机械力诱导的四苯乙烯-萘查尔酮异构体的发光增强和显色性。

IF 4.6 2区化学 Q1 SPECTROSCOPY

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy Pub Date : 2025-09-21 DOI:10.1016/j.saa.2025.126978

Hanrong Liu , Huizhuan Zhu , Hui Wang , Baobei Liu , Jiakun Bai , Huijuan Zhang , Junhui Jia

{"title":"机械力诱导的四苯乙烯-萘查尔酮异构体的发光增强和显色性。","authors":"Hanrong Liu , Huizhuan Zhu , Hui Wang , Baobei Liu , Jiakun Bai , Huijuan Zhang , Junhui Jia","doi":"10.1016/j.saa.2025.126978","DOIUrl":null,"url":null,"abstract":"<div><div>Two new donor-acceptor (D-A) tetraphenylethylene-naphthalene chalcone isomers, (<em>E</em>)-1-(naphthalen-2-yl)-3-(4-(1,2,2-triphenylvinyl)phenyl) prop-2-en-1-one (<strong>1N3T</strong>) and (<em>E</em>)-3-(naphthalen-2-yl)-1-(4-(1,2,2-triphenylvinyl)phenyl)prop-2-en-1-one (<strong>3N1T</strong>), were designed and synthesized to investigate their structure-dependent photophysical properties, aggregation-induced emission enhancement (AIEE), and mechanoresponsive behaviors. These two isomers feature tetraphenylethylene (TPE), a well-known aggregation-induced emission luminogen (AIEgen), coupled with a naphthalene chalcone moiety, where the positional isomerism arises from the distinct spatial arrangement of donor (naphthalene) and acceptor (chalcone) groups. Systematic characterization revealed intramolecular charge transfer (ICT) characteristics in solution, as evidenced by solvent-dependent fluorescence emission spectra. Density functional theory (DFT) calculations corroborated the ICT mechanism, demonstrating HOMO-LUMO localization patterns that align with the D-A configurations. Notably, both isomers exhibited exceptional mechanochromic sensitivity. Grinding-induced amorphization led to a remarkable enhancement in solid-state fluorescence quantum yields (QYs), increasing by 27-fold (<strong>1N3T</strong>) and 79-fold (<strong>3N1T</strong>). Powder X-ray diffraction (PXRD) and field emission scanning electron microscopy (FESEM) confirmed a reversible crystalline-to-amorphous phase transition, with the disordered amorphous state suppressing non-radiative decay pathways (e.g., π-π interactions) and unlocking enhanced emission. The superior mechanoresponsiveness of <strong>3N1T</strong> was attributed to its optimized D-A geometry, which facilitates efficient structural disruption under mechanical stress. This work elucidates critical structure-property relationships governing AIEE and mechanochromism, emphasizing the role of positional isomerism in modulating solid-state packing and stimuli-responsive luminescence. The findings advance the rational design of adaptive optoelectronic materials for applications in pressure-sensitive sensors, smart coatings, and rewritable optical storage systems.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":"347 ","pages":"Article 126978"},"PeriodicalIF":4.6000,"publicationDate":"2025-09-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Mechanical force-induced luminescence enhancement and Chromism of donor-acceptor Tetraphenylethylene-naphthalene Chalcone isomers\",\"authors\":\"Hanrong Liu , Huizhuan Zhu , Hui Wang , Baobei Liu , Jiakun Bai , Huijuan Zhang , Junhui Jia\",\"doi\":\"10.1016/j.saa.2025.126978\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Two new donor-acceptor (D-A) tetraphenylethylene-naphthalene chalcone isomers, (<em>E</em>)-1-(naphthalen-2-yl)-3-(4-(1,2,2-triphenylvinyl)phenyl) prop-2-en-1-one (<strong>1N3T</strong>) and (<em>E</em>)-3-(naphthalen-2-yl)-1-(4-(1,2,2-triphenylvinyl)phenyl)prop-2-en-1-one (<strong>3N1T</strong>), were designed and synthesized to investigate their structure-dependent photophysical properties, aggregation-induced emission enhancement (AIEE), and mechanoresponsive behaviors. These two isomers feature tetraphenylethylene (TPE), a well-known aggregation-induced emission luminogen (AIEgen), coupled with a naphthalene chalcone moiety, where the positional isomerism arises from the distinct spatial arrangement of donor (naphthalene) and acceptor (chalcone) groups. Systematic characterization revealed intramolecular charge transfer (ICT) characteristics in solution, as evidenced by solvent-dependent fluorescence emission spectra. Density functional theory (DFT) calculations corroborated the ICT mechanism, demonstrating HOMO-LUMO localization patterns that align with the D-A configurations. Notably, both isomers exhibited exceptional mechanochromic sensitivity. Grinding-induced amorphization led to a remarkable enhancement in solid-state fluorescence quantum yields (QYs), increasing by 27-fold (<strong>1N3T</strong>) and 79-fold (<strong>3N1T</strong>). Powder X-ray diffraction (PXRD) and field emission scanning electron microscopy (FESEM) confirmed a reversible crystalline-to-amorphous phase transition, with the disordered amorphous state suppressing non-radiative decay pathways (e.g., π-π interactions) and unlocking enhanced emission. The superior mechanoresponsiveness of <strong>3N1T</strong> was attributed to its optimized D-A geometry, which facilitates efficient structural disruption under mechanical stress. This work elucidates critical structure-property relationships governing AIEE and mechanochromism, emphasizing the role of positional isomerism in modulating solid-state packing and stimuli-responsive luminescence. The findings advance the rational design of adaptive optoelectronic materials for applications in pressure-sensitive sensors, smart coatings, and rewritable optical storage systems.</div></div>\",\"PeriodicalId\":433,\"journal\":{\"name\":\"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy\",\"volume\":\"347 \",\"pages\":\"Article 126978\"},\"PeriodicalIF\":4.6000,\"publicationDate\":\"2025-09-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1386142525012855\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"SPECTROSCOPY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1386142525012855","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"SPECTROSCOPY","Score":null,"Total":0}

引用次数: 0

摘要

设计并合成了两种新的供体-受体（D-A）四苯基乙烯-萘查酮异构体(E)-1-（萘-2-基）-3-（4-（1,2,2-三苯基乙烯）苯基）-1-（4-（1,2,2-三苯基乙烯）苯基）- 2-烯-1- 1 (3N1T)，研究了它们的结构依赖性光物理性质、聚集诱导发射增强（AIEE）和机械反应行为。这两种异构体的特征是四苯基乙烯（TPE），一种众所周知的聚集诱导发光原（AIEgen），与萘查尔酮部分偶联，其中位置异构体是由给体（萘）和受体（查尔酮）基团的不同空间排列引起的。系统表征揭示了溶液中的分子内电荷转移（ICT）特征，并通过溶剂依赖的荧光发射光谱证明了这一点。密度泛函理论（DFT）计算证实了ICT机制，证明了HOMO-LUMO定位模式与D-A构型一致。值得注意的是，这两种异构体都表现出特殊的机械变色敏感性。研磨诱导的非晶化导致固态荧光量子产率（QYs）显著增强，分别增加了27倍（1N3T）和79倍（3N1T）。粉末x射线衍射（PXRD）和场发射扫描电镜（FESEM）证实了可逆的晶向非晶相变，无序的非晶态抑制了非辐射衰变途径（如π-π相互作用）并解锁了增强的发射。3N1T优异的机械响应性归功于其优化的D-A几何结构，这有助于在机械应力下有效地破坏结构。这项工作阐明了控制AIEE和机械致色性的关键结构-性质关系，强调了位置异构在调节固态包装和刺激响应发光中的作用。这些发现推动了自适应光电材料的合理设计，可用于压敏传感器、智能涂层和可重写光存储系统。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Mechanical force-induced luminescence enhancement and Chromism of donor-acceptor Tetraphenylethylene-naphthalene Chalcone isomers

查看原文本刊更多论文

Mechanical force-induced luminescence enhancement and Chromism of donor-acceptor Tetraphenylethylene-naphthalene Chalcone isomers

Two new donor-acceptor (D-A) tetraphenylethylene-naphthalene chalcone isomers, (E)-1-(naphthalen-2-yl)-3-(4-(1,2,2-triphenylvinyl)phenyl) prop-2-en-1-one (1N3T) and (E)-3-(naphthalen-2-yl)-1-(4-(1,2,2-triphenylvinyl)phenyl)prop-2-en-1-one (3N1T), were designed and synthesized to investigate their structure-dependent photophysical properties, aggregation-induced emission enhancement (AIEE), and mechanoresponsive behaviors. These two isomers feature tetraphenylethylene (TPE), a well-known aggregation-induced emission luminogen (AIEgen), coupled with a naphthalene chalcone moiety, where the positional isomerism arises from the distinct spatial arrangement of donor (naphthalene) and acceptor (chalcone) groups. Systematic characterization revealed intramolecular charge transfer (ICT) characteristics in solution, as evidenced by solvent-dependent fluorescence emission spectra. Density functional theory (DFT) calculations corroborated the ICT mechanism, demonstrating HOMO-LUMO localization patterns that align with the D-A configurations. Notably, both isomers exhibited exceptional mechanochromic sensitivity. Grinding-induced amorphization led to a remarkable enhancement in solid-state fluorescence quantum yields (QYs), increasing by 27-fold (1N3T) and 79-fold (3N1T). Powder X-ray diffraction (PXRD) and field emission scanning electron microscopy (FESEM) confirmed a reversible crystalline-to-amorphous phase transition, with the disordered amorphous state suppressing non-radiative decay pathways (e.g., π-π interactions) and unlocking enhanced emission. The superior mechanoresponsiveness of 3N1T was attributed to its optimized D-A geometry, which facilitates efficient structural disruption under mechanical stress. This work elucidates critical structure-property relationships governing AIEE and mechanochromism, emphasizing the role of positional isomerism in modulating solid-state packing and stimuli-responsive luminescence. The findings advance the rational design of adaptive optoelectronic materials for applications in pressure-sensitive sensors, smart coatings, and rewritable optical storage systems.

求助全文

通过发布文献求助，成功后即可免费获取论文全文。去求助

来源期刊

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 物理-光谱学

CiteScore

8.40

自引率

11.40%

发文量

1364

审稿时长

40 days

期刊介绍： Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy (SAA) is an interdisciplinary journal which spans from basic to applied aspects of optical spectroscopy in chemistry, medicine, biology, and materials science. The journal publishes original scientific papers that feature high-quality spectroscopic data and analysis. From the broad range of optical spectroscopies, the emphasis is on electronic, vibrational or rotational spectra of molecules, rather than on spectroscopy based on magnetic moments. Criteria for publication in SAA are novelty, uniqueness, and outstanding quality. Routine applications of spectroscopic techniques and computational methods are not appropriate. Topics of particular interest of Spectrochimica Acta Part A include, but are not limited to: Spectroscopy and dynamics of bioanalytical, biomedical, environmental, and atmospheric sciences, Novel experimental techniques or instrumentation for molecular spectroscopy, Novel theoretical and computational methods, Novel applications in photochemistry and photobiology, Novel interpretational approaches as well as advances in data analysis based on electronic or vibrational spectroscopy.