In inorganic and materials chemistry, it is customary for researchers to label metal–organic frameworks (MOFs) using the abbreviation of the institution at which any new family of these materials were first synthesized. Now, with a new paper in the special New Talent: Americas, 2024 issue of Dalton Transactions, the Korzyński Bespoke Materials Laboratory (KBML) at the Department of Chemistry has disclosed the first MOF family named after the University of Toronto.
MOFs are a burgeoning class of materials that exhibit exceptional crystallinity and high porosity. These porous materials are remarkable playgrounds for synthetic chemists due to their atomically precise structure, which makes them desirable for a myriad of applications.
Some of these uses include drug delivery, biosensing, and environmental cleanups—MOFs can sense pollutants, clean contaminants from both water and air, and break down organic pollutants. In the renewable energy space, they are utilized for hydrogen production in photocatalytic processes that use solar energy for water splitting reactions, whose products are hydrogen and oxygen molecules. In chemical industry they can be used as formidable heterogeneous catalysts. MOF chemistry is also under exploration for energy storage applications such as formation of new generation of batteries and super capacitors.
KBML, which is located on the U of T Mississauga campus, applies the principles of traditional molecular synthetic inorganic chemistry to push the frontiers of MOF synthetic elaboration. Recognizing the limitations of existing MOFs, the KBML group has recently focused lately on a search for new olefinic pillared MOFs that feature large pores, ones that could easily be accessed by bulkier reactants. The result? Design and synthesis of pillared metal–organic frameworks featuring olefinic fragments, whose authors include Professor Maciej Korzyński and U of T Ph.D. student Rachel Mander, as well as collaborators from Bruker.
These pillared MOFs would expand the capacity of alkene-based MOFs, which are limited by their microporosity. As the paper’s authors put it, “Because of the small pore sizes and/or apertures, there is only a limited array of molecules that can be introduced into the framework."
Chemistry Stories asked Rachel Mander to tell us more.
What makes the UofT MOFs unique and noteworthy?
One of the key building blocks of MOFs is the organic linker. These organic linkers can incorporate a wide variety of functional groups, which can be used for further chemical elaboration of the material.
Our lab has recently become fascinated with MOFs featuring olefinic fragments, since they can be further modified in an endless number of ways to tailor the properties of the material to its end application. Despite these prospects, the selection of olefinic MOFs available for us to use is still limited. One of the most glaring limitations is the small pore openings typically found in these materials that limit the size of the reactants that can be introduced into pores. As a result, we cannot take full advantage of olefinic fragments embedded within the MOF.
In our recent work we address this challenge by introducing Ni-based material, UofT-2(Ni), with pores large enough to circumvent limitations of the existing olefinic MOFs. Crucially, these pores can be vacated and filled with other molecules without the decomposition of the MOF.
Rachel, what drew you to this particular area of study?
I was drawn to this project because I’m interested in material design and modification, specifically targeted towards green chemistry developments, like carbon capture and clean energy sources. The tunability of MOFs makes them perfect platforms to explore these research areas.
Working on this gave me the opportunity to explore material design and learn more about the intricacies of MOF chemistry. I’m excited to utilize UofT MOFs to advance my research interests in green chemistry applications.
How do you envision them being utilized?
We are convinced that UofT MOFs, in particular UofT-2(Ni), will become a go-to platform — not only for us, but also other researchers in the field — for exploration of new chemical methods of post-synthetic tuning of MOF properties that specifically target olefinic fragments. With the increased pore sizes, we will be able to use reactants that could not be used before to achieve this goal. Imagine all the possibilities!
Then there are specific applications your lab is focused on? Crucial tasks where existing MOFs, with their small pore sizes, don’t perform well?
As a coordination chemist at heart, I am eager to explore the chemistry of UofT MOFs with metal complexes. These complexes are typically large (on a molecular scale) and our UofT-2(Ni) MOF is perfect for accommodating such bulky guests. By doing so we are hoping to generate new catalytic materials that will lead to a more sustainable chemical industry.
Asked how it felt to have a hand in disclosing the first U of T MOFs, Prof. Korzyński said: “It is both exciting and a great privilege to bring UofT name into the realm of MOFs, particularly for a young faculty member at the beginning of an independent career. Considering the human capital and incredible resources available at University of Toronto, I hope that this is only the beginning of a new chapter in ground-breaking MOF research done at UofT.
Learn more about KBML here: https://bespoke-materials.com/