Zhang Jianyu, Shen Hanchen, Xiong Zuping, Du Lidong, Li Moxin, Ou Xinwen, Zhu Xinyan, Lam Jacky W Y, Liu Tzu-Ming, Xu Changhuo, Zhang Haoke, Zhong Tang Ben
MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou, 3100587, China.
Department of Chemistry, Hong Kong Branch of Chinese National Engineering Research Center for Tissue Restoration and Reconstruction, The Hong Kong University of Science and Technology Clear Water Bay, Kowloon, Hong Kong, 999077, China.
Angew Chem Int Ed Engl. 2025 Jan 2;64(1):e202413751. doi: 10.1002/anie.202413751. Epub 2024 Oct 21.
Clusteroluminescence (CL) materials without largely conjugated structures have gained significant attention due to their unique photophysical properties and potential in bioimaging. However, low luminescence efficiency and short emission wavelength limit their development. This work designs three luminogens with CL properties (CLgens) by introducing n-electron-involved through-space conjugation (TSC) into diarylmethane. Apart from single-photon excited long-wavelength (686 nm) and high-efficiency (29 %) CL, two-photon clusteroluminescence (TPCL) is successfully achieved in such small luminogens with only two isolated heteroatomic units. TSC stabilized in the aggregate state has been proven to realize efficient spatial electron delocalization similar to conventionally conjugated compounds. Encouraged by the excellent TPCL properties, two-photon imaging of blood vessels in vivo and biocompatibility verification utilizing CLgens are also achieved. This work illustrates the essential role of TSC in promoting nonlinear optical properties of CLgens and may facilitate further design and development of the next generation of bioprobes with excellent biocompatibility.
由于其独特的光物理性质和在生物成像方面的潜力，没有大量共轭结构的聚集发光（CL）材料受到了广泛关注。然而，低发光效率和短发射波长限制了它们的发展。这项工作通过将涉及n电子的空间共轭（TSC）引入二芳基甲烷，设计了三种具有CL性质的发光体（CLgens）。除了单光子激发的长波长（686 nm）和高效（29%）的CL外，在仅具有两个孤立杂原子单元的如此小的发光体中成功实现了双光子聚集发光（TPCL）。已证明在聚集态中稳定的TSC能够实现类似于传统共轭化合物的高效空间电子离域。受优异的TPCL性质的鼓舞，还实现了体内血管的双光子成像以及利用CLgens进行的生物相容性验证。这项工作阐明了TSC在促进CLgens的非线性光学性质方面的重要作用，并可能有助于进一步设计和开发具有优异生物相容性的下一代生物探针。
