Abstract
Chirality is fundamental to molecular recognition, critically influencing pharmaceutical interactions, biomolecular sensing, and chiroptical device performance. While chiroptical luminophores hold transformative potential for optoelectronic innovation and precision bioimaging, their rational engineering remains constrained by synthetic limitations. Here, we report a streamlined and programmable asymmetric synthesis platform enabling systematic construction of boron-stereogenic boron dipyrromethene (BODIPYs) with near-infrared (NIR) chiroptical activity. This approach enables precise functionalization of prochiral BODIPYs via catalytic enantioselective cross-coupling, affording increased π-conjugated dyes with excellent enantiomeric excess and tunable photophysical properties. Further study demonstrates that molecular chirality plays a critical role in cellular recognition, as our chiral BODIPY dyes exhibit enantioselective uptake and distinct subcellular localization in cells. When formulated as nanoparticles, these dyes enable high-resolution NIR-II vascular imaging. This work not only establishes boron-centered stereogenicity as a design paradigm for advanced chiroptical bioimaging probes but also unveils dimensions in chiral organoboron chemistry with implications spanning from targeted therapeutics to chiral photonics.