Synthesis, crystal structure and charge transport characteristics of stable peri-tetracene analogues.

Abstract

peri-Acenes have shown great potential for use as functional materials because of their open-shell singlet biradical character. However, only a limited number of peri-acene derivatives larger than peri-tetracene have been synthesized to date, presumably owing to the low stability of the target compounds in addition to the complicated synthesis scheme. Here, a very simple synthesis route for the tetrabenzo[a,f,j,o]perylene (TBP) structure enables the development of highly stable peri-tetracene analogues. Despite a high degree of singlet biradical character, the compounds with four substituents at the zigzag edge show a remarkable stability in solution under ambient conditions, which is better than that of acene derivatives with a closed-shell electronic configuration. The crystal structures of the TBP derivatives were obtained for the first time; these are valuable to understand the relationship between the structure and biradical character of peri-acenes. The application of peri-acenes in electronic devices should also be investigated. Therefore, the semiconducting properties of the TBP derivative were investigated by fabricating the field-effect transistors.