Endowing single-crystal polymers with circularly polarized luminescence.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 39747830.
- Also identified by DOI 10.1038/s41467-024-55181-2 and PMC identifier 11696868.
- Licence recorded as CC BY-NC-ND.
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Abstract
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]<sub>2</sub> showing yellow CPL with a high luminescent dissymmetry factor |g<sub>lum</sub>| 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]<sub>2</sub> 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<sub>lum</sub>| 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.