Article
Electronic, Molecular, and Solid-state Structural Effects of Strong Electron Withdrawing and Donating Groups in Functionalized Fluorophthalonitriles
Journal of Porphyrins and Phthalocyanines
(2021)
Abstract
Perfluoro phthalonitrile substituted separately with perfluoroalkyl (EW) and NH2, NHMe, and NMe2 (ED) groups generate a series of aromatic CH 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 the solidstate 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.
Disciplines
Publication Date
January 22, 2021
DOI
10.1142/S1088424621500164
Citation Information
Marius Pelmus, Jeffrey G. Raab, Hemantbhai H. Patel, Christopher Colomier, et al.. "Electronic, Molecular, and Solid-state Structural Effects of Strong Electron Withdrawing and Donating Groups in Functionalized Fluorophthalonitriles" Journal of Porphyrins and Phthalocyanines (2021) ISSN: 1099-1409 Available at: http://works.bepress.com/stephen_kelty/15/