Li Zhong-Qiu, Meng Li, Chen Zili, Zhong Yu-Wu
Key Laboratory for Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China.
Beijing National Laboratory for Molecular Sciences, Beijing, China.
Nat Commun. 2025 Jan 2;16(1):234. doi: 10.1038/s41467-024-55181-2.
The preparation of single-crystal polymers with circularly polarized luminesce (CPL) remains a challenging task in chemistry and materials science. Herein, we present the single-crystal-to-single-crystal topochemical photopolymerization of a chiral organic salt to achieve this goal. The in-situ reaction of 1,4-bis((E)-2-(pyridin-4-yl)vinyl)benzene (1) with chiral (+)- or (-)-camphorsulfonic acid (CSA) gives the monomer crystal 1[( + )/( - )-CSA] showing yellow CPL with a high luminescent dissymmetry factor |g| of 0.035 and emission quantum yield Φ of 49.7%. Upon photo-induced topochemical [2 + 2] polymerization, single-crystal polyionic polymers of poly-1[( + )/( - )-CSA] are obtained. The single-crystal-to-single-crystal (SCSC) photopolymerization is revealed by in situ powder X-ray diffraction, single-crystal X-ray, optical microscopy, infrared, circular dichroism, and CPL spectroscopic analyzes. Interestingly, the photopolymer crystals show blue and handedness-inverted CPL with |g| of 0.011 (Φ = 14.2%), with respect to the yellow CPL of the monomer crystal. Furthermore, patterned circularly-polarized photonic heterojunctions with alternate blue and yellow CPL sub-blocks are prepared by a mask-assisted photopolymerization method. Our findings provide a vision for fabricating high-performance CPL-active crystalline polymer materials, paving the way for the further development of photo-response chiral systems.
制备具有圆偏振发光（CPL）的单晶聚合物在化学和材料科学领域仍然是一项具有挑战性的任务。在此，我们展示了一种手性有机盐的单晶到单晶拓扑化学光聚合反应以实现这一目标。1,4-双（（E）-2-（吡啶-4-基）乙烯基）苯（1）与手性（+）-或（-）-樟脑磺酸（CSA）的原位反应生成单体晶体1[（+）/（-）-CSA]，其呈现出黄色CPL，具有0.035的高发光不对称因子|g|和49.7%的发射量子产率Φ。通过光诱导拓扑化学[2 + 2]聚合反应，可获得聚-1[（+）/（-）-CSA]的单晶聚离子聚合物。通过原位粉末X射线衍射、单晶X射线、光学显微镜、红外光谱、圆二色光谱和CPL光谱分析揭示了单晶到单晶（SCSC）光聚合反应。有趣的是，相对于单体晶体的黄色CPL，光聚合晶体呈现出蓝色且手性反转的CPL，|g|为0.011（Φ = 14.2%）。此外，通过掩膜辅助光聚合方法制备了具有交替蓝色和黄色CPL子块的图案化圆偏振光子异质结。我们的研究结果为制备高性能CPL活性晶体聚合物材料提供了思路，为光响应手性系统的进一步发展铺平了道路。
