Charge transport properties of open-shell graphene fragments: a computational study of the phenalenyl tilings

Abstract

Thinking outside the box of the phenalenyl radical: a systematic structure design strategy, phenalenyl tiling, is found to benefit the electron transport properties of open-shell graphene fragments with one free radical. Compared with the closed-shell species, phenalenyl-based π-radicals exhibit smaller intramolecular reorganization energies and larger intermolecular electronic couplings. However, the on-site Coulomb repulsion can be too strong and impedes the charge transport efficiency of such materials. The repulsion can be weakened in radical species by spin delocalization. In this paper, the extended π-radicals we studied are categorized into three types of open-shell structures: the zigzag, the armchair and the discotic odd alternant hydrocarbons. The latter two belong to phenalenyl tilings. We found that the phenalenyl tilings fully inherit the desirable features of the singly occupied molecular orbital of the phenalenyl radical in a predictable and delocalized fashion, and their on-site Coulomb repulsion is effectively reduced. The zigzag π-radicals are less satisfactory. Therefore, the phenalenyl tilings are favorable candidates for charge transporting materials.