Double-Helical Assembly of a Copper-Silver Hydride Cluster Exhibiting Thermally Activated Delayed Fluorescence

IF 9.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY CCS Chemistry Pub Date : 2024-09-16 DOI:10.31635/ccschem.024.202404213
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
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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 &gt; x &gt; 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}
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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.

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铜-银氢化物簇的双螺旋组装显示热激活延迟荧光
用原子精度的构建模块合成具有高级功能的螺旋纳米结构很有吸引力,但仍然是一项重大挑战。在这项工作中,我们报告了两种原子精确的金属氢化物团簇:Cu24H6L12(PPh3)2Pz6(Cu@Cu23H6)和 Cu24-xAgxH6L12(PPh3)2Pz6 (0 >;x > 1)(Ag@Cu23H6)(L= CH3OPhC≡C-, Pz = 3,5-(CF3)2-吡唑烷),含有 D3 对称的 M@Cu23(M=Cu/Ag)核。单晶 X 射线衍射结果表明,通过 Cu@Cu23H6 和 Ag@Cu23H6 的自分层组装,在链内和链间超分子相互作用(包括弱氢键(即 C-H-F/O/C)和范德华相互作用(即 C-F 和 F-F))的驱动下形成了类似 DNA 的双螺旋纳米结构。此外,Cu@Cu23H6 还具有非辐射性。掺入银后,Ag@Cu23H6 在固态和溶液中都表现出热激活延迟荧光(TADF),这在高核团簇中很少出现。实验和理论计算表明,与 Cu@Cu23H6 相比,Ag@Cu23H6 的最高占有分子轨道和最低未占有分子轨道的有效分离以及更大的自旋轨道耦合是产生 TADF 的原因。这项工作不仅为深入研究双螺旋纳米结构的自分层组装机制提供了一个平台,而且证明了掺杂策略可以赋予螺旋纳米结构有趣的发光行为。
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来源期刊
CCS Chemistry
CCS Chemistry Chemistry-General Chemistry
CiteScore
13.60
自引率
13.40%
发文量
475
审稿时长
10 weeks
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.
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