Nonplanar Nanographene: A Hydrocarbon Hole‐Transporting Material That Competes with Triarylamines

Hole‐transporting materials (HTMs) are essential for optoelectronic devices, such as organic light‐emitting diodes (OLEDs), dye‐sensitized solar cells, and perovskite solar cells. Triarylamines have been employed as HTMs since they were introduced in 1987. However, heteroatoms or side chains embedded in the core skeleton of triarylamines can cause thermal and chemical stability problems. Herein, we report that hexabenzo[a,c,fg,j,l,op]tetracene (HBT), a small nonplanar nanographene, functions as a hydrocarbon HTM with hole transport properties that match those of triarylamine‐based HTMs. X‐ray structural analysis and theoretical calculations revealed effective multidirectional orbital interactions and transfer integrals for HBT. In‐depth experimental and theoretical analyses revealed that the nonplanarity‐inducing annulative π‐extension can achieve not only a stable amorphous state in bulk films, but also a higher increase in the highest occupied molecular orbital level than conventional linear or cyclic π‐extension. Furthermore, an in‐house manufactured HBT‐based OLED exhibited excellent performance, featuring superior curves for current density–voltage, external quantum efficiency–luminance, and lifetime compared to those of representative triarylamine‐based OLEDs. A notable improvement in device lifetime was observed for the HBT‐based OLED, highlighting the advantages of the hydrocarbon HTM. This study demonstrates the immense potential of small nonplanar nanographenes for optoelectronic device applications.