Interaction of Fe3+meso-tetrakis (2,6-dichloro-3-sulfonatophenyl) porphyrin with cationic bilayers: magnetic switching of the porphyrin and magnetic induction at the interface

An organized multilayer was constructed by the layer-by-layer technique in which alternating layers of metalloporphyrin and dioctadecyldimethylammonium bromide bilayers were deposited onto an indium tin oxide surface electrode. The porphyrin molecules that are organized in the different layers showed a strong electroactivity with a well-defined electrochemical process. In LbL, electroactivity could be explained only by the occurrence of electron hoping. Thus, total Kohn?CSham density functional theory (KS-DFT) was performed to better understand the conditions responsible for the electroactivity of the metalloporphyrin layers intercalated by an insulating material. Total KS-DFT theory involves local density approximation energy calculations based on spin-polarized variant of KS-DFT theory. The results revealed a magnetization switching of the metalloporphyrin induced by the interaction with the surfactant bilayer accompanied by spin polarization of the porphyrin-interacting surfactant molecule. Although discrete, the surfactant magnetization had significant repercussions on the electron conductivity. Calculations also demonstrated loss of porphyrin symmetry promoted by a parent surfactant with a shorter hydrocarbon chain, ditetradecyldimethylammonium bromide. The calculation results were corroborated by experimental results obtained by the electron paramagnetic resonance and magnetic circular dichroism techniques.