Tuning the emission and lighting the circularly polarized luminescence of polyfluorene by incorporating a non-emissive polycarbene,Polymer Chemistry

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Tuning the emission and lighting the circularly polarized luminescence of polyfluorene by incorporating a non-emissive polycarbene
Polymer Chemistry ( IF 4.1 ) Pub Date : 2023-02-14 , DOI: 10.1039/d3py00056g
Chao Wang ₁ , Li Zhou ₁ , Yuan-Yuan Zhu ₁ , Na Liu ₂ , Zong-Quan Wu ₃

Affiliation

Facile fabrication and control over the self-assembly of π-conjugated block copolymers are greatly desired in the field of organic semiconducting materials. In this work, polyfluorenes carrying a Ni(II)-terminal were first prepared via Ni(II)-catalyzed quasi-living Kumada catalyst-transfer polymerization, the chain of which is extended with chiral diazoacetates carrying an S- or R-methylbenzyl ester, giving poly(fluorene)-b-polycarbene copolymers in high yield with controlled molar mass and low dispersity. Although the monomers have different structures and polymerization mechanisms, the one-pot block copolymerization proceeded in a living manner. The diazoacetate chirality induced an asymmetric polymerization, rendering the polycarbene block to adopt a one-handed preferred helix. Interestingly, polyfluorene showed blue emission with circularly polarized luminescence (CPL) silent, whereas the resulting block copolymers showed cyan emission with clear CPL. Further studies revealed that the block copolymers self-assembled into one-handed helical nanofibers with defined handedness. Through asymmetric self-assembly, the chirality was transferred to the supramolecular assemblies, endowing the achiral polyfluorene with high optical activity and CPL.

中文翻译：

通过加入非发射性聚碳烯来调节发射和点亮聚芴的圆偏振发光

有机半导体材料领域非常需要易于制造和控制 π 共轭嵌段共聚物的自组装。在这项工作中，首先通过Ni( II ) 催化的准活性 Kumada 催化剂转移聚合制备了带有Ni( II )- 末端的聚芴，其链被带有S - 或R - 甲基苄酯的手性重氮乙酸酯延长, 给出聚（芴）- b-具有可控摩尔质量和低分散性的高产率聚卡宾共聚物。尽管单体具有不同的结构和聚合机理，但一锅式嵌段共聚以活泼的方式进行。重氮乙酸盐的手性引起不对称聚合，使聚卡宾嵌段采用单手优选螺旋结构。有趣的是，聚芴显示蓝色发射且圆偏振发光 (CPL) 无声，而所得嵌段共聚物显示青色发射且 CPL 清晰。进一步的研究表明，嵌段共聚物自组装成具有确定的旋向性的单手螺旋纳米纤维。通过不对称自组装，手性转移到超分子组装体上，赋予非手性聚芴高光学活性和CPL。

更新日期：2023-02-14

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