Covalently Linked 5,6,11,12-Tetraazanaphthacene Dimer and Its Triptycene-Capped Derivatives as Electron Acceptors

The development of electron transport and n-type materials is still largely dominated by a limited number of organic semiconductors, with fullerenes at the forefront. In contrast, substantial progress has been made in developing hole transport and p-type materials. Therefore, expanding the range of electron acceptors, making them solution-processable, and elucidating their structural arrangement by X-ray crystallography is essential. We synthesised 2,2'-bi-(5,6,11,12-tetraazanaphthacene) (bi-TANC) and its triptycene end-capped derivative, 2,2'-bi(8,13-dihydro-8,13-[1,2]benzenonaphtho-5,6,15,16-tetraazanaphthacene) (bi-TpTANC), as electron acceptors. Bi-TANC exhibits a herringbone-like crystal packing with intermolecular π-π overlap, which is observed in typical organic n-type semiconductors. However, it showed poor solubility, similar to larger acenes. In contrast, bi-TpTANC exhibited favourable solubility, and its electrochemistry in solution was investigated. In the cyclic voltammogram of bi-TpTANC, reversible redox waves corresponding to 3-step/4-electron transfer were observed at -0.795 V (1e^-), -0.927 V (1e^-), and -1.44 V (2e^-) as half-wave potentials. The redox wave associated with the two-electron transfer on the negative low-potential side indicates the presence of through-bond charge delocalisation in the monoanionic state. Furthermore, the LUMO level of bi-TpTANC is -4.1 eV, which indicates its potential as a promising air-stable n-type material.