Uniform and Simultaneous Orthogonal Functionalization of a Metal-Organic Framework Material

We report the construction of a large-channel MOF material composed of two linkers that bear orthogonally reactive groups, azides and hydroxyls, that can be addressed independently. The two linkers also have distinct coordination chemistry and assemble in well-defined positions relative to each other throughout the MOF crystals. The subsequent covalent grafting of two different chemical functionalities onto these reactive linkers is both independent and quantitative, yielding uniformly multifunctional confined spaces. To further demonstrate the advantage of orthogonal reactivity, we performed the uniform and quantitative binary MOF functionalization in a simultaneous, one-pot reaction.