Coordination bonding of Ni(II) tetraazamacrocyclic (TAMC) complexes to carboxylic groups of organic polymers and graphene oxide paper (GOP) is proposed for a facile generation of paramagnetic centers by combining two diamagnetic components. The coordination functionalization occurs under basic conditions in water solution at room temperature. The coordination configuration of central Ni(II) changes from tetracoordinated square-planar to hexacoordinated pseudooctahedral, which implies the conversion from low-spin to high-spin nickel centers. In the case of organic polymers, the coordination bonding of Ni(II) macrocycles gives rise to characteristic changes in coloration (from yellow-orange to violet-blue), as well as clearly manifests itself in UV–visible, FTIR and EPR spectra. In the case of GOP, in addition to evident changes in FTIR spectra, morphological alterations in the mat surface and an increase in the mat thickness are observed in SEM images, which can be explained by an intercalating effect of voluminous macrocyclic cations, as well as by partial disintegration of GOP structure due to the liquid-phase treatment. The effective magnetic moments of tetraazamacrocycles attached to organic polymers vary from 0.88 to 1.47 BM, whereas for GOP considerably higher values of 2.10 and 2.87 BM were obtained.
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Financial support from the National Autonomous University of Mexico (UNAM, grant DGAPA-IN101118) and from the National Council of Science and Technology of Mexico (CONACYT, Grant 250655) is greatly appreciated. The authors acknowledge the University Laboratory of Spectroscopic Characterization of UNAM (Laboratorio Universitario de Caracterización Espectroscópica, LUCE_ICAT_UNAM) for the opportunity to measure FTIR, Raman and UV–visible spectra, and Dr. Victor Meza-Laguna (Instituto de Ciencias Nucleares UNAM) for the acquisition of SEM images and EDS spectra. V. A. B. and E. V. B. also thank the “Programa de Apoyos para la Superación del Personal Académico” (PASPA) UNAM for supporting their sabbatical stay at CIICAp UAEM. C. C. O.-B. is indebted to the Master Degree Program in Chemical Sciences of UNAM and to CONACyT for MSc scholarship.
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Basiuk, E.V., Ocampo-Bravo, C.C., Gómez-Vidales, V. et al. Generation of paramagnetic centers in carboxylated materials via coordination attachment of diamagnetic tetraazamacrocyclic complexes of nickel(II). J Mater Sci 55, 5364–5377 (2020). https://doi.org/10.1007/s10853-020-04372-5