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Eur J Org Chem - 2026 - Achilleos - Toward Sustainable NHC‐Based Photosensitizers Scalable Synthesis and.pdf
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  • Achilleos, KaterinaInstitut de la Matière Condensée et des Nanosciences (IMCN) Molecular Chemistry Materials and Catalysis (MOST, Université catholique de Louvain (UCLouvain) Louvain‐la‐Neuve Belgium
    Author
  • Ranjan, PrabhatInstitut de la Matière Condensée et des Nanosciences (IMCN) Molecular Chemistry Materials and Catalysis (MOST, Université catholique de Louvain (UCLouvain) Louvain‐la‐Neuve Belgium
    Author
  • Baroudi, GhenaInstitut de la Matière Condensée et des Nanosciences (IMCN) Molecular Chemistry Materials and Catalysis (MOST, Université catholique de Louvain (UCLouvain) Louvain‐la‐Neuve Belgium
    Author
  • Glaser, FelixInstitut de la Matière Condensée et des Nanosciences (IMCN) Molecular Chemistry Materials and Catalysis (MOST, Université catholique de Louvain (UCLouvain) Louvain‐la‐Neuve Belgium
    Author
  • Troian‐gautier, Ludovicorcid-logoInstitut de la Matière Condensée et des Nanosciences (IMCN) Molecular Chemistry Materials and Catalysis (MOST, Université catholique de Louvain (UCLouvain) Louvain‐la‐Neuve Belgium
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Abstract
Iron-NHC (N-heterocyclic carbene) complexes hold strong promise as earth-abundant alternatives to Ru-and Ir-based photo-sensitizers, but their synthesis represents additional challenges. Here, we present a systematic study aimed at developing a robust, reproducible, and scalable protocol for the synthesis of [Fe(Brphtmeimb) 2 ] + that is suitable for researchers of all skill levels. By examining the effects of base, solvent, temperature, concentration, and iron source, we identified several previously overlooked parameters, including FeBr 2 solubility, temperature-dependent precipitation, and solvent quality, that significantly impact reaction outcome. Optimization revealed that low-temperature addition of LiHMDS and dilute reaction conditions (0.02 M) afford consistently improved yields. Further adjustment of ligand and base stoichiometry enabled reliable scale-up, delivering the target complex in 64% yield on a 1 mmol scale. This practical procedure provides broad, dependable access to [Fe(Brphtmeimb) 2 ] + , facilitating its use across catalysis, materials chemistry, and related fields. Furthermore, we show postfunctionalization routes of [Fe(Brphtmeimb) 2 ] + via Suzuki-type coupling and expand the reaction scope to include additional transition metals such as Mn(IV) and Co(III).
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Citations

Achilleos, K., Ranjan, P., Baroudi, G., Glaser, F., Abudayyeh, A., Narayan, L., Thunissen, T., Robeyns, K., & Troian‐gautier, L. (2026). Toward Sustainable NHC‐Based Photosensitizers: Scalable Synthesis and Postfunctionalization of Fe, Co, and Mn Complexes. European Journal of Organic Chemistry, e70518. https://doi.org/10.1002/ejoc.70518 (Original work published 2026)