Learn about all of the exciting research going on in the Anderson Lab.
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Hybrid inorganic-organic materials such as Metal Organic Frameworks (MOFs) show a wide range of physical and chemical properties that can be tuned by selecting and tailoring the metal nodes and organic linkers. Our research interests are focused on hybrid materials that display integrated properties of redox activity, electrical conductivity, porosity, and magnetism, which have potential for spintronics, batteries, supercapacitors, and data storage devices.
Most MOFs utilize long, rigid linkers containing carboxylates and diamagnetic metal centers to obtain robust, porous structures. However, this approach usually results in weak electronic and magnetic coupling between metal nodes, leading to insulating materials without interesting electronic or magnetic properties. In pursuit of novel multifunctional hybrid materials, we propose several strategies: (1) use of S-based linkers, (2) use of redox-active nodes and linkers, and (3) installation of radical linkers.
Controlling the movement of protons and electrons is fundamental to harnessing chemical reactions towards useful products. While some precious metal catalysts are highly effective at mediating multi-proton/multi-electron processes, these types of reactions are often significantly more difficult when using more economical first-row metals. To lessen the burden on these metals, metal-ligand cooperativity is often used where the ligand can also participate in proton or electron transfer to more efficiently carry out these multi-proton or multi-electron processes.
Redox-active ligands and ligands with pendant acidic or basic functionalities have been well studied and are very effective for improving the reactivity of first-row metals. However, few ligand systems incorporate both redox-activity and pendant protons to enable H-atom or H2 transfer from the ligand to mediate very challenging catalytic transformations. We have been studying diimino- and dihydrazono-pyrrole ligands to investigate this type of reactivity.
Transition metal oxo complexes are implicated in a wide variety of enzymatic and synthetic reactions, from C-H bond activation to O-O bond formation. There have been many examples of isolable metal oxo complexes which are overwhelmingly found in tetragonal ligand environments and feature early transition metals such as Mn and Fe. Studies of the reactivity of these complexes has focused on understanding the paradigms that guide C-H activation, O-atom transfer, and O-O bond formation.
To explore new areas in the field, the Anderson lab focuses efforts on exploiting atypical coordination environments and incorporation of electrostatic interactions to manipulate metal oxo chemistry. Due to changes in electronic structure, use of alternative coordination geometries allows for the isolation of complexes with high d-electron count metal ions. Such species are expected to have unusual properties, such as altered basicity or radical character on O, that may result in unique C-H activation and O-O bond forming reactions. In particular, we have focused on studying pseudo-tetrahedral oxo complexes featuring Co, Ni, and Cu to investigate these possibilities. Alternatively, a new means of manipulating the properties of metal oxo complexes is the utilization of electric fields. We propose to synthesize ligands containing distal anionic charges to perturb the electronic structure of oxo complexes and probe the agency of O radical character in their reactivity.