Hao-Ting Qu, Iida Partanen, Kai-Hsin Chang, Yan-Ding Lin, Igor O Koshevoy, Andrey Belyaev, Pi-Tai Chou
{"title":"Insights into the photoinduced anion translocation of the Donor-π-Acceptor+(ion)- molecules","authors":"Hao-Ting Qu, Iida Partanen, Kai-Hsin Chang, Yan-Ding Lin, Igor O Koshevoy, Andrey Belyaev, Pi-Tai Chou","doi":"10.1039/d4sc04738a","DOIUrl":null,"url":null,"abstract":"By strategic design and synthesis of a new series of phosphonium salts (compounds 1–7[OTf]), where [OTf]- stands for the trifluoromethanesulfonate anion, we performed comprehensive spectroscopic and dynamic studies on the photoinduced anion migration in toluene. Our aim is to probe if the anion migration is associated with an intrinsic barrier or is barrier free. After the occurrence of excited-state intramolecular charge transfer (ESICT) in 1–7, the charge redistribution of the cation triggers the translocation of the counter anion [OTf]–, resulting in emission spectral temporal evolution. As a result, we describe the photoinduced anion migration by introducing spectral response function C(t), a concept adopted from the solvent diffusional relaxation. The experimental results indicate that the anion migration lacks intrinsic barrier, i.e., the relaxation dynamics can be described by a biased Brownian motion along the charge transfer direction. The experimental findings are also qualitatively supported by theoretical calculations including restrained electrostatic potential (RESP) and hole-electron distribution analyses.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"95 1","pages":""},"PeriodicalIF":7.6000,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Science","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4sc04738a","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
By strategic design and synthesis of a new series of phosphonium salts (compounds 1–7[OTf]), where [OTf]- stands for the trifluoromethanesulfonate anion, we performed comprehensive spectroscopic and dynamic studies on the photoinduced anion migration in toluene. Our aim is to probe if the anion migration is associated with an intrinsic barrier or is barrier free. After the occurrence of excited-state intramolecular charge transfer (ESICT) in 1–7, the charge redistribution of the cation triggers the translocation of the counter anion [OTf]–, resulting in emission spectral temporal evolution. As a result, we describe the photoinduced anion migration by introducing spectral response function C(t), a concept adopted from the solvent diffusional relaxation. The experimental results indicate that the anion migration lacks intrinsic barrier, i.e., the relaxation dynamics can be described by a biased Brownian motion along the charge transfer direction. The experimental findings are also qualitatively supported by theoretical calculations including restrained electrostatic potential (RESP) and hole-electron distribution analyses.
期刊介绍:
Chemical Science is a journal that encompasses various disciplines within the chemical sciences. Its scope includes publishing ground-breaking research with significant implications for its respective field, as well as appealing to a wider audience in related areas. To be considered for publication, articles must showcase innovative and original advances in their field of study and be presented in a manner that is understandable to scientists from diverse backgrounds. However, the journal generally does not publish highly specialized research.