A hydrogen-bonded organic framework possessing one-dimensional wide channels surrounded by the naphthalenediimide plane.

π-Conjugated molecule-based porous organic frameworks that possess both one-dimensionally π-stacked columnar domains and pore channels surrounded by the π-conjugated surface are a sophisticated platform for optoelectronic materials responsive to chemical stimuli. In this paper, we report a hydrogen-bonded organic framework (HOF) with a wide inclusion channel whose surfaces are composed of the π-conjugated plane of naphthalenediimide (NDI). The Brunauer-Emmett-Teller surface area was determined to be 1410 m2 g-1. Slip-stacking of a hydrogen-bonded two-dimensional network composed of tetracarboxylic acid NDITA with an NDI core provides both electron-conductive π-stacked NDI domains and pore channels surrounded by the NDI surface. Since aromatic solvents can come into contact with the NDI moieties in the pores, the HOF exhibits solvent-dependent photophysical behaviors. In particular, inclusion of dimethoxybenzene (DMB) into the pores enhances charge-transfer interactions, resulting in significant changes in absorption and emission spectra as well as electron conductivity.