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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

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Abstract

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–Sham 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.

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Acknowledgments

We are grateful to FAPESP, CNPq, and CAPES. KCUM is research fellow supported by a FAPESP fellowship. We thank also to Karl J. Jalkanen, FAPESP-supported visitor professor of Universidade do Vale do Paraíba (UNIVAP), Brazil for the invitation to contribute our work to the Imamura Festschrift Issue of TCA and by the critical reading and comments contributing to improve the manuscript. We thank UFABC and CENAPAD-Campinas/SP (Centro Nacional de Processamento de Alto Desempenho) for the computational facilities.

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  1. Centro de Ciências Naturais e Humanas (CCNH), Universidade Federal do ABC, Rua Santa Adélia, 166, Santo André, SP, 09210-170, Brazil

    Katia C. U. Mugnol, Marccus V. A. Martins, Edvaldo C. Nascimento, Otaciro R. Nascimento, Frank N. Crespilho & Iseli L. Nantes

  2. Centro de Engenharia, Modelagem e Ciências Sociais Aplicadas (CECS), Universidade Federal do ABC, Rua Santa Adélia, 166, Santo André, SP, 09210-0170, Brazil

    Jeverson T. Arantes

  3. Grupo de Biofísica “Sergio Mascarenhas”, Universidade de São Paulo, São Carlos, SP, Brazil

    Otaciro R. Nascimento

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  1. Katia C. U. Mugnol
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  2. Marccus V. A. Martins
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  3. Edvaldo C. Nascimento
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Correspondence to Jeverson T. Arantes or Iseli L. Nantes.

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Dedicated to Professor Akira Imamura on the occasion of his 77th birthday and published as part of the Imamura Festschrift Issue.

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Mugnol, K.C.U., Martins, M.V.A., Nascimento, E.C. et al. 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. Theor Chem Acc 130, 829–837 (2011). https://doi.org/10.1007/s00214-011-1055-0

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