摘要： A feasible strategy relies on using heteroatom replacement which is namely chemical modification to the organic compound. Here we present this design concept for donor-acceptor complexes, which involves introducing nitrogen atoms to the middle ring of donor molecules to promote short contacts and reduce steric effect of the mixed framework. These nitrogen modified complexes are able to possess shorter molecular distance besides the mixed stacking pathway, enlarged π–π interactions or even a scarce 1:2.5 molar ratio through extra acceptor insertion. As a result, the unique 1:2 complex with nitrogen atoms on the different sides demonstrated stable electron field-effect mobility performance, while the binary system with no nitrogen replacement or N atoms on the identical side displayed poor ambipolar properties. These results confirmed that the heteroatom replacement is a powerful molecular design tool to fine tune the molecular packing of organic donor-acceptor complexes and their corresponding electronic properties.