A supramolecular engineering approach has been developed for a novel family of N-salicylidene aniline derivatives to control their thermo-and photochromic behaviours. Hsaltrz, Habs, Hsalphen, Hsaltz and Ksaltz are versatile molecules built from N-heterocycles, which drive the molecular arrangement to form a controlled crystal packing with predesigned optical properties. A complete structural, optical and computational study of powders of these new molecular nanoswitches is presented. An N-salicylidene aniline derivative possessing no thermo-or photoinduced chromic properties thanks to a specific molecular geometry was sought, and Habs and Hsalphen were designed to enhance π-π stacking