Electronic, molecular, and solid-state structural effects of strong electron withdrawing and donating groups in functionalized fluorophthalonitriles

Perfluoro phthalonitrile substituted separately with perfluoroalkyl (EWG) and NH22, NHMe, and NMe22 (EDG) groups generate a series of aromatic C-H bonds-free nitriles that can now lose electrons, whose HOMO-LUMO gap is narrowed by EDG beyond the level induced by EWG, and whose dipole moments double. Molecular parameters vary linearly with Hammett's free-energy constants, their electronic underpinning being uncovered by DFT calculations. The phthalonitriles' assembling in solid-state structures is determined by forces that transition from van der Waals, in the case of EWG, to H-bonding and/or π-stacking interactions in the case of EDG, as revealed by their single-crystal X-ray structures.