To explore the photo-physical properties of the chiral macrocycles and corresponding chiral POPs, the UV-vis absorption spectra of these chiral materials were firstly recorded (Table ). The chiral macrocycles with diverse substitutions exhibited similar absorption maximal around 363 nm (Figure ), and the optical band gap (E opt ) for these compounds was estimated to be 3.04 eV for SBT-H, 3.0 eV for SBT-Br, 2.96 eV for SBT-OMe, and 2.93 eV for SBT-2N in THF (Figure ). This trend was well consistent with the simulated band gap for these series of chiral macrocycles based on DFT calculation on the basis set of b3lyp/6-31G(d), in which the band gap gradually decreased from 3.51 eV for SBT-H and 3.45 eV for SBT-Br, to 3.41 eV for SBT-OMe and 3.30 eV for SBT-2N (Figure ). By contrast, the chiral POPs PRBT and PSBT exhibited obviously redshifted absorption band at 383 nm relative to their monomers, whereas the E opt had also decreased to 2.42 eV owing to the extended π-conjugation (Figure ) .