Recent literature reports indicate that derivatives of benzothiadiazole (BT) and benzobis(thiadiazole) (BBT), which differs from BT by an extra thiadiazole ring, exhibit good semiconducting properties, such as high electron mobility and low-lying lowest unoccupied molecular-orbital (LUMO) levels. In this study herein, computational techniques like density functional theory (DFT), spin-flip DFT and valence-bond methods are used to analyze the semiconducting properties of these molecules. Calculations at the B3LYP/cc-pVTZ level reveal that all the BBT molecules, including the bare BBT ring, have lower lying LUMO energies (3.70–4.11 eV) compared to the BT derivatives (2.56–3.41 eV) with similar substitution. The reorganization energies (λ+/λ−) obtained at this level of theory of the BT derivatives are around (225–333)/(246–315) meV, while BBT derivatives have much smaller reorganization energies and these are in the range of (129–259)/(150–230) meV. We observe that the different behavior of BBT is due to the inherited biradicaloid character from the parent molecule tetramethylenebenzene (TMB), a disjoint non-Kekule biradical having non-bonding molecular orbitals (NBMOs) as the highest occupied molecular orbital (HOMO) and LUMO. Additionally, the perturbation of the orbitals of the biradical TMB to obtain BBT is the major cause for the BBT derivatives to have a larger electron affinity (EA) and a smaller HOMO–LUMO gap (HLG) compared to BT derivatives.