Materials Chemistry

Augmented Magnetic Response and Spin-Transfer in Copper Corrole/Graphene Hybrids - A DFT Study

Authors

  • Kerry Wrighton-Araneda Programa Institucional de Fomento a la Investigación, Desarrollo e Innovación, Universidad Tecnológica Metropolitana, Ignacio Valdivieso 2409, San Joaquín, Santiago, Chile & Universidad Bernardo O’Higgins, Centro Integrativo de Biología y Química Aplicada (CIBQA), General Gana 1702, Santiago, Chile, 8370854 ,
  • Diego Cortés-Arriagada Programa Institucional de Fomento a la Investigación, Desarrollo e Innovación, Universidad Tecnológica Metropolitana, Ignacio Valdivieso 2409, San Joaquín, Santiago, Chile. ,
  • Paulina Dreyse Universidad Técnica Federico Santa María, San Joaquín, Santiago, Chile ,
  • Simon Pascal Aix-Marseille Univ, CNRS, CINaM, UMR 7325, Campus de Luminy, 13288 Marseille Cedex 09, France ,
  • Gabriel Canard Aix-Marseille Univ, CNRS, CINaM, UMR 7325, Campus de Luminy, 13288 Marseille Cedex 09, France ,
  • Luis Sanhueza Departamento de Ciencias Biológicas y Químicas, Facultad de Recursos Naturales, Universidad Católica de Temuco, Temuco, Chile & Núcleo de Investigación en Bioproductos y Materiales Avanzados (BioMA), Universidad Católica de Temuco, Av. Rudecindo Ortega 02950, Temuco, Chile

Abstract

The search for hybrid materials with outstanding electronic performance is highly demanding Since copper corroles have emerged as versatile building blocks providing outstanding electronic, and reactivity properties, a new series of non-covalent hybrid materials were computationally investigated based on pristine graphene and A3-type copper corrole complexes. The corrole complexes contain strong electron-withdrawing fluorinated substituents at the meso positions. Our results show that the non-innocent character of corrole moiety modulates the structural, electronic, and magnetic properties of the hybrid systems. The graphene-corrole hybrids display outstanding stability via the interplay of dispersion and electrostatic driving forces while graphene act as an electron reservoir for more conductive cases. Furthermore, the hybrid structures display an intriguing magneto-chemical performance since a detailed analysis of magnetic properties evidence how structural and electronic changes contribute to the amplification of the magnetic response also for ferromagnetic and antiferromagnetic cases. This amplification is accompanied by the spin transfer which characterized by a directional spin polarization from the corrole through the graphene surface. Main results suggest that graphene-corrole hybrids are excellent candidates for technologic applications due to the ferromagnetic tendency, the augmented magnetic response, the tunability due to substituents, and the potential conductive properties. Finally, a statistical analysis of magnetic properties suggests correlations between spin transfer, augmented magnetic response, and the geometrical distortion of the copper ligand field, offering exciting hints about how to modulate the magnetic response in the studied hybrid systems.

Content

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Supplementary material

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Supporting Information Augmented Magnetic Response and Spin-Transfer in Copper Corrole/Graphene Hybrids: A DFT Study
This supplementary material contains seven figures related to the main manuscript including frontier molecular orbital, spin density, and independent gradient model surfaces, correlations plots of electronic properties, among others. A full Dataset of the most important files supports the investigation (DOI: 10.17632/p3d2xtfgcn.3).