The emergence, amplifification, and manipulation of
chiroptical activity in self-assembled nanostructures, including circularly
polarized absorbance and luminescence (CPL), remain considerable
challenges. Here, we report the high-throughput synthesis of nanostruc
tures with fifinely tailored chiroptical activities. Two fully π-conjugated
benzimidazoles formed H-bonded complexes with natural hydroxyl acids
(tartaric acid and mandelic acid), which self-assembled into diversifified
macroscopically chiral nanostructures. Synergistic coassembly allows for
the emergence of Cotton effffects and CPL with high dissymmetry g-factors
(gabs up to 8 × 10−3, glum up to 3 × 10−3
). The tartaric acid coassembled
system exhibits enantiomer-independent left-handed CPL, which trans
forms into a cooperative ternary coassembly appended with enantiomer
resolved CPL with extended emission wavelength upon selective
transition metal ion chelation. This H-boned coassembly system provides
a vast number of chiral nanostructures with flflexibly tuned Cotton effffects and CPL, which also behaves as a selective chiroptical
sensor to metal ions.