Tetrabenzoporphyrins as organic semiconductors for high-performance organic field-effect transistors: a structure-property perspective

Organic electronic materials are crucial for next-generation flexible and lightweight devices. This review critically examines tetrabenzoporphyrins (BPs) as highly promising organic semiconductors for organic field-effect transistors (OFETs), with a particular focus on the impact of peripheral substituents on charge transport properties. We detail the synthetic methodologies for pristine and substituted BPs, including thermal precursor conversion, oxidative aromatization, and Heck reactions, enabling the precise introduction of meso- and benzo-substituents. Strategic derivatization with groups such as trimethylsilylethynyl, triisopropylsilylethynyl, alkyl, and aryl is shown to modulate intermolecular CH–π and π–π interactions, leading to diverse packing motifs such as one-dimensional slip-stacked, brickwork, herringbone, and layered structures. These varied molecular arrangements are demonstrated to critically influence carrier mobility and device performance. The review also discusses recent advances in tetrabenzodiazaporphyrins and supramolecular assemblies, highlighting their roles in enhancing thermal stability and charge transport. Experimental results, particularly single-crystal X-ray diffraction analyses and OFET characterizations, corroborate the significance of molecular packing in optimizing device performance. By elucidating the effects of substituent size, shape, and placement on molecular aggregation, this work provides comprehensive insights into BP-based OFETs. Ultimately, understanding these structure–function correlations offers valuable guidelines for the rational design of high-mobility, thermally robust organic semiconductors, paving the way for innovative applications in flexible electronics and advanced device architectures. This critical analysis provides strategic directions for future research and development, advancing the field of organic electronics.