Li Xiaonan, Liu Lin, Jia Luyang, Lian Zhe, He Jing, Guo Shengzhu, Wang Ying, Chen Xuebo, Jiang Hua
College of Chemistry, Beijing Normal University, Beijing, 100875, P.R. China.
Nat Commun. 2025 Jan 7;16(1):467. doi: 10.1038/s41467-025-55895-x.
Developing donor-acceptor [n]cycloparaphenylenes (D-A [n]CPPs) with multiple emissions from different emissive states remains challenging yet crucial for achieving white-light emission in single-molecule. Here, we report our explorations into acceptor engineering of quinone-based D-A [10]CPPs (Nq/Aq/Tq[10]CPPs) via a post-lateral annulation using Diels-Alder reactions of oxTh[10]CPP. X-ray analysis reveals that Nq[10]CPP displays a side by side packing via naphthoquione stacking while Aq[10]CPP adopts an intercalated conformation through anthraquinone interaction. Fluorescence investigations reveal that the quinone-based [10]CPPs display distinctive acceptor-dependent dual-emission from both the locally excited state and charge transfer state after single-wavelength excitation in organic solvents, consequently leading to multicolor emissions, in particular, white-light emission in CHCl for Aq[10]CPP. In THF/water mixture, quinone-based [10]CPPs and oxTh[10]CPP display a wide range of fluorescence emissions including white-light emission as increasing the fraction of water, accompanying by the formation of nanoparticles as demonstrated by Tyndall effect and SEM. Interestingly, the fluorescence of Aq[10]CPP can be switched from white to blue in CHCl upon redox. Our investigations demonstrate that acceptor engineering not only endows quinone-based [10]CPPs with two distint emissive states for achieving white-light emission but also highlights an effective post-synthetic strategy for functionalizing CPP nanohoops with desirable properties.
开发具有来自不同发射态的多种发射的供体-受体[n]环对亚苯基（D-A [n]CPPs）对于实现单分子白光发射而言仍然具有挑战性，但至关重要。在此，我们报告了通过使用oxTh[10]CPP的狄尔斯-阿尔德反应进行后侧向环化对基于醌的D-A [10]CPPs（Nq/Aq/Tq[10]CPPs）进行受体工程的探索。X射线分析表明，Nq[10]CPP通过萘醌堆积呈现并排堆积，而Aq[10]CPP通过蒽醌相互作用采取插层构象。荧光研究表明，基于醌的[10]CPPs在有机溶剂中单波长激发后，从局部激发态和电荷转移态均呈现出独特的受体依赖性双发射，从而导致多色发射，特别是Aq[10]CPP在CHCl中发射白光。在THF/水混合物中，随着水含量的增加，基于醌的[10]CPPs和oxTh[10]CPP呈现出包括白光发射在内的广泛荧光发射，并伴有纳米颗粒的形成，廷德尔效应和扫描电子显微镜证明了这一点。有趣的是，Aq[10]CPP的荧光在CHCl中经氧化还原后可从白色切换为蓝色。我们的研究表明，受体工程不仅赋予基于醌的[10]CPPs两种不同的发射态以实现白光发射，而且突出了一种有效的合成后策略，用于官能化具有所需性质的CPP纳米环。
