Control of the Electronic and Optical Properties of Aminoxyl Radicals via Boron Complexation

IF 3.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Dalton Transactions Pub Date : 2024-11-20 DOI:10.1039/d4dt02973a

Takuma AGOU Kuroda, Peiyuan Yang, Marika Nakamura, Risa Hyakutake, Hiroki Fukumoro, Toshiyuki Oshiki, Yuta Nishina, Koichiro Masada, Takahiro Sasamori, Yoshiyuki Mizuhata, Kazuya Kubo, Ryo Inoue, Tomohiro Agou

{"title":"Control of the Electronic and Optical Properties of Aminoxyl Radicals via Boron Complexation","authors":"Takuma AGOU Kuroda, Peiyuan Yang, Marika Nakamura, Risa Hyakutake, Hiroki Fukumoro, Toshiyuki Oshiki, Yuta Nishina, Koichiro Masada, Takahiro Sasamori, Yoshiyuki Mizuhata, Kazuya Kubo, Ryo Inoue, Tomohiro Agou","doi":"10.1039/d4dt02973a","DOIUrl":null,"url":null,"abstract":"Stable radicals have attracted increasing attention in recent years because of their unique electronic and optical characteristics. Aminoxyl radicals are one of the most widely studies stable radicals to date, but their applications in opto-functional materials have yet to be explored in detail. Our group previously reported the boron complexes of aminoxyl radicals exhibit near-infrared (NIR) absorption. In this work, an aminoxyl radical without boron-complexation was synthesized to elucidate the effects of boron coordination on the properties of the aminoxyl radicals. The results of electron spin resonance spectroscopy, ultraviolet-visible-NIR absorption measurements, and density functional theory calculations indicated that boron complexation facilitated spin delocalization over the radical π-frameworks. Furthermore, a π-extended aminoxyl radical-boron complex exhibited a significant wavelength-shift to longer wavelengths in the NIR-II absorption region, thereby reflecting its larger π-conjugated radical skeleton.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":"7 1","pages":""},"PeriodicalIF":3.5000,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4dt02973a","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}

引用次数: 0

Abstract

Stable radicals have attracted increasing attention in recent years because of their unique electronic and optical characteristics. Aminoxyl radicals are one of the most widely studies stable radicals to date, but their applications in opto-functional materials have yet to be explored in detail. Our group previously reported the boron complexes of aminoxyl radicals exhibit near-infrared (NIR) absorption. In this work, an aminoxyl radical without boron-complexation was synthesized to elucidate the effects of boron coordination on the properties of the aminoxyl radicals. The results of electron spin resonance spectroscopy, ultraviolet-visible-NIR absorption measurements, and density functional theory calculations indicated that boron complexation facilitated spin delocalization over the radical π-frameworks. Furthermore, a π-extended aminoxyl radical-boron complex exhibited a significant wavelength-shift to longer wavelengths in the NIR-II absorption region, thereby reflecting its larger π-conjugated radical skeleton.

查看原文本刊更多论文

通过硼络合控制氨基氧自由基的电子和光学特性

近年来，稳定自由基因其独特的电子和光学特性而受到越来越多的关注。氨氧自由基是迄今为止研究最为广泛的稳定自由基之一，但其在光功能材料中的应用还有待深入探讨。我们的研究小组以前曾报道过氨基氧自由基的硼络合物具有近红外（NIR）吸收。在这项工作中，我们合成了一种没有硼络合物的氨基氧自由基，以阐明硼配位对氨基氧自由基性质的影响。电子自旋共振光谱、紫外-可见-近红外吸收测量和密度泛函理论计算的结果表明，硼络合促进了自由基π-框架的自旋析出。此外，π-扩展的氨基羰基-硼络合物在近红外-II 吸收区表现出明显的波长偏移，波长更长，从而反映了其较大的π-共轭自由基骨架。

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

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.