Enantiotopic-group-selective coupling for unified access to carbazole atropisomers as versatile chiral chromophores.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 41271723.
- Also identified by DOI 10.1038/s41467-025-65243-8 and PMC identifier 12638793.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Chiral organic chromophores are foundational for advanced optical and electronic devices. Despite the widespread use of N-aryl carbazoles in visible-luminescent materials, chiroptical applications of their atropisomers have remained underdeveloped due to the synthetic challenge of achieving remote atroposelectivity necessitated by extended π-systems. Here, we present a unified strategy for the efficient synthesis of enantioenriched N-C and N-N carbazole atropisomers. By integrating <sup>13</sup>C NMR-based ligand parameterization, we achieve enantiotopic-group-selective coupling reactions that simultaneously incorporate tailored π-functionalities and establish axial chirality (up to >99:1 er) using synthetic pathways established in carbazole chemistry. Through covalent modulation and noncovalent complexation, we investigate novel chiroptical functions of carbazole atropisomers, including circular dichroism (CD), circularly polarized luminescence (CPL), charge-transfer CPL (CT-CPL), and circularly polarized thermally activated delayed fluorescence (CP-TADF). By establishing an electrostatic steering strategy for remote atroposelectivity, our work paves the way for integrating multifunctional carbazoles into advanced optical and optoelectronic technologies.