Strong π-stacking causes unusually large anisotropic thermal expansion and thermochromism.

π-stacking in ground-state dimers/trimers/tetramers of N-butoxyphenyl(naphthalene)diimide (BNDI) exceeds 50 kcal ⋅ mol-1 in strength, drastically surpassing that for the *3[pyrene]2 excimer (∼30 kcal ⋅ mol-1; formal bond order = 1) and similar to other weak-to-moderate classical covalent bonds. Cooperative π-stacking in triclinic (BNDI-T) and monoclinic (BNDI-M) polymorphs effects unusually large linear thermal expansion coefficients (α a , α b , α c , β) of (452, -16.8, -154, 273) × 10-6 ⋅ K-1 and (70.1, -44.7, 163, 177) × 10-6 ⋅ K-1, respectively. BNDI-T exhibits highly reversible thermochromism over a 300-K range, manifest by color changes from orange (ambient temperature) toward red (cryogenic temperatures) or yellow (375 K), with repeated thermal cycling sustained for over at least 2 y.