.6 %, respectively. The efficiency roll-offs are relatively small for all these devices. The device based on TrZ-S-Cz exhibits deep blue electroluminescence spectrum with peak at 456 nm and a CIE coordinate of (0.15, 0.14). These results demonstrate that incorporating the sulfur atom is an effective way to construct efficient TADF emitters.

深蓝热激活延迟荧光（TADF）发射器的开发仍然是一个很大的挑战。本研究以咔唑（Cz）衍生物为供体单元，三苯基三嗪（Trz）为受体片段，制备了四种供体-桥接-受体型含硫TADF发射器。以硫原子为桥接物构建了Trz-S-Cz和Trz-S-tBuCz，以砜基构建了Trz-SO2-Cz和Trz-SO2-tBuCz。sp3硫桥中断了Cz和Trz基团之间的共轭，导致完全分离的轨道分布。与含硫原子的发射体相比，缺电子的砜基加深了LUMO能级并产生了红移的发射波长。四种发射体均表现出蓝色发射、优异的热稳定性和较小的ΔEST值。基于TrZ-S-Cz和Trz-S-tBuCz的优化oled的外量子效率（EQEs）最高，分别为22.0%和18.2%。含有发射体TrZ-SO2-Cz和TrZ-SO2-tBuCz的砜基团的EQEs最大值分别为20.1%和19.6%。所有这些设备的效率下降相对较小。基于TrZ-S-Cz的器件呈现出深蓝色的电致发光光谱，峰值在456nm处，CIE坐标为（0.15,0.14）。这些结果表明，加入硫原子是构建高效TADF发射体的有效途径。

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引用次数: 0