The role of branching in the ultrafast dynamics and two-photon absorption of two pyrimidine push–pull molecules†

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2025-05-07 DOI:10.1039/D5CP00589B

Alexandros Katsidas, Michaela Fecková, Filip Bureš, Sylvain Achelle and Mihalis Fakis

{"title":"The role of branching in the ultrafast dynamics and two-photon absorption of two pyrimidine push–pull molecules†","authors":"Alexandros Katsidas, Michaela Fecková, Filip Bureš, Sylvain Achelle and Mihalis Fakis","doi":"10.1039/D5CP00589B","DOIUrl":null,"url":null,"abstract":"The dynamics and two-photon absorption (2PA) properties of two pyrimidine chromophores are studied using femtosecond time-resolved fluorescence and two-photon excited fluorescence techniques. The pyrimidine is used as an electron withdrawing group and is substituted at the C2 position with a phenylacridan fragment, while diphenylaministyryl donor moieties are appended at positions C4/6 to afford the pseudo-dipolar and pseudo-quadrupolar molecules 1 and 2, respectively. Chromophore 2 shows more efficient fluorescence emission, while 1 exhibits larger Stokes shifts. Their decay pathways are discussed through an emission from a Franck–Condon charge transfer (FC-CT) and a relaxed charge transfer (R-CT) state. Ultrafast dynamics in tetrahydrofuran show population of the R-CT state for 1 that is faster than solvation, while for 2, due to its pseudo-quadrupolar nature, R-CT population is slower and occurs from the solvated FC-CT state. Finally, molecule 2 shows better 2PA properties with cross sections reaching 560 GM at 820 nm.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 22","pages":" 11649-11658"},"PeriodicalIF":2.9000,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cp/d5cp00589b?page=search","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Chemistry Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/cp/d5cp00589b","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

Abstract

The dynamics and two-photon absorption (2PA) properties of two pyrimidine chromophores are studied using femtosecond time-resolved fluorescence and two-photon excited fluorescence techniques. The pyrimidine is used as an electron withdrawing group and is substituted at the C2 position with a phenylacridan fragment, while diphenylaministyryl donor moieties are appended at positions C4/6 to afford the pseudo-dipolar and pseudo-quadrupolar molecules 1 and 2, respectively. Chromophore 2 shows more efficient fluorescence emission, while 1 exhibits larger Stokes shifts. Their decay pathways are discussed through an emission from a Franck–Condon charge transfer (FC-CT) and a relaxed charge transfer (R-CT) state. Ultrafast dynamics in tetrahydrofuran show population of the R-CT state for 1 that is faster than solvation, while for 2, due to its pseudo-quadrupolar nature, R-CT population is slower and occurs from the solvated FC-CT state. Finally, molecule 2 shows better 2PA properties with cross sections reaching 560 GM at 820 nm.

Abstract Image

查看原文本刊更多论文

支化对两个嘧啶推拉分子的超快动力学和双光子吸收的影响

采用飞秒时间分辨荧光和双光子激发荧光技术研究了两种嘧啶发色团的动力学和双光子吸收特性。嘧啶作为吸电子基团，在C2位置被苯吖啶酮片段取代，而在C4/6位置，二苯基胺基给体部分被附加，分别得到伪偶极和伪四极性分子1和2。发色团2表现出更有效的荧光发射，而发色团1表现出更大的斯托克斯位移。通过法兰克-康登电荷转移（FC-CT）和弛豫CT （R-CT）态的发射讨论了它们的衰变途径。四氢呋喃中的超快动力学表明，1的R-CT态的排族速度比溶剂化快，而2的R-CT由于其伪四极性性质，排族速度较慢，并且是从溶剂化的FC-CT态开始的。最后，分子2表现出较好的2PA性能，在820 nm处横截面达到560 GM。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.