Tetrabenzo‐10‐Heterocorroles as π‐Extended Porphyrinoid Semiconductors: Synthesis, Properties, Structure, and OFET Performance

Tetrabenzo-10-heterocorrole metal complexes were successfully synthesized. These π-extended molecules exhibited narrow HOMO–LUMO energy gaps due to the effective π-delocalization incorporating the heteroatom. Single crystal X-ray diffraction revealed that tetrabenzothiacorrole Ni^II complex (Ni-BSC) adopts a highly planar structure. The organic field-effect transistor based on Ni-BSC showed hole transporting property with the mobility of 1.3 × 10⁻² cm² V⁻¹ s⁻¹.

Abstract

There has been renewed interest in the development of 10-heterocorrole metal complexes, which are a type of ring-contracted porphyrinoids, due to their intriguing photophysical and electrochemical properties based on the unique macrocyclic structures. In this study, we synthesized and characterized a series of tetrabenzo-10-heterocorrole metal complexes to investigate their structure–property relationships and explore potential application in organic semiconductors. Experimental and theoretical studies indicated that tetrabenzo-10-heterocorroles have narrow HOMO–LUMO energy gaps due to the extended backbone with effective π-delocalization. Single crystal X-ray diffraction analysis revealed that tetrabenzo-10-thiacorrole Ni^II complex (Ni-BSC) adopts a highly planar structure. Furthermore, the OFET device based on the polycrystalline thin film of Ni-BSC, where the molecules take 1D slipped antiparallel stacking to counteract the dipole moment of the molecule, exhibited hole transport with the mobility of 1.3 × 10⁻² cm² V⁻¹ s⁻¹. These findings suggest that tetrabenzo-10-heterocorroles are potential candidates for future exploration in organic electronic applications.

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