Spin in a Closed‐Shell Organic Molecule on a Metal Substrate Generated by a Sigmatropic Reaction

Abstract

Inert metal surfaces present more chances of hosting organic intact radicals than other substrates,but large amounts of delocalized electronic states favor charge transfer and thus spin quenching. Lowering the molecule-substrate interaction is ausual strategy to stabilizeradicals on surfaces.Insome works, thin insulating layers were introduced to provideacontrollable degree of electronic decoupling.R ecently,r etinoid molecules adsorbed on gold have been manipulated with as canning tunneling microscope (STM) to exhibit al ocalized spin, but calculations failed to find ar adical derivative of the molecule on the surface.Now the formation of aneutral radical spatially localized in at ilted and lifted cyclic end of the molecule is presented. An allene moiety provokes ap erpendicular tilt of the cyclic end relative to the rest of the conjugated chain, thus localizing the spin of the dehydrogenated allene in its lifted subpart. DFT calculations and STM manipulations give support to the proposed mechanism.

Observation of Biradical Spin Coupling through Hydrogen Bonds

“…The dehydrogenation process has been used to generate spin on the graphene nanostructure [39]. In a previous report, a magnetic ReA molecule was considered as a radical that was generated by H-atom transfer and sigmatropic reaction [40]. However, the mechanism leads to a localized spin.…”

Observation of biradical spin coupling through hydrogen bonds

“…The dehydrogenation process has been used to generate spin on the graphene nanostructure [30]. In a previous report, a magnetic ReA molecule was considered as a radical which was generated by H-atom transfer and sigmatropic reaction [31]. However, the mechanism leads to a localized spin.…”