A collaborative research effort led by the University of Wisconsin-Madison, in partnership with Colorado State University and the University of Colorado Boulder, has demonstrated a novel approach to electron-transfer chemistry that addresses a fundamental constraint in molecular synthesis.
Traditionally, electron-transfer reactions follow predictable patterns based on thermodynamic preferences. When two molecules compete for a single electron, the electron naturally transfers to the molecule most capable of stabilizing the extra charge. This inherent selectivity has long restricted chemists’ ability to direct reactions toward alternative outcomes, limiting the types of molecular connections that can be formed through single-electron transfer—a widely used technique in pharmaceutical development, materials science, and biomimetic synthesis.
The new research introduces a different conceptual framework by employing a catalyst that directly ejects electrons into the surrounding solvent rather than attempting to manage electron transfer through conventional chemical selectivity. Once released into solution, the free electron becomes highly reactive and indiscriminate, readily attaching to the first available molecule. This contrasts sharply with the typical situation, where electrons preferentially target molecules with favorable reduction potentials.
Computational analysis conducted at Colorado State University and spectroscopic investigations at the University of Colorado Boulder revealed the mechanism underlying this unexpected selectivity. The critical distinction does not occur during initial electron transfer but rather in the subsequent reaction steps. The desired product-forming molecule proceeds along its reaction pathway while the thermodynamically favored molecule returns to its starting state, effectively being recycled rather than consumed.
Professor Zachary Wickens, who led the Wisconsin team, characterized the findings as representing a fundamental shift in reaction design strategy. The research, recently published in Nature, suggests that modifying assumptions about when and where selectivity is determined in electron-transfer chemistry could significantly expand the repertoire of achievable molecular couplings and create opportunities for synthetic pathways previously considered inaccessible.
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