Redox-triggered switching in three-dimensional covalent organic frameworks

The tuning of molecular switches in solid state toward stimuli-responsive materials has attracted more and more attention in recent years. Herein, we report a switchable three-dimensional covalent organic framework (3D COF), which can undergo a reversible transformation through a hydroquinone/quinone redox reaction while retaining the crystallinity and porosity. Our results clearly show that the switching process gradually happened through the COF framework, with an almost quantitative conversion yield. In addition, the redox-triggered transformation will form different functional groups on the pore surface and modify the shape of pore channel, which can result in tunable gas separation property. This study strongly demonstrates 3D COFs can provide robust platforms for efficient tuning of molecular switches in solid state. More importantly, switching of these moieties in 3D COFs can remarkably modify the internal pore environment, which will thus enable the resulting materials with interesting stimuli-responsive properties. Tuning of molecular switches in solid state toward stimuli-responsive materials attracted attention in recent years but has not yet been realized in three-dimensional (3D) covalent organic frameworks (COFs). Herein, the authors demonstrate a stable and switchable 3D COF which undergoes reversible transformation through a hydroquinone/quinone redox reaction.