Near‐Infrared‐Emitting Helically Twisted Conjugated Frameworks Consisting of Alternant Donor‐π‐Acceptor Units and Multiple Boron Atoms

A novel design strategy to construct bright and narrow near-infrared (NIR) emission materials with suppressed shoulder peaks can significantly enhance their performance in various applications. Herein, we have successfully synthesized a series of helically twisted D-π-A conjugated systems bridged by boron atoms, achieving bright red to near-infrared (NIR) emissions with notably narrow full-width at half-maximum (FWHM) values of 35 nm (0.08 eV) and photoluminescence quantum yields (PLQY) up to 80 %. These compounds display red-shifted emissions up to 753 nm in higher concentrations. Cis/trans configurational isomers of multi-boron-bridged molecule BN3 exhibit similar photophysical properties. The unique combination of boron-induced coordination-enhanced charge transfer (CE-CT) and the helically twisted conjugated framework is pivotal in achieving the red-shifted, narrowband emission. X-ray crystallographic analysis of BN2 and BN3-a reveals that the extension of boron-bridged D-π-A skeletons significantly increases the distortion of the skeleton. Systematic theoretical calculations show how the boron CE-CT mechanism, in conjunction with the helical twist, leads to the narrowing of emission bands while simultaneously red-shifting them into the NIR region. This work could open new avenues for the development of advanced materials with tailored optical properties, particularly in the challenging and highly sought-after NIR spectrum.