Physical insight into optical spectroscopy of chiral covalent organic pillars as molecular nanotubes

In this paper, we theoretically investigate chiral covalent organic pillars synthesized by connecting rim-desymmetrized macrocycle, stimulated by recent experimental synthesis [Nat. Synth. 2023, 2, 395–402]. Transition densities reveal physical mechanism of spectral intensity in one-photon absorption (OPA) and two-photon absorption (TPA), and solvent effect strongly influence the spectral profile and intensity in TPA, but little influence the spectrum in OPA. The intra-unit and inter-unit charge transfer are visualized in five phenylenediamine linkers. The chirality of covalent organic pillars is revealed by electronic circular dichroism (ECD) spectroscopy, and interpreted by the visualized transition electric and magnetic dipole moments. Molecular vibrational information is demonstrated by normal and resonance Raman spectra and vibrational modes. The visualization of static and dynamic (hyper) polarization can reveal the physical mechanisms of polarization dependent normal and resonance Raman scattering. Our results provide deeper understanding on the physical mechanism of chiral covalent organic pillars as molecular nanotubes.