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Copper (II) complexes with novel Schiff-based ligands: synthesis, crystal structure, thermal (TGA–DSC/FT-IR), spectroscopic (FT-IR, UV-Vis) and theoretical studies

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Abstract

This study aimed to synthesize two novel Schiff-base ligands through the condensation between N-(2-aminoethyl)pyrazoles and 2-hydroxy-1-naphthaldehyde, which are: NaphPz ((E)-1-(((2-(1H-pyrazol-1-yl)ethyl)imino)methyl)naphthalen-2-ol)) and NaphDPz ((E)-1-(((2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl)imino)methyl)naphthalen-2-ol). These novel pyrazole-imines were synthesized, characterized and used as copper (II) ion complexing agents. Different synthetic routes have been adapted to obtain the [Cu(NaphPz)Cl], [Cu(NaphDPz)Cl] and [Cu(NaphPz)2] complexes in the solid state, the first two in the crystalline form and the latter as a powder. The minimum metal–ligand stoichiometry for the three complexes was defined by TGA–DSC thermoanalytical data and by single-crystal X-ray diffraction for the crystalline samples which belong to the P21/n space group. The products of the thermal decomposition of the material were also monitored by TGA–DSC/FT-IR in air and N2 atmospheres in order to suggest how thermal decomposition of the organic portion of the complex occurs. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations compared to experimental results (UV-Vis and FT-IR) show a high degree of correlation. From HOMO/LUMO orbitals, the main major charge distributions, responsible for the absorption bands of the complexes, were determined.

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Acknowledgements

The authors thank Brazilian Foundations CNPq, Fundect, Capes and Finep for financial support, and are grateful to Professor Massao Ionashiro for allowing us to carry out measurements in the Ivo Giolito Thermal Analysis Laboratory (LATIG) – UNESP, and Professional Noemi Marques de Carvalho for English reviewing.

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Authors and Affiliations

  1. Federal University of Grande Dourados, UFGD, CP 364, Dourados, MS, 79804–970, Brazil

    Jeniffer Meyer Moreira, Guilherme Fava Campos, Cristiane Storck Schwalm & Cláudio Teodoro de Carvalho

  2. Federal University of Mato Grosso do Sul, Campo Grande, MS, 79074-460, Brazil

    Leandro Moreira de Campos Pinto & Gabriel Rodrigues Martins

  3. Federal University of Santa Maria, UFSM, Santa Maria, RS, 97105-900, Brazil

    Bárbara Tirloni

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  1. Jeniffer Meyer Moreira
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Correspondence to Cláudio Teodoro de Carvalho.

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Moreira, J.M., Campos, G.F., de Campos Pinto, L.M. et al. Copper (II) complexes with novel Schiff-based ligands: synthesis, crystal structure, thermal (TGA–DSC/FT-IR), spectroscopic (FT-IR, UV-Vis) and theoretical studies. J Therm Anal Calorim 147, 4087–4098 (2022). https://doi.org/10.1007/s10973-021-10803-5

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