Lighting up aggregate emission of perylene diimide by leveraging polymerization-mediated through-space charge transfer and π-π stacking  

作　　者：Suiying Ye Désirée Füglistaller Tian Tian Anjay Manian Sudhir Kumar Celine Nardo Andrew J.Christofferson Salvy P.Russo Chih-Jen Shih Jean-Christophe Leroux Yinyin Bao 

机构地区：[1]Institute of Pharmaceutical Sciences,Department of Chemistry and Applied Biosciences,ETH Zurich,Vladimir-Prelog-Weg 3,8093 Zurich,Switzerland [2]Institute for Chemical and Bioengineering,Department of Chemistry and Applied Biosciences,ETH Zurich,Vladimir-Prelog-Weg 1-5/10,8093 Zurich,Switzerland [3]ARC Centre of Excellence in Exciton Science,School of Science,RMIT University,Melbourne,Victoria,3001,Australia [4]School of Science,STEM College,RMIT University,Melbourne,Victoria 3001,Australia

出　　处：《Science China Chemistry》2024年第12期4218-4233,共16页中国科学（化学英文版）

基　　金：supported by Swiss National Science Foundation(190313);Fondation Claude et Giuliana(1-005137);the Australian Research Council(ARC)under the Centre of Excellence Scheme(CE170100026)。

摘　　要：The molecular engineering of fluorescent organic/polymeric materials,specifically those emitting in the deep red to near-infrared spectrum,is vital for advancements in optoelectronics and biomedicine.Perylene diimide(PDI),a well-known fluorescent scaffold,offers high thermal and photophysical stability but suffers from fluorescence quenching in solid or aggregate states due to intenseπ-πinteractions.To mitigate this,simple and versatile methods for strong PDI aggregate emission without extensive synthetic demands are highly desirable but still lacking.Here,we report a straightforward strategy to enhance the solid-state emission of PDI by introducing certain degree of through-space charge transfer(TSCT)via controlled radical polymerization,which can efficiently distort the typical face-to-face PDI stacking,enabling greatly enhanced deep red emission.This is achieved by growing electron-donating star-shape styrenic(co)polymers from a multidirectional electron-accepting PDI initiator.The incorporation of polycyclic aromatic monomers further shifted the emission into the near-infrared region,albeit with a reduced intensity.Overall,the emission of the PDI-based TSCT polymers can be systematically manipulated by leveraging the balance between PDI stacking and the TSCT degree,as confirmed by both experimental study and theoretical calculations.Our approach circumvents complex synthetic procedures,offering highly emissive materials with large Stokes shifts and showing broad potential for optoelectronic technology.

关 键 词：through-space charge transfer controlled radical polymerization solid-state emission perylene diimide 

分 类 号：O631[理学—高分子化学]