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The present work provides an alternative mechanism of SMT and demonstrates that the composition gradient across the vdW gap in the bilayer materials can be another degree of freedom to tune the band gaps without introducing extrinsic elements. Our findings will benefit the material design for small-scale and energy-efficient electronic devices.We report two families of naphthalenediimides (NDIs) symmetrically functionalized with discrete carbon chains comprising up to 55 carbon atoms (C n -NDI-C n , n = 39, 44, 50, and 55) and their sel