激发波长对涤纶单分子光化学的意外影响。

IF 2.3 3区 化学 Q3 CHEMISTRY, PHYSICAL Chemphyschem Pub Date : 2025-01-08 DOI:10.1002/cphc.202400996
Rana Mhanna, Julia Berger, Matthias Jourdain, Stephan Muth, Roger Jan Kutta, Gregor Jung
{"title":"激发波长对涤纶单分子光化学的意外影响。","authors":"Rana Mhanna, Julia Berger, Matthias Jourdain, Stephan Muth, Roger Jan Kutta, Gregor Jung","doi":"10.1002/cphc.202400996","DOIUrl":null,"url":null,"abstract":"<p><p>The reaction of terrylene in p-terphenyl with molecular oxygen is reinvestigated by TIRF-microscopy with λ<sub>exc</sub>=488 nm or λ<sub>exc</sub>=561 nm and 488 nm. A similar range of fluorescent products is obtained under both experimental conditions with a reaction quantum yield Φ<sub>r</sub>>10<sup>-7</sup> for those molecules which undergo the photoreaction. The majority of these oxygen-susceptible molecules reacts via an electronically relaxed, dark intermediate, presumably an endoperoxide, with a lifetime of <t<sub>off</sub>>~20 s. From this time constant, an activation energy E<sub>A</sub><0.8 eV is estimated for the transition from the intermediate to the final product, the diepoxide, which nicely agrees with values calculated for the terrylene-derivative TDI. However, ~20 % of all reacting molecules at λ<sub>exc</sub>=561 nm and even ~40 % at λ<sub>exc</sub>=488 nm show an immediate change of the fluorescence colour within the time resolution of the experiment, bypassing any dark intermediate. Based on this experimentally observed impact of the excitation energy and the lack of relevant excited-state absorption, we hypothesize that oxygen forms a complex with ground-state terrylene which then undergoes a quasi-unimolecular reaction in the excited-state before vibrational relaxation takes place.</p>","PeriodicalId":9819,"journal":{"name":"Chemphyschem","volume":" ","pages":"e202400996"},"PeriodicalIF":2.3000,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Effect of Excitation Wavelength in Single-Molecule Photochemistry of Terrylene.\",\"authors\":\"Rana Mhanna, Julia Berger, Matthias Jourdain, Stephan Muth, Roger Jan Kutta, Gregor Jung\",\"doi\":\"10.1002/cphc.202400996\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>The reaction of terrylene in p-terphenyl with molecular oxygen is reinvestigated by TIRF-microscopy with λ<sub>exc</sub>=488 nm or λ<sub>exc</sub>=561 nm and 488 nm. A similar range of fluorescent products is obtained under both experimental conditions with a reaction quantum yield Φ<sub>r</sub>>10<sup>-7</sup> for those molecules which undergo the photoreaction. The majority of these oxygen-susceptible molecules reacts via an electronically relaxed, dark intermediate, presumably an endoperoxide, with a lifetime of <t<sub>off</sub>>~20 s. From this time constant, an activation energy E<sub>A</sub><0.8 eV is estimated for the transition from the intermediate to the final product, the diepoxide, which nicely agrees with values calculated for the terrylene-derivative TDI. However, ~20 % of all reacting molecules at λ<sub>exc</sub>=561 nm and even ~40 % at λ<sub>exc</sub>=488 nm show an immediate change of the fluorescence colour within the time resolution of the experiment, bypassing any dark intermediate. Based on this experimentally observed impact of the excitation energy and the lack of relevant excited-state absorption, we hypothesize that oxygen forms a complex with ground-state terrylene which then undergoes a quasi-unimolecular reaction in the excited-state before vibrational relaxation takes place.</p>\",\"PeriodicalId\":9819,\"journal\":{\"name\":\"Chemphyschem\",\"volume\":\" \",\"pages\":\"e202400996\"},\"PeriodicalIF\":2.3000,\"publicationDate\":\"2025-01-08\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemphyschem\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1002/cphc.202400996\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemphyschem","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/cphc.202400996","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0

摘要

在λexc = 488 nm、λexc = 561 nm和488 nm的条件下,用红外光谱显微镜重新研究了涤纶与对ter苯基的反应。在两种实验条件下获得了相似范围的荧光产物,反应量子产率为Φr > 10-7。这些氧易感分子中的大多数通过电子松弛的暗中间体(可能是内过氧化物)反应,其寿命约为20秒。从这个时间常数,估计中间产物到最终产物二氧化物的转变活化能EA < 0.8 eV,这与乙烯衍生物TDI的计算值很好地吻合。然而,在λexc = 561 nm处~ 20%的反应分子,甚至在λexc = 488 nm处~ 40%的反应分子,在实验的时间分辨率内,荧光颜色立即发生变化,绕过了任何深色中间体。基于实验观察到的激发能的影响和相关激发态吸收的缺乏,我们假设氧与基态涤纶形成配合物,然后在激发态发生准单分子反应,然后发生振动弛豫。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
查看原文
分享 分享
微信好友 朋友圈 QQ好友 复制链接
本刊更多论文
Effect of Excitation Wavelength in Single-Molecule Photochemistry of Terrylene.

The reaction of terrylene in p-terphenyl with molecular oxygen is reinvestigated by TIRF-microscopy with λexc=488 nm or λexc=561 nm and 488 nm. A similar range of fluorescent products is obtained under both experimental conditions with a reaction quantum yield Φr>10-7 for those molecules which undergo the photoreaction. The majority of these oxygen-susceptible molecules reacts via an electronically relaxed, dark intermediate, presumably an endoperoxide, with a lifetime of off>~20 s. From this time constant, an activation energy EA<0.8 eV is estimated for the transition from the intermediate to the final product, the diepoxide, which nicely agrees with values calculated for the terrylene-derivative TDI. However, ~20 % of all reacting molecules at λexc=561 nm and even ~40 % at λexc=488 nm show an immediate change of the fluorescence colour within the time resolution of the experiment, bypassing any dark intermediate. Based on this experimentally observed impact of the excitation energy and the lack of relevant excited-state absorption, we hypothesize that oxygen forms a complex with ground-state terrylene which then undergoes a quasi-unimolecular reaction in the excited-state before vibrational relaxation takes place.

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
Chemphyschem
Chemphyschem 化学-物理:原子、分子和化学物理
CiteScore
4.60
自引率
3.40%
发文量
425
审稿时长
1.1 months
期刊介绍: ChemPhysChem is one of the leading chemistry/physics interdisciplinary journals (ISI Impact Factor 2018: 3.077) for physical chemistry and chemical physics. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies. ChemPhysChem is an international source for important primary and critical secondary information across the whole field of physical chemistry and chemical physics. It integrates this wide and flourishing field ranging from Solid State and Soft-Matter Research, Electro- and Photochemistry, Femtochemistry and Nanotechnology, Complex Systems, Single-Molecule Research, Clusters and Colloids, Catalysis and Surface Science, Biophysics and Physical Biochemistry, Atmospheric and Environmental Chemistry, and many more topics. ChemPhysChem is peer-reviewed.
期刊最新文献
Modification of Graphene Oxide Aerogel Monolith by Gamma Irradiation. Photoinduced Dynamics of [N(C3H7)4]2Cu4Br6 Thin Films with Dual Self-Trapped Exciton Emission and Negative Thermal Quenching. Exploring novel interfacial charge transfer complexes between TiO2 and flavonoids: Theoretical study. Studies of Catalytic Activity of New Nickel(II) Compounds Containing Pyridine Carboxylic Acids Ligands in Oligomerization Processes of Selected Olefins and Cyclohexyl Isocyanide. Molecular Insights into Alkali Metal Interaction with Redox Active Covalent Organic Framework as Cathode in Batteries.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
已复制链接
已复制链接
快去分享给好友吧!
我知道了
×
扫码分享
扫码分享
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1