Circularly Polarized Luminescence with Large Dissymmetry Factor over 10 <sup>−1</sup> Based on Flexible Point‐Chirality via Programming at Molecular Level
Abstract
Abstract In this work, we report a series of small Spirocyclic Chiral Fluorophores (SCFs) with donor‐acceptor type small‐ π emitters. These SCFs induce mimic α ‐helix supramolecular packing modes via adjustments at the molecular level (e.g., hydrogen bonding sites, positions of fused rings). This approach not only enhances circularly polarized luminescence (CPL) with the luminescence dissymmetry factor ( g lum ) up to 0.18 in assembled materials but also enables inversion of the chiral signal. Moreover, unlike most CPL materials with a single point‐chiral center that are CPL‐silent at the molecular state, the spirocyclic configuration can enhance efficient point‐chirality transfer to the fluorophores owing to the self‐rigidified skeleton, consequently enable efficient CPL with the g l um in the order of 10 −3 even in the molecular solutions. The mechanistic insights are revealed by experimental investigation including the femtosecond transient absorption (fs‐TA) spectroscopy and single‐crystal analysis, as well as DFT calculation. This study opens new avenues for developing organic CPL materials with large g values based on low‐molecular‐weight flexible point‐chiral fluorophores, offering great potential for future applications in biotechnology and circularly polarized organic light‐emitting diodes (CP‐OLEDs).
Article Details
Authors (9)
Shi‐Qiang Wei
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs State Key Laboratory of Synergistic Chem‐Bio Synthesis & School of Chemistry and Chemical Engineering Shanghai Jiao Tong University Shanghai 200240 P.R. China
Zi‐Hao Li
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs State Key Laboratory of Synergistic Chem‐Bio Synthesis & School of Chemistry and Chemical Engineering Shanghai Jiao Tong University Shanghai 200240 P.R. China
Chun‐Lin Sun
State Key Laboratory of Natural Product Chemistry College of Chemistry and Chemical Engineering Lanzhou University Lanzhou 730000 China
Yae Li
State Key Laboratory of Natural Product Chemistry College of Chemistry and Chemical Engineering Lanzhou University Lanzhou 730000 China
Xiao‐Yu Wang
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs State Key Laboratory of Synergistic Chem‐Bio Synthesis & School of Chemistry and Chemical Engineering Shanghai Jiao Tong University Shanghai 200240 P.R. China
Ding Tong‐Mei
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs State Key Laboratory of Synergistic Chem‐Bio Synthesis & School of Chemistry and Chemical Engineering Shanghai Jiao Tong University Shanghai 200240 P.R. China
Xuefeng Zhu
Yong‐Qiang Tu
School of Pharmaceutical Sciences School of Chemistry and Chemical Engineering Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs State Key Laboratory of Synergistic Chem‐Bio Synthesis Shanghai Jiao Tong University Shanghai China
Shu‐Yu Zhang
School of Pharmaceutical Sciences School of Chemistry and Chemical Engineering Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs State Key Laboratory of Synergistic Chem‐Bio Synthesis Shanghai Jiao Tong University Shanghai China