Molecular cylinders with donor–acceptor structure and swinging motion

Abstract

The construction of three-dimensional nanocarbon structures with well-defined molecular dynamics is a challenging yet rewarding task in material science and supramolecular chemistry. Herein, we report the synthesis of two highly defective, nitrogen-doped molecular cylinders, namely MC1 and MC2, with a length of 1.4 nm and 2.7 nm, respectively. These molecular cylinders are constructed by connecting the cycloparaphenylene endcaps and fused aromatic pillars using a cyclocondensation reaction, affording a distinct donor-acceptor structure. An X-ray crystallographic analysis reveals a tilted cylindrical shape for MC1, and nuclear magnetic resonance spectroscopy and calculations indicate the occurrence of a dynamic swinging motion in solution. The elongation of conjugation in the cylinders attenuates the charge transfer character in the first excited state, resulting in remarkable length-dependent photophysical properties.