As part of the Donostia International Physics Centre (DIPC), we are currently offering a paid summer internship for two months, aimed at last-year Master students interested in further pursuing a PhD. More information below.

Position details:

  • Title: Unlocking direct C-H activation with radical pairs

  • Duration: 8 weeks

  • Start Date: Flexible - June to July preferred.

  • Location: Faculty of Chemistry, UPV/EHU, San Sebastian, Basque Country, Spain.

  • How to Apply: Info here

Research Focus:

Saturated hydrocarbons represent the most abundant carbon feedstocks, yet their chemical valorisation is severely limited by the intrinsic inertness of aliphatic C–H bonds, which are strong, non-polar, and difficult to differentiate selectively. Conventional functionalization strategies therefore rely on pre-functionalization or harsh oxidative conditions, increasing synthetic inefficiency and waste. Radical-based approaches to direct C–H activation offer a compelling alternative, as open-shell intermediates enable C–H cleavage under comparatively mild conditions while providing access to reactivity patterns inaccessible to closed-shell pathways [1]. By allowing selective hydrogen-atom abstraction and subsequent functionalization without pre-installed handles, radical C–H activation not only improves step and atom economy but also reframes C–H bonds as programmable reaction sites for the late-stage and sustainable upgrading of saturated hydrocarbons.

In our group, we combine experimental and computational strategies to advance radical-based chemistry. In particular, we have recently shown that nitrobenzene induces the formation of potent hydrogen-atom transfer (HAT) radicals [2], opening the door to direct C–H activation under remarkably simple conditions. After HAT from a saturated hydrocarbon, the resulting carbon-centered radicals are primed to engage with the persistent nitrobenzene radical, providing an ideal reaction partner for subsequent radical cross-coupling reactions. This dual reactivity unlocks C–H activation via HAT and C(sp³)–C(sp²) bond formation in one pot, allowing C(sp²) functionalization to occur concomitantly with radical generation. As such, nitrobenzene serves not only as a C–H activation trigger but also as a built-in radical acceptor, unifying activation and functionalization within a single radical manifold.

Building on ongoing studies at the group, you will contribute to our most recent efforts by expanding the scope of C-H activation using radical chemistry. In particular, you will:

  • Perform reactions to assess C-H activation and radical cross-coupling reactions. This will involve reaction work-up, product separation by column chromatography and product characterisation by NMR spectroscopy and crystallisation techniques.

  • Characterise radical formation by means of electron paramagnetic resonance (EPR) spectroscopy.

  • Learn how to work on a glovebox for handling air and moisture sensitive radicals.

  • Expand the scope to other nitroaromatic compounds.

  • Learn the programming language Python, as an effective way to treat, organise and visualise data.

The candidate is expected to have a good knowledge of organic chemistry and electronic structure of molecules.

References:
[1] Z. Lu et al., Nature, 2023, 619, 514–520.
[2] S. A. Balahoju et al., ACS Omega 2025, 10, 22, 23798–23807