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

Significance π-stacking of polynuclear aromatic rings encompasses fundamental scientific phenomena in chemical bonding and photophysics with strong impacts on societal aspects that include electronic devices, DNA/RNA intercalation, and optical sensing of environmental pollutants. This work describes unusually strong π-stacking in a recently synthesized naphthalene-diimide derivative, as well as a prototypical π-stacked molecule, pyrene. The infinite/cooperative π-stacking in the former and dimer stacking in the latter are much stronger than previously thought to be possible for this type of supramolecular interaction, reaching ∼50 and 20 kcal ⋅ mol−1, respectively. This has led to unusually large anisotropic thermal expansion and multicycle/multicolor thermochromism in BNDI-T, whereas multiple unusual binding and photophysical properties have been discovered for the classical organic chromophore pyrene. 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 (αa, αb, αc, 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.