Engineering LE–CT State Synergy in Aminoboranes for Single Molecule White Light Emission and Dual‐Mode Chiroptical/Phosphorescence Output

Axially chiral aminoboranes that integrate multiple emissive functions within a single molecular framework are reported. These compounds exhibit dual emission, originating from two electronically distinct excited states: high‐energy fluorescence from a binaphthyl‐localized state and low‐energy emission from an aminoborane‐centered charge‐transfer state. Circularly‐polarized luminescence is observed exclusively from the high‐energy channel, directly linking chiroptical activity to the binaphthyl‐localized excited state. Restricting intramolecular motion enhances high‐energy emission. In contrast, incorporation into a rigid polymer matrix enables efficient triplet harvesting, affording persistent room‐temperature phosphorescence with lifetimes on the order of seconds. This RTP feature further enables time‐gated optical encoding, highlighting the potential of these materials for anti‐counterfeiting applications. The combination of white‐light emission, selective circular polarization, and ultralong phosphorescence in a single scaffold establishes a molecular design strategy for multifunctional chiroptical materials.