ArticleAngewandte Chemie (International ed. in English)2026
Dispersion-Clamped Crystalline Supramolecular Columnar π-Stacks of Adamantyl-Substituted Pyrenes.
Article in Angewandte Chemie (International ed. in English), 2026. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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Abstract
Despite their importance in supramolecular chemistry, zero-offset columnar π-stacks of polycyclic aromatic hydrocarbons (PAHs) are rarely observed in crystals because close cofacial packing is penalized by Pauli repulsion. Here we show a crystalline phase (CP) of adamantyl-substituted pyrene that exhibits one-dimensional, translationally aligned columnar π-stacks enabled by dispersion-assisted adamantyl "clamps". Single-crystal x-ray diffraction reveals an exceptionally short interplanar separation of 3.297(3) Å at 100 K. Energy-decomposition analysis shows that the adamantyl substituents provide larger dispersion stabilization relative to their Pauli penalty, rationalizing the formation of the zero-offset π-columns. The solution-to-crystal color shift is exceptionally large (ΔE
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