Mapping of N−C Bond Formation from a Series of Crystalline Peri‐Substituted Naphthalenes by Charge Density and Solid‐State NMR Methodologies

A combination of charge density studies and solid state nuclear magnetic resonance (NMR) 1JNC coupling measurements supported by periodic functional theory (DFT) calculations is used to characterise the transition from an n–π* interaction bond formation between a nucleophilic nitrogen atom electrophilic sp2 carbon in series crystalline peri-substituted naphthalenes. As N⋅⋅⋅C distance reduces there sharp decrease Laplacian derived increasing two groups at ca. = 1.8 Å, with DFT predicting, heteronuclear spin-echo NMR confirming, couplings ≈3–6 Hz for long C−N bonds (1.60–1.65 Å), <1 >2.1 Å.