General routes to confined spaces of welldefined chemical composition and complex three-dimensional structure have long been sought by materials chemists. Here, we introduce metal−organic framework (MOF) materials as an ideal scaffold upon which such organized complexity can be built. Employing an orthogonal coordination strategy, we constructed a large-pore MOF material with two different modifiable linkers in well-defined positions relative to each other. The independent and quantitative covalent grafting of two distinct chemical groups onto these differently reactive linkers yielded a uniformly bifunctionalized MOF material. Not only does this methodology offer an efficient route via which the properties of well-defined microporous materials can be fine-tuned, but it also creates a solid-state platform for synthetically accessing constructs that better emulate the well-ordered intricacy of biological structures.

We exploit orthogonal chemical reactivity to generate uniformly multifunctionalized confined spaces in a simultaneous, one-pot reaction.

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.

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