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基于荧光团溶剂诱导静电势分布的具有颜色可调性的非常规发光聚合物。

Unconventional Luminescence Polymer with Color-Tunability based on Solvent-Induced Electrostatic Potential Distribution of Fluorophore.

作者信息

He Yanyun, Qiao Yujie, Li Zheng, Feng Weixu, Zhao Yan, Tian Wei, Zhong Tang Ben, Yan Hongxia

机构信息

Shaanxi Key Laboratory of Macromolecular Science and Technology, Xi'an Key Laboratory of Hybrid Luminescent Materials and Photonic Device, School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, 710129, Xi'an, China.

Shenzhen Institute of Aggregate Science and Technology, School of Science and Engineering, The Chinese University of Hong Kong, Shenzhen, 518172, Shenzhen, Guangdong, China.

出版信息

Angew Chem Int Ed Engl. 2024 Nov 18;63(47):e202413425. doi: 10.1002/anie.202413425. Epub 2024 Oct 15.

Abstract

Tuning full-color emission of polymers holds significant promise. However, preparing unconventional luminescence polymers with color-tunability in dilute solution and understanding the relationship between non-covalent interactions and luminescent behavior remains a great challenge. We report two emitters (P1 and P2) incorporating tetracoordinate boron. The P1 with non-conjugated D-π-A structure, exhibited red delayed fluorescence at 645 nm with quantum yield of 9.15 % in aggregates. Notably, the emission wavelength of P1 can be tuned from 418 to 588 nm at different solvent. Similarly, the emission wavelength of P2 can also be adjusted by manipulating the interactions between the solvent and fluorophore. Experimental characterization and theoretical calculations indicate that the B←N bond and electronic interactions between solvent and fluorophore significantly regulate the equilibrium the electrostatic potential (ESP) and the intramolecular O⋅⋅⋅O interactions of P1, thereby modulating its emission wavelength. Additionally, these polymers showed excellent potential in fluoride ions detection. This work provides new insights into the complex effects of intermolecular interactions on luminescent properties.

摘要

调节聚合物的全色发射具有重大前景。然而,制备在稀溶液中具有颜色可调性的非常规发光聚合物并理解非共价相互作用与发光行为之间的关系仍然是一个巨大的挑战。我们报道了两种含有四配位硼的发光体(P1和P2)。具有非共轭D-π-A结构的P1在聚集体中于645 nm处呈现红色延迟荧光,量子产率为9.15%。值得注意的是,P1的发射波长在不同溶剂中可从418 nm调至588 nm。同样,P2的发射波长也可通过控制溶剂与荧光团之间的相互作用来调节。实验表征和理论计算表明,B←N键以及溶剂与荧光团之间的电子相互作用显著调节了P1的静电势(ESP)平衡和分子内O⋅⋅⋅O相互作用,从而调节其发射波长。此外,这些聚合物在氟离子检测方面显示出优异的潜力。这项工作为分子间相互作用对发光性质的复杂影响提供了新的见解。

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