Single‐Crystal Organic Field‐Effect Transistors Based on 5,15‐Bisaryl‐Tetrabenzoporphyrins: Synthesis, Structure, and Charge Transport Properties

Abstract This study reports the fabrication and performance of single‐crystal organic field‐effect transistors (SC‐OFETs) based on three 5,15‐bisaryl‐tetrabenzoporphyrin ( BP ) derivatives: C8Ph‐BP , C8Ph‐Ph‐BP , and Ph‐BP , where C8Ph and Ph are 4‐ n ‐octylphenyl and phenyl groups, respectively. These compounds are designed to investigate how meso ‐substituted C8Ph and Ph groups affect molecular packing and charge transport properties of BP derivatives. X‐ray crystallography analysis confirms that all derivatives exhibit a herringbone packing structure. SC‐OFETs using single crystals of each derivative demonstrate maximum hole mobilities of 1.64 cm ² V ⁻ ¹ s ⁻ ¹ for C8Ph‐BP , 0.89 cm ² V ⁻ ¹ s ⁻ ¹ for C8Ph‐Ph‐BP , and 1.21 cm ² V ⁻ ¹ s ⁻ ¹ for Ph‐BP . The high mobility of C8Ph‐BP is attributed to its interdigitated parallel π‐stacking, enhanced by van der Waals interactions between n ‐octyl groups. In contrast, Ph‐BP and C8Ph‐Ph‐BP show lower charge mobilities. This work demonstrates the influence of the n ‐octyl and meso ‐phenyl groups on the packing arrangements and the charge transport efficiency in SC‐OFETs, offering insights into optimizing organic semiconductors for high‐performance electronic applications.