Shuhai Qiu, Li Zhang, Xin Jin, Chengxi Zhao, Junzhi Liu, Da-Hui Qu, Wei Jiang, Zhaohui Wang
{"title":"具有超低 LUMO 水平的四氮杂并二亚胺","authors":"Shuhai Qiu, Li Zhang, Xin Jin, Chengxi Zhao, Junzhi Liu, Da-Hui Qu, Wei Jiang, Zhaohui Wang","doi":"10.31635/ccschem.024.202404126","DOIUrl":null,"url":null,"abstract":"Azaacene diimides are expected to possess deep LUMO levels and narrower band gaps while maintaining excellent solubility and enhanced stability compared to their parent acenes. However, the synthesis of fully conjugated azaacenes has posed a long-term challenge. In this study, we report a stepwise oxidation approach to successfully synthesize a series of fully conjugated tetraazahexacene diimides (<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\n<bold>TAHDIs</bold></b>). Through periphery engineering, the targeted <b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\n<bold>TAHDIs</bold></b>, featuring electron-donating ethylenedioxy rings, exhibited significantly enhanced stability, with a half-life time of up to 65 h under ambient conditions. Furthermore, single-crystal structural elucidation revealed the nearly planar geometry, with imide rings slightly deviating from the skeleton plane. Notably, the LUMO levels were determined to be as low as -4.68 eV for <b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\n<bold>TAHDI-<i>ad</i></bold></b> and could be noticeably elevated to -4.53 eV through the attachment of electron-donating groups (<b xmlns:bkstg=\"http://www.atypon.com/backstage-ns\" xmlns:fn=\"http://www.w3.org/2005/xpath-functions\" xmlns:pxje=\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\" xmlns:urlutil=\"java:com.atypon.literatum.customization.UrlUtil\" xmlns:xlink=\"http://www.w3.org/1999/xlink\">\n<bold>TAHDI-<i>ce</i></bold></b>). This work represents a rare example of an experimetally evidenced low-lying LUMO level, providing an alternative strategy for developing higher fully conjugated azacene diimides which have great promise in electronics and molecular electronics.\n<figure><img alt=\"\" data-lg-src=\"/cms/asset/32c34bb3-8f6e-4ded-afd7-f937100eed74/keyimage.jpg\" data-src=\"/cms/asset/d758ba1b-92d5-4045-9a97-f39bb70d7fcb/keyimage.jpg\" src=\"/specs/ux3/releasedAssets/images/loader-7e60691fbe777356dc81ff6d223a82a6.gif\"/><ul>\n<li>Download figure</li>\n<li>Download PowerPoint</li>\n</ul>\n</figure>","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":null,"pages":null},"PeriodicalIF":9.4000,"publicationDate":"2024-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Tetraazahexacene Diimides with Ultralow LUMO Levels\",\"authors\":\"Shuhai Qiu, Li Zhang, Xin Jin, Chengxi Zhao, Junzhi Liu, Da-Hui Qu, Wei Jiang, Zhaohui Wang\",\"doi\":\"10.31635/ccschem.024.202404126\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Azaacene diimides are expected to possess deep LUMO levels and narrower band gaps while maintaining excellent solubility and enhanced stability compared to their parent acenes. However, the synthesis of fully conjugated azaacenes has posed a long-term challenge. In this study, we report a stepwise oxidation approach to successfully synthesize a series of fully conjugated tetraazahexacene diimides (<b xmlns:bkstg=\\\"http://www.atypon.com/backstage-ns\\\" xmlns:fn=\\\"http://www.w3.org/2005/xpath-functions\\\" xmlns:pxje=\\\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\\\" xmlns:urlutil=\\\"java:com.atypon.literatum.customization.UrlUtil\\\" xmlns:xlink=\\\"http://www.w3.org/1999/xlink\\\">\\n<bold>TAHDIs</bold></b>). Through periphery engineering, the targeted <b xmlns:bkstg=\\\"http://www.atypon.com/backstage-ns\\\" xmlns:fn=\\\"http://www.w3.org/2005/xpath-functions\\\" xmlns:pxje=\\\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\\\" xmlns:urlutil=\\\"java:com.atypon.literatum.customization.UrlUtil\\\" xmlns:xlink=\\\"http://www.w3.org/1999/xlink\\\">\\n<bold>TAHDIs</bold></b>, featuring electron-donating ethylenedioxy rings, exhibited significantly enhanced stability, with a half-life time of up to 65 h under ambient conditions. Furthermore, single-crystal structural elucidation revealed the nearly planar geometry, with imide rings slightly deviating from the skeleton plane. Notably, the LUMO levels were determined to be as low as -4.68 eV for <b xmlns:bkstg=\\\"http://www.atypon.com/backstage-ns\\\" xmlns:fn=\\\"http://www.w3.org/2005/xpath-functions\\\" xmlns:pxje=\\\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\\\" xmlns:urlutil=\\\"java:com.atypon.literatum.customization.UrlUtil\\\" xmlns:xlink=\\\"http://www.w3.org/1999/xlink\\\">\\n<bold>TAHDI-<i>ad</i></bold></b> and could be noticeably elevated to -4.53 eV through the attachment of electron-donating groups (<b xmlns:bkstg=\\\"http://www.atypon.com/backstage-ns\\\" xmlns:fn=\\\"http://www.w3.org/2005/xpath-functions\\\" xmlns:pxje=\\\"java:com.atypon.frontend.services.impl.PassportXslJavaExtentions\\\" xmlns:urlutil=\\\"java:com.atypon.literatum.customization.UrlUtil\\\" xmlns:xlink=\\\"http://www.w3.org/1999/xlink\\\">\\n<bold>TAHDI-<i>ce</i></bold></b>). This work represents a rare example of an experimetally evidenced low-lying LUMO level, providing an alternative strategy for developing higher fully conjugated azacene diimides which have great promise in electronics and molecular electronics.\\n<figure><img alt=\\\"\\\" data-lg-src=\\\"/cms/asset/32c34bb3-8f6e-4ded-afd7-f937100eed74/keyimage.jpg\\\" data-src=\\\"/cms/asset/d758ba1b-92d5-4045-9a97-f39bb70d7fcb/keyimage.jpg\\\" src=\\\"/specs/ux3/releasedAssets/images/loader-7e60691fbe777356dc81ff6d223a82a6.gif\\\"/><ul>\\n<li>Download figure</li>\\n<li>Download PowerPoint</li>\\n</ul>\\n</figure>\",\"PeriodicalId\":9810,\"journal\":{\"name\":\"CCS Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":9.4000,\"publicationDate\":\"2024-04-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"CCS Chemistry\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.31635/ccschem.024.202404126\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"CCS Chemistry","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.31635/ccschem.024.202404126","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Tetraazahexacene Diimides with Ultralow LUMO Levels
Azaacene diimides are expected to possess deep LUMO levels and narrower band gaps while maintaining excellent solubility and enhanced stability compared to their parent acenes. However, the synthesis of fully conjugated azaacenes has posed a long-term challenge. In this study, we report a stepwise oxidation approach to successfully synthesize a series of fully conjugated tetraazahexacene diimides (TAHDIs). Through periphery engineering, the targeted TAHDIs, featuring electron-donating ethylenedioxy rings, exhibited significantly enhanced stability, with a half-life time of up to 65 h under ambient conditions. Furthermore, single-crystal structural elucidation revealed the nearly planar geometry, with imide rings slightly deviating from the skeleton plane. Notably, the LUMO levels were determined to be as low as -4.68 eV for TAHDI-ad and could be noticeably elevated to -4.53 eV through the attachment of electron-donating groups (TAHDI-ce). This work represents a rare example of an experimetally evidenced low-lying LUMO level, providing an alternative strategy for developing higher fully conjugated azacene diimides which have great promise in electronics and molecular electronics.
期刊介绍:
CCS Chemistry, the flagship publication of the Chinese Chemical Society, stands as a leading international chemistry journal based in China. With a commitment to global outreach in both contributions and readership, the journal operates on a fully Open Access model, eliminating subscription fees for contributing authors. Issued monthly, all articles are published online promptly upon reaching final publishable form. Additionally, authors have the option to expedite the posting process through Immediate Online Accepted Article posting, making a PDF of their accepted article available online upon journal acceptance.