Research

Drawing inspiration from transition metal chemistry, our research group focuses on translating two powerful concepts to the main group: valence tautomerism and element-ligand cooperativity (ELC). Valence tautomerism arises when redox-non-innocent ligands facilitate reversible electron transfer with the central element, blurring the lines of formal oxidation states. While historically rare in main-group compounds, the drastically different reactivities of low- and high-oxidation state main-group elements offer immense, untapped potential. We are actively exploring main-group systems where these valence tautomeric transitions can be precisely triggered by external stimuli, such as light or Lewis bases, paving the way for advanced chemosensors, photoswitches, and photocatalysts.

Concurrently, we leverage ELC to activate small-molecule substrates cooperatively across an electrophilic central element and a nucleophilic ligand backbone. Our ultimate vision is to seamlessly merge these two paradigms. By combining stimulus-responsive valence tautomerism with ELC, we aim to access entirely novel reactivity channels, unlocking true catalytic turnover and novel transformations using molecular main-group systems.

The study of multiple bonds between heavier main-group elements has fundamentally revolutionized main-group chemistry, successfully dismantling long-held paradigms like the 'double-bond rule.' Once considered impossible to isolate, these inherently reactive species are now at the forefront of small molecule activation and are emerging in catalytic applications. Historically, the field has relied on kinetic stabilization, encasing the reactive main-group centers in extremely bulky substituents. In our research we are exploring novel, charged aromatic frameworks that support unusual main-group multiple bonds through thermodynamic means. By abandoning the need for heavy steric shielding, our systems leave the highly reactive main-group centers fully accessible, unlocking new avenues for molecular reactivity.

The introduction of highly fluorinated, electron-withdrawing ligand environments is a well-established and powerful concept in modern chemistry. By depleting the electron density of a central element, its acceptor properties are dramatically enhanced, enabling the design of exceedingly strong Lewis acids (LAs) for a variety of catalytic transformations. Furthermore, these robust Lewis acids serve as crucial electrophilic components of Frustrated Lewis Pairs (FLPs), which are widely used as cooperative, metal-free catalysts in a range of applications.

Building upon this established foundation, our research focuses on pushing the limits of these electron-withdrawing environments. We are investigating novel, highly fluorinated ligands to be paired with main-group compounds thereby enabling the generation of compounds with exceptionally high acceptor properties. By maximizing this Lewis acidity, we are developing next-generation systems tailored for advanced applications in both LA and FLP catalysis.

While Frustrated Lewis Pairs (FLPs) operate via polar, two-electron processes for the heterolytic cleavage of substrates, an exciting frontier emerges when single-electron transfer (SET) is introduced into the FLP framework. This generates Frustrated Radical Pairs (FRPs), fundamentally shifting the system from traditional polar reactivity to radical-driven homolytic bond activation. Because FRPs are remarkably reactive, they are capable of attacking notoriously inert chemical linkages, including difficult-to-polarize aliphatic C–H bonds.

Building on this, our group explores tethered FRP scaffolds as versatile platforms for advanced photocatalyzed transformations. We are actively working to extend and generalize the catalytic capabilities of FRPs, with the ultimate goal to unlock metal-free, direct C–H functionalizations, paving the way for new synthetic methodologies.