Covalent Organic Frameworks: Reversible 3D Coalesce via Interlocked Skeleton-Pore Actions and Impacts on π Electronic Structures.

Covalent organic frameworks (COFs) create extended two-dimensional (2D) skeletons and aligned one-dimensional (1D) channels, constituting a class of novel π architectures with predesignable structural ordering. A distinct feature is that stacks of π building units in skeletons shape the pore walls, onto which a diversity of different units can be assembled to form various pore interfaces, opening a great potential to trigger a strong structural correlation between the skeleton and the pore. However, such a possibility has not yet been explored. Herein, we report reversible three-dimensional (3D) coalescence and interlocked actions between the skeleton and pore in COFs by controlling hydrogen-bonding networks in the pores. Introducing carboxylic acid units to the pore walls develops COFs that can confine water molecular networks, which are locked by the surface carboxylic acid units on the pore walls via multipoint, multichain, and multidirectional hydrogen-bonding interactions. As a result, the skeleton undergoes an interlocked action with pores to shrink over the x - y plane and to stack closer along the z direction upon water uptake. Remarkably, this interlocked action between the skeleton and pore is reversibly driven by water adsorption and desorption and triggers profound effects on π electronic structures and functions, including band gap, light absorption, and emission.