Theoretical Study on Charge Transport Properties of a Series of “H-type” Acene Derivatives

Abstract

Linear fused acenes exhibit excellent charge transport properties but suffer from poor solubility and stability. This study investigates “H-type” acene derivatives to address the poor solubility and stability of linear acenes by Marcus theory and kinetic Monte Carlo simulations. The findings reveal that “H-type” conjugation enhances photostability, oxidative stability, and solubility compared to linear acenes, with series a exhibiting superior solubility. The reorganization energy decreases with molecular extension, following trends similar to linear acenes. Key electronic structure differences were identified: thiophene substitution (series b) localizes the highest occupied molecular orbital (HOMO) on the bridging carbon atoms, while benzene substitution (series a) localizes it on the central acene core. Crucially, a strong correlation is established between the molecular structure parameter |ΔR| and crystal packing modes: |ΔR|<0.7 yields 1D/2D stacking; 0.7<|ΔR|<1.1 produces herringbone packing; and |ΔR|>1.1 leads to beneficial pitched π-stacking. Mobility calculations showed benzene-extended derivatives exhibit strong anisotropy. Thiophene expansion (b-3) reduces anisotropy, and benzothiophene (b-3*) improves the anisotropic mobility of molecules. This is attributed to favorable S…C interactions that suppress detrimental molecular slip. These results provide a critical theoretical framework for future development of “H-type” acene materials.

Keywords

Acene derivative / Charge transport / Molecular stacking

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