On-surface homocoupling reactivity of a chiral bifunctional bromoindanone molecule on Cu(111)

Fatima Hussein (1) , Corentin Pigot (2) , Francisco Romero Lairado (3) , Marco Minissale (3) , Eric Salomon (3) , Thierry Angot (3) , Frédéric Dumur (2) , Malek Nechab (2) , Didier Gigmes (2) , Sylvain Clair (1) , Luca Giovanelli (1)

1 IM2NP - Institut des Matériaux, de Microélectronique et des Nanosciences de Provence
2 ICR - Institut de Chimie Radicalaire
3 PIIM - Physique des interactions ioniques et moléculaires

On-surface synthesis has provided exciting concepts for the building of covalently bonded molecular nanostructures as well as the exploration of new synthetic pathway alternatives to chemical synthesis in solution. The surface-supported reaction of precursor molecules can result in the formation of 2D molecular networks as well as novel 0D molecular structures. In this study, we investigate in ultrahigh vacuum by low-temperature scanning tunneling microscopy the adsorption of the chiral molecule (R)-6-bromo-3-phenyl-2,3-dihydro-1H-inden-1-one (BrPhINDO) on the Cu(111) surface. Annealing an as-deposited layer of molecules allows to activate two kinds of homocoupling reactions, the Ullmann-like coupling and the Knoevenagel reaction, resulting in the formation of various low-dimensional structures. By studying their prochirality and comparing with the products obtained with the enantiomer precursor, we demonstrate adsorption-induced chiral inversion inducing partial racemization.

Domaines: Science des matériaux [cond-mat.mtrl-sci]; Matériaux

Fatima Hussein, Corentin Pigot, Francisco Romero Lairado, Marco Minissale, Eric Salomon, et al.. On-surface homocoupling reactivity of a chiral bifunctional bromoindanone molecule on Cu(111). New Journal of Chemistry, 2022, 46 (47), pp.22869-22876. ⟨10.1039/D2NJ04708J⟩. ⟨hal-03888491⟩