Developing synthetic methodology to crystallize extended covalent structures has been an
important pursuit of reticular chemistry. Here, we report a homogeneous synthetic route for
imine covalent organic frameworks (COFs) where crystallites emerge from clear solutions
without forming amorphous polyimine precipitates. The key feature of this route is the
utilization of tert-butyloxycarbonyl group protected amine building blocks, which are
deprotected in situ and gradually nucleate the crystalline framework. We demonstrate the …