Hu Yang, Su-Kao Peng, Wenbin Chen, Dong Luo, Shibo Xi, Shuai Lu, Yong-Liang Huang, De-Bo Hao, Bincheng Cai, Heng Wang, Mo Xie, Ming-De Li, Xiaopeng Li, Guo-Hong Ning, Dan Li
{"title":"Double-Helical Assembly of a Copper-Silver Hydride Cluster Exhibiting Thermally Activated Delayed Fluorescence","authors":"Hu Yang, Su-Kao Peng, Wenbin Chen, Dong Luo, Shibo Xi, Shuai Lu, Yong-Liang Huang, De-Bo Hao, Bincheng Cai, Heng Wang, Mo Xie, Ming-De Li, Xiaopeng Li, Guo-Hong Ning, Dan Li","doi":"10.31635/ccschem.024.202404213","DOIUrl":null,"url":null,"abstract":"<p>The synthesis of helical nanostructures with advanced functions from atomically precise building blocks is attractive, but remains a significant challenge. In this work, we report two atomically precise metal hydride clusters, Cu<sub>24</sub>H<sub>6</sub>L<sub>12</sub>(PPh<sub>3</sub>)<sub>2</sub>Pz<sub>6</sub> (<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>Cu@Cu<sub>23</sub>H<sub>6</sub></bold></b>,) and Cu<sub>24-x</sub>Ag<sub>x</sub>H<sub>6</sub>L<sub>12</sub>(PPh<sub>3</sub>)<sub>2</sub>Pz<sub>6</sub> (0 > x > 1) (<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>Ag@Cu<sub>23</sub>H<sub>6</sub></bold></b>) (L= CH<sub>3</sub>OPhC≡C<sup>−</sup>, Pz = 3,5-(CF<sub>3</sub>)<sub>2</sub>-pyrazolate), containing M@Cu<sub>23</sub> (M=Cu/Ag) kernels with D<sub>3</sub>-symmetry. Single crystal X-ray diffraction results reveal that the DNA-like double-helical nanostructures driven by intrastrand and interstrand supramolecular interactions, including weak hydrogen bonds (i.e., C–H···F/O/C) and van der Waal’s interactions (i.e., C···F and F···F), are formed through the self-hierarchical assembly of<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> Cu@Cu<sub>23</sub>H<sub>6</sub></bold></b> and <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>Ag@Cu<sub>23</sub>H<sub>6</sub></bold></b>. In addition, <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>Cu@Cu<sub>23</sub>H<sub>6</sub></bold></b> is nonemissive. After doping with Ag, <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>Ag@Cu<sub>23</sub>H<sub>6</sub></bold></b> exhibits thermally activated delayed fluorescence (TADF) both in the solid state and in solution, which was seldom presented in high-nuclear clusters. Experimental and theoretical calculations suggest that the efficient separation of highest occupied molecular orbital and lowest unoccupied molecular orbital as well as larger spin–orbit coupling of <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>Ag@Cu<sub>23</sub>H<sub>6</sub></bold></b> than <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>Cu@Cu<sub>23</sub>H<sub>6</sub></bold></b> are responsible for the TADF. This work not only provides a platform to facilitate the in-depth investigation of self-hierarchical assembly mechanisms of double-helical nanostructures but also demonstrates that the doping strategy can endow helical nanostructures with interesting luminescent behavior.</p>","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":"33 1","pages":""},"PeriodicalIF":9.4000,"publicationDate":"2024-09-16","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.024.202404213","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
The synthesis of helical nanostructures with advanced functions from atomically precise building blocks is attractive, but remains a significant challenge. In this work, we report two atomically precise metal hydride clusters, Cu24H6L12(PPh3)2Pz6 (Cu@Cu23H6,) and Cu24-xAgxH6L12(PPh3)2Pz6 (0 > x > 1) (Ag@Cu23H6) (L= CH3OPhC≡C−, Pz = 3,5-(CF3)2-pyrazolate), containing M@Cu23 (M=Cu/Ag) kernels with D3-symmetry. Single crystal X-ray diffraction results reveal that the DNA-like double-helical nanostructures driven by intrastrand and interstrand supramolecular interactions, including weak hydrogen bonds (i.e., C–H···F/O/C) and van der Waal’s interactions (i.e., C···F and F···F), are formed through the self-hierarchical assembly of Cu@Cu23H6 and Ag@Cu23H6. In addition, Cu@Cu23H6 is nonemissive. After doping with Ag, Ag@Cu23H6 exhibits thermally activated delayed fluorescence (TADF) both in the solid state and in solution, which was seldom presented in high-nuclear clusters. Experimental and theoretical calculations suggest that the efficient separation of highest occupied molecular orbital and lowest unoccupied molecular orbital as well as larger spin–orbit coupling of Ag@Cu23H6 than Cu@Cu23H6 are responsible for the TADF. This work not only provides a platform to facilitate the in-depth investigation of self-hierarchical assembly mechanisms of double-helical nanostructures but also demonstrates that the doping strategy can endow helical nanostructures with interesting luminescent behavior.
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.