Stepwise Synthesis of Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) are a category of porous materials that offer unparalleled control over their surface areas (demonstrated as higher than for any other material), pore characteristics, and functionalization. This allows them to be customized for exceptional performance in a wide variety of applications, most commonly including gas storage and separation, drug delivery, luminescence, or heterogeneous catalysis. In order to optimize biomimicry, controlled separations and storage of small molecules, and detailed testing of structure-property relationships, one major goal of MOF research is "rational design" or "pore engineering", or precise control of the placement of multiple functional groups in pores of chosen sizes and shapes. MOF crystal growth can be controlled through judicious design of stepwise synthetic routes, which can also allow functionalization of MOFs in ways that were previously synthetically inaccessible. Organic chemists have developed a library of powerful techniques over the last century, allowing the total synthesis and detailed customization of complex molecules. Our hypothesis is that total synthesis is also possible for customized porous materials, through the development of similar multistep techniques. This will enable the rational design of MOFs, which is a major goal of many researchers in the field. We have begun developing a library of stepwise synthetic techniques for MOFs, allowing the synthesis of ultrastable MOFs with multiple crystallographically ordered and customizable functional groups at controlled locations within the pores. In order to design MOFs with precise control over pore size and shape, stability, and the placement of multiple different functional groups within the pores at tunable distances from one another, we have concentrated on methods which allow us to circumvent the lack of control inherent to one-pot MOF crystallization. Kinetically tuned dimensional augmentation (KTDA) is an approach using preformed metal clusters as starting materials and monotopic carboxylates as equilibrium shifting agents to make single crystals of ultrastable MOFs. Postsynthetic metathesis and oxidation (PSMO) takes advantage of the fast ligand exchange rate of a metal ion at the low oxidation state as well as the kinetic inertness of the same metal at high oxidation state to make ultrastable and highly crystalline MOFs. Multiple similar strategies have been successful for the metathesis of Fe-based MOFs to Cr3+. Several highly crystalline Ti-MOFs have also been prepared. Kinetically controlled linker installation and cluster metalation methods utilize a stable MOF with inherent coordinatively unsaturated sites as matrix and postsynthetically install linkers or grow clusters on the matrix, so that a robust MOF with precisely placed functionalities is realized. This method has diverse applications especially when specific functional groups or metals having synergistic effects are desired in the proper proximity. Exceptional porosity and stability are required for many potential applications. We have demonstrated several of these, including entrapment of nanoscaled functional moieties such as enzymes. We have developed a series of metal-organic frameworks (PCN-333) with rationally designed ultralarge mesoporous cages as single-molecule traps for enzyme encapsulation. We successfully incorporated metalloporphyrins, well-known biofunctional moieties, into robust MOFs for biomimetic catalytic applications. By rationally tuning the synthetic conditions, we obtained several different porphyrinic Zr-, Fe-, and Ti-MOFs with distinct pore size and concentrated acid or base stability, which offer eligible candidates for different applications. These and other stepwise kinetic tuning and catalyst incorporation methods are small steps toward achieving the grand challenge of detailed control of the placement of matter on an atomic and molecular level.