Hindered Tetraphenylethylene Helicates: Chiral Fluorophores with Deep‐Blue Emission, Multiple‐Color CPL, and Chiral Recognition Ability

New hindered tetraphenylethylene (TPE) helicates with substitution at 2,6‐position of phenyl rings were designed and synthesized. Due to the increased hindrance, the TPE helicates emit strong deep‐blue to violet fluorescence both in the solid state and in solution, and could be resolved into enantiomers that emit strong and multicolor circularly polarized luminescence (CPL), and exhibit a high enantioselective recognition of chiral tartaric acid and its derivatives. Surprisingly, the derived helicate tetramines possess amino groups with an unpredented planar structure and sp2‐hybridized nitrogen, arousing the change between AIE effect and ACQ phenomenon through photoinduced electron transfer (PET). With advantages of short synthetic route, many modification positions, deep‐blue to violet emission, wide CPL tuning, and high chiral recognition ability, the hindered TPE helicates show broad prospects as chiral materials. Hindered tetraphenylethylene (TPE) helicates, with a completely immobilized propeller‐like conformation through substitution at the 2,6‐positions of the phenyl rings, were prepared by a short synthetic route. These helicates, with their many modification positions, show deep‐blue to violet emission, circularly polarized luminescence (CPL) that can be tuned over a wide range, and highly enantioselective chiral recognition.