Ion valence-gated photochromism of an aza-crowned diarylethene.

IF 3.2 3区 化学 Q3 BIOCHEMISTRY & MOLECULAR BIOLOGY
Photochemical & Photobiological Sciences Pub Date : 2024-01-01 Epub Date: 2023-12-22 DOI:10.1007/s43630-023-00508-z
Ayaka Takeguchi, Azusa Kikuchi, Kazuhide Ueno, Shinji Ishihara, Aki Nitta, Tetsuya Nakagawa, Takashi Ubukata, Yasushi Yokoyama
{"title":"Ion valence-gated photochromism of an aza-crowned diarylethene.","authors":"Ayaka Takeguchi, Azusa Kikuchi, Kazuhide Ueno, Shinji Ishihara, Aki Nitta, Tetsuya Nakagawa, Takashi Ubukata, Yasushi Yokoyama","doi":"10.1007/s43630-023-00508-z","DOIUrl":null,"url":null,"abstract":"<p><p>A non-photochromic diarylethene 2o with an N-phenylaza-15-crown-5 was synthesized. When the nitrogen atom in the aza-crown ring was protonated, it became photochromic due to the prevention of a twisted intramolecular charge transfer (TICT). Although addition of a monovalent metal cation (Li<sup>+</sup>, Na<sup>+</sup>, K<sup>+</sup>, Rb<sup>+</sup>, Cs<sup>+</sup>, Cu<sup>+</sup>, Ag<sup>+</sup>) in acetonitrile could not stop the TICT so that it was not photochromic, the addition of a multivalent metal cation (Mg<sup>2+</sup>, Ca<sup>2+</sup>, Sr<sup>2+</sup>, Ba<sup>2+</sup>, Fe<sup>2+</sup>, Ni<sup>2+</sup>, Al<sup>3+</sup>, Sb<sup>5+</sup>) changed 2o to be photochromic due to the strong attraction of the lone pair on the nitrogen atom. In the presence of excess Cu<sup>2+</sup>, 2o was oxidized to be EPR-detectable 2o<sup>·+</sup>, which was thermally unstable as well as inert towards visible-light irradiation. However, 2o<sup>·+</sup> was further oxidized to be fairly stable 2o<sup>2+</sup> by the irradiation of 365-nm light in the presence of Cu<sup>2+</sup>. ESI-MS measurements strongly suggested the generation of 2o<sup>·+</sup> by mixing 2o with Cu(ClO<sub>4</sub>)<sub>2</sub> in acetonitrile, and the transformation of 2o<sup>·+</sup> to 2o<sup>2+</sup> by successive 365-nm light irradiation. Fe<sup>3+</sup> similarly worked as the oxidant, but the two-step oxidation of 2o to 2o<sup>2+</sup> occurred more easily.</p>","PeriodicalId":98,"journal":{"name":"Photochemical & Photobiological Sciences","volume":" ","pages":"133-151"},"PeriodicalIF":3.2000,"publicationDate":"2024-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Photochemical & Photobiological Sciences","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1007/s43630-023-00508-z","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2023/12/22 0:00:00","PubModel":"Epub","JCR":"Q3","JCRName":"BIOCHEMISTRY & MOLECULAR BIOLOGY","Score":null,"Total":0}
引用次数: 0

Abstract

A non-photochromic diarylethene 2o with an N-phenylaza-15-crown-5 was synthesized. When the nitrogen atom in the aza-crown ring was protonated, it became photochromic due to the prevention of a twisted intramolecular charge transfer (TICT). Although addition of a monovalent metal cation (Li+, Na+, K+, Rb+, Cs+, Cu+, Ag+) in acetonitrile could not stop the TICT so that it was not photochromic, the addition of a multivalent metal cation (Mg2+, Ca2+, Sr2+, Ba2+, Fe2+, Ni2+, Al3+, Sb5+) changed 2o to be photochromic due to the strong attraction of the lone pair on the nitrogen atom. In the presence of excess Cu2+, 2o was oxidized to be EPR-detectable 2o·+, which was thermally unstable as well as inert towards visible-light irradiation. However, 2o·+ was further oxidized to be fairly stable 2o2+ by the irradiation of 365-nm light in the presence of Cu2+. ESI-MS measurements strongly suggested the generation of 2o·+ by mixing 2o with Cu(ClO4)2 in acetonitrile, and the transformation of 2o·+ to 2o2+ by successive 365-nm light irradiation. Fe3+ similarly worked as the oxidant, but the two-step oxidation of 2o to 2o2+ occurred more easily.

Abstract Image

氮冠二元噻吩的离子价门控光致变色。
我们合成了一种具有 N-苯基氮杂-15-冠-5 的非光致变色二元蒽 2o。当氮杂皇冠环中的氮原子被质子化时,由于防止了分子内电荷转移(TICT),它变得具有光致变色性。虽然在乙腈中加入一价金属阳离子(Li+、Na+、K+、Rb+、Cs+、Cu+、Ag+)不能阻止 TICT,从而使其不具有光致变色性,但加入多价金属阳离子(Mg2+、Ca2+、Sr2+、Ba2+、Fe2+、Ni2+、Al3+、Sb5+)后,由于氮原子上孤对电子的强大吸引力,2o 变成了光致变色。在过量 Cu2+ 的存在下,2o 被氧化成 EPR 可检测到的 2o-+ ,这种 2o-+ 热不稳定,对可见光照射惰性。然而,在 Cu2+ 的存在下,2-o+ 在 365 纳米光的照射下进一步氧化成相当稳定的 2o2+。ESI-MS 测量结果强烈表明,2o+ 是通过在乙腈中将 2o 与 Cu(ClO4)2 混合生成的,并通过连续的 365-nm 光照射将 2o-+ 转化为 2o2+。Fe3+ 同样可以作为氧化剂,但更容易发生 2o 到 2o2+ 的两步氧化。
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
Photochemical & Photobiological Sciences
Photochemical & Photobiological Sciences 生物-生化与分子生物学
CiteScore
5.60
自引率
6.50%
发文量
201
审稿时长
2.3 months
期刊介绍: A society-owned journal publishing high quality research on all aspects of photochemistry and photobiology.
×
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
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
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 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信