Tetrazine-based linkers as intrinsically tagged alternatives for click functionalization of metal-organic frameworks

Reticular chemistry has in the post-synthetic modification (PSM) of frameworks one of the most versatile tools to adapt the systems' physicochemical properties to the specific requirements which are imposed by their application in different contexts. We can safely say that PSM methodologies in all their variants are currently one of the main resources that reticular chemists turn to when they need to diversify a framework compositionally. Practically all these modifications require the integration of functional groups appended to the organic linkers in the framework, either by direct synthesis or by post-synthetic exchange. The reactivity of these tags allows, at a subsequent stage, covalent modification of the framework under conditions that ideally respect its structural integrity. In this perspective article we introduce the use of tetrazine-based linkers as intrinsically tagged alternatives to integrate PSM with click chemistry reactivity. This strategy is ideally suited to molecular frameworks, as it combines very mild modification conditions with direct control over the organisation of built-in appendices and the acknowledged potential of click chemistry to build framework libraries.