Charge transfer in superbase n-type doping of PCBM induced by deprotonation

N-type electronic doping of organic semiconductors (OSCs) by using superbase compounds shows high doping efficiency (Adv. Mater. 2023, 35, 2300084). While a deprotonation reaction is believed to trigger the doping process, the detailed mechanism therein is not yet fully understood. In the present work we theoretically study the electronic structure of the deprotonated Phenyl-C61-butyric acid methyl ester (PCBM) molecule, as well as the charge transfer (CT) between PCBM and its deprotonated species. We find that deprotonated PCBM without formation of a new bond between the deprotonated side chain and fullerene induces electronic structure with broken spin symmetry, where an in-gap state is singly occupied by an unpaired electron. A second scenario that we find to be possible is the formation of a new bond between the deprotonated side chain and a fullerene. This leads to a spin symmetric electronic structure with partially localized in-gap state, which is expected to contribute less to the effective doping. These results show that the deprotonated PCBM species without new bond formation predominantly accounts for the effective n-type doping of PCBM, an insight that will be useful for optimization of this recently discovered doping method.