Molecular Charge-to-Spin Conversion to Access Organic Radicals – EPR Characterisation, DFT Mechanism & Synthetic Applications.

Organic radicals are key intermediates in chemistry and biology, yet their controlled generation, detailed characterization, and targeted application remain significant challenges owing to their intrinsic reactivity and the strict structural requirements often imposed on radical precursors. Rather than relying on conventional approaches, our research explores how electron-transfer processes can induce charge-to-spin conversion in stable molecules, creating new opportunities to access radical species across broad and previously unexplored regions of chemical space. In this lecture, I will present the research activities of my group aimed at understanding, controlling, and exploiting these phenomena through the combined use of electron paramagnetic resonance (EPR) spectroscopy, quantum chemistry, and organic chemistry. In particular, I will discuss recent results on single-electron transfer in Lewis pairs and show how the resulting mechanistic insights define a previously unrecognized reactivity manifold capable of unifying disparate experimental observations reported in the literature. I will also demonstrate how these concepts provide a straightforward route to radical generation under remarkably mild conditions across the chemically important family of nitroaromatics. Together, these studies illustrate how the integration of EPR spectroscopy, electronic-structure theory, and organic chemistry provides a powerful framework for transforming charge into spin and, ultimately, spin into chemical reactivity.