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The effect of alkyl substituents in the β-side on the conformation, molecular structure, and copper-oxygen bond strength of bis(β-diketonato)copper(II) complexes by DFT results and experimental vibrational and UV spectra

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Abstract

The conformation, geometry, and relative energies of bis (2,6-dimethylheptane-3,5-dionato)copper(II), (Cu(DIMHD)2), and bis (5,5-dimethylhexane-2,4-dionato)copper(II), Cu(DMHD)2 have been assayed through using calculated results from atoms-in-molecules (AIM) analysis, time-dependent density functional theory (TD-DFT), natural bond orbital (NBO), and density functional theory (DFT). The electronic and vibrational spectra of these compounds have also been studied using experimental infrared, Raman, and ultraviolet (UV) spectra. All theoretical and empirical vibrational frequencies of the mentioned compounds have been assigned. The DFT was used to characterize the conformers of the complexes mentioned above, as well as the observed vibrational and UV spectra. Similar complexes, including copper (II) acetylacetonate Cu(AA)2, bis(3,5-heptanedionato)copper(II) (Cu(HPD)2), and copper (II) 2,2,6,6-tetramethylheptane-3,5-dionate (Cu(TMHD)2), have been chosen to evaluate the influence of isopropyl (iPr) and tert-Butyl (t-Bu) groups substituents instead of methyl and ethyl groups. All experimental, spectroscopic, and DFT results confirmed that the O-Cu bond strength in Cu(DIMHD)2 and Cu(DMHD)2 is between Cu(TMHD)2 and Cu(AA)2 and close to Cu(HPD)2.

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Acknowledgements

Support of this investigation by Ferdowsi University of Mashhad (project number 45085) is gratefully acknowledged.

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The authors did not receive support from any organization for the submitted work.

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Authors and Affiliations

  1. Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad, Mashhad, Iran

    Mahnoosh Hakimi-Tabar, Mohammad Vakili, Vahidreza Darugar, Sayyed Faramarz Tayyari & Mohammad Reza Housaindokht

  2. UNESCO-UNISA Africa Chair in Nanoscience and Nanotechnology (U2ACN2), College of Graduate Studies, University of South Africa (UNISA), Pretoria, South Africa

    Mahmood Akbari

  3. Material Research Division, Nanoscience African Network (NANOAFNET), iThemba LABS-National Research Foundation, Somerset Africa West, 7129, South Africa

    Mahmood Akbari

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  1. Mahnoosh Hakimi-Tabar
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Contributions

M. H-T. helped in conceptualization and data curation; M. V. contributed to supervision, review, and editing; V. D. Advisor was involved in writing original draft preparation; M. A. Advisor was involved in review and editing final draft; S. F. T. Advisor was involved in review and editing; M. R. H. was involved in supervision, review, and editing; all authors have read and agreed to the published version of the manuscript.

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Correspondence to Mohammad Vakili.

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Hakimi-Tabar, M., Vakili, M., Darugar, V. et al. The effect of alkyl substituents in the β-side on the conformation, molecular structure, and copper-oxygen bond strength of bis(β-diketonato)copper(II) complexes by DFT results and experimental vibrational and UV spectra. Transit Met Chem 48, 315–329 (2023). https://doi.org/10.1007/s11243-023-00545-8

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