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Facile Multicomponent Polymerizations toward Unconventional Luminescent Polymers with Readily Openable Small Heterocycles
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-04-09 , DOI: 10.1021/jacs.8b01991
Ting Han 1, 2 , Haiqin Deng 1, 2 , Zijie Qiu 1, 2 , Zheng Zhao 1, 2 , Haoke Zhang 1, 2 , Hang Zou 1, 2 , Nelson L. C. Leung 1, 2 , Guogang Shan 1, 2 , Mark R. J. Elsegood 3 , Jacky W. Y. Lam 1, 2 , Ben Zhong Tang 1, 2, 4
Affiliation  

Heterocyclic polymers have gained enormous attention for their unique functionalities and wide applications. In contrast with the well-studied polymer systems with five- or six-membered heterocycles, functional polymers with readily openable small-ring heterocycles have rarely been explored due to their large synthetic difficulty. Herein, a facile one-pot multicomponent polymerization to such polymers is developed. A series of functional polymers with multisubstituted and heteroatom-rich azetidine frameworks are efficiently generated at room temperature in high atom economy from handy monomers. The four-membered azetidine rings in the polymer skeletons can be easily transformed into amide and amidine moieties via a fast and efficient acid-mediated ring-opening reaction, producing brand-new polymeric materials with distinctive properties. All the as-prepared azetidine-containing polymers exhibit intrinsic visible luminescence in the solid state under long-wavelength UV irradiation even without conventionally conjugated structures. Such unconventional luminescence is attributed to the clusteroluminogens formed by through-space electronic interactions of heteroatoms and phenyl rings. All the obtained polymers show excellent optical transparency, high and tunable refractive indices, low optical dispersions and good photopatternability, which make them promising materials in various advanced electronic and optoelectronic devices. The ring-opened polymers can also function as a lysosome-specific fluorescent probe in biological imaging.

中文翻译:

易于打开的小杂环非常规发光聚合物的简便多组分聚合

杂环聚合物因其独特的功能和广泛的应用而备受关注。与经过充分研究的具有五元或六元杂环的聚合物体系相比,具有易于打开的小环杂环的功能聚合物由于合成难度大而很少被探索。在此,开发了对此类聚合物的简便的一锅多组分聚合。一系列具有多取代和富含杂原子的氮杂环丁烷骨架的功能聚合物在室温下以高原子经济性从方便的单体中有效生成。聚合物骨架中的四元氮杂环丁烷环可以通过快速有效的酸介导的开环反应轻松转化为酰胺和脒部分,从而产生具有独特性能的全新聚合物材料。即使没有常规的共轭结构,所有制备的含氮杂环丁烷的聚合物在长波长紫外线照射下也能在固态下显示出固有的可见光。这种非常规的发光归因于杂原子和苯环的空间电子相互作用形成的团簇发光体。所有获得的聚合物都表现出优异的光学透明度、高且可调的折射率、低光学色散和良好的光图案化能力,这使其成为各种先进电子和光电器件中的有前途的材料。开环聚合物还可在生物成像中用作溶酶体特异性荧光探针。
更新日期:2018-04-09
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