Imine‐based covalent organic frameworks (COFs) are a widely studied class of functional, crystalline, and porous nanostructures which combine a relatively facile crystallization with tuneable compositions and porosities. However, the imine linkage constitutes an intrinsic limitation due to its reduced stability in harsh chemical conditions and its unsuitability for in‐plane π‐conjugation in COFs. Urgent solutions are therefore required in order to exploit the full potential of these materials, thereby enabling their technological application in electronics, sensing, and energy storage devices. In this context, the advent of a new generation of linkages derived from the chemical conversion and locking of the imine bond represents a cornerstone for the synthesis of new COFs. A marked increase in the framework robustness is in fact often combined with the incorporation of novel functionalities including, for some of these reactions, an extension of the in‐plane π‐conjugation. This Minireview describes the most enlightening examples of one‐pot reactions and post‐synthetic modifications towards the chemical locking of the imine bond in COFs.

Metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) have attracted enormous attention in recent years.R ecently,M OF@COF are emerging as hybrid architectures combining the unique features of the individual components to enable the generation of materials displaying novel physicochemical properties.Herein we report an unprecedented use of aza-Diels-Alder cycloaddition reaction as post-synthetic modification of MOF@COF-LZU1, to generate aza-MOFs@COFs hybrid porous materials with extended p-delocalization. Aaproof-of-concept, the obtained aza-MOFs@COFs is used as electrode in supercapacitors displaying specific capacitance of 20.35 mFcm À2 and high volumetric energy density of 1.16 Fcm À3 .O ur approach of post-synthetic modification of MOFs@COFs hybrids implement rational design for the synthesis of functional porous materials and expands the plethora of promising application of MOFs@COFs hybrid porous materials in energy storage applications.