Tetrazine‐Based Metal‐Organic Frameworks as Scaffolds for Post‐Synthetic Modification by the Click Reaction

Abstract

Metal‐organic frameworks are one of the most active research fields today. Despite the progress in recent years, synthesis of highly porous structures bearing functional groups for specific applications remains a challenge. Here, we describe synthesis of Zr(IV) and Hf(IV)‐based tetrazine containing metal‐organic frameworks, ZrTz‐68 and HfTz‐68 with pore size of 2.1 nm, specific surface area up to 4217 m 2 g –1 , and a UiO‐68 topology. The synthesis can be done on a multi‐gram scale from inexpensive linker 4,4'‐(1,2,4,5‐tetrazine‐3,6‐diyl)dibenzoic acid (H 2 TzDB). Moreover, because of the π‐conjugated tetrazine groups these MOFs can be easily post‐synthetically modified by a “click” reaction maintaining the crystallinity of the framework. Due to the diversity of “clickable” substituents, this strategy represents highly versatile tool for a wide range of applications.