• • NTI-BTT achieves an electron mobility of 0.13 cm2 V−1 s−1, quadrupling the 0.0325 cm2 V−1 s−1 of the NDI-based counterpart, directly enabling faster n-type OFETs for complementary logic.
• • Thiophene fusion in NTI-BT causes a mobility collapse to 0.004 cm2 V−1 s−1, a 32.5-fold reduction versus NTI-BTT, due to grain-boundary-induced trap states in polycrystalline films.
• • Thiophene spacer insertion in NTI-BTT yields a π-π stacking distance of 3.45 Å, enhancing intermolecular electronic coupling and charge transport.
• • NTI-terminated triads exhibit deeper LUMO levels and more planar backbones than NDI analogs, improving electron injection and ambient stability for n-type operation.