Molecules, Vol. 28, Pages 4405: Syntheses and Electrochemical and EPR Studies of Porphyrins Functionalized with Bulky Aromatic Amine Donors

Molecules, Vol. 28, Pages 4405: Syntheses and Electrochemical and EPR Studies of Porphyrins Functionalized with Bulky Aromatic Amine Donors

Molecules doi: 10.3390/molecules28114405

Authors: Mary-Ambre Carvalho Khalissa Merahi Julien Haumesser Ana Mafalda Vaz Martins Pereira Nathalie Parizel Jean Weiss Maylis Orio Vincent Maurel Laurent Ruhlmann Sylvie Choua Romain Ruppert

A series of nickel(II) porphyrins bearing one or two bulky nitrogen donors at the meso positions were prepared by using Ullmann methodology or more classical Buchwald–Hartwig amination reactions to create the new C-N bonds. For several new compounds, single crystals were obtained, and the X-ray structures were solved. The electrochemical data of these compounds are reported. For a few representative examples, spectroelectrochemical measurements were used to clarify the electron exchange process. In addition, a detailed electron paramagnetic resonance (EPR) study was performed to estimate the extent of delocalization of the generated radical cations. In particular, electron nuclear double resonance spectroscopy (ENDOR) was used to determine the coupling constants. DFT calculations were conducted to corroborate the EPR spectroscopic data.