International E-publication: Publish Projects, Dissertation, Theses, Books, Souvenir, Conference Proceeding with ISBN.  International E-Bulletin: Information/News regarding: Academics and Research

New one-pot synthetic route and spectroscopic characterization of Hydroxo-bridged Stepped-cubane Copper(II) complexes

    ,

Author Affiliations

  • 1Department of Chemistry, Federal University Otuoke, P.M.B. 126, Yenagoa, Bayelsa State, Nigeria
  • 2Department of Chemistry, University of Ilorin, P.M.B. 1515, Ilorin, Kwara State, Nigeria

Res.J.chem.sci., Volume 13, Issue (2), Pages 1-9, June,18 (2023)

Abstract

A new convenient and efficient route for the synthesis of two very important hydroxo-bridged stepped-cubane copper complexes viz: [Cu4(bpy)4Cl2(OH)4]Cl2.6H2O (1) and [Cu4(phen)4Cl2(OH)4]Cl2.6H2O (2) have been obtained. This synthetic route from the mononuclear CubpyCl2complex is easier, more reproducible and afforded the complex in a much higher yield than the other two previously reported procedures which were equally serendipitously discovered. The purity and formation of the complexes were confirmed with elemental (C,H,N) analysis and the details of the UV-Vis, Fourier transform infrared, electrospray ionization mass spectra of both complexes and the single crystal X-ray crystallography of 1 are presented and discussed. X-ray crystallography confirms the absolute structure of the complexes. The complexes were formed via the connection of four copper atoms to four hydroxide bridging ligands and four bipyridyl ligands with two chloride ligands. There are two coordinate environments around two pairs of copper atoms (CuN2ClO2 and CuN2O3) and each copper atom is pentacoordinate with square pyramidal geometry.

References

  1. Moustakas, M. (2021)., The Role of Metal Ions in Biology, Biochemistry and Medicine., Materials (Basel, Switzerland), 14(3), 549. https://doi.org/10.3390/ ma14030549
  2. Tsang, T., Davis, C.I. and Brady, D.C. (2021)., Copper Biology., Curr Biol., 31(9), R421-R427. https://doi.org/10.1016/j.cub.2021.03.054
  3. Wang, P., Yuan, Y., Xu, K., Zhong, H., Yang, Y., Jin, S., Yang, K. and Qi, X. (2021)., Biological applications of copper-containing materials., Bioactive materials, 6(4), 916-927.
  4. Sagar, S., Sengupta, S., Mota, A.J., Chattopadhyay, S.K., Ferao, A.E., Riviere, E., Lewis, E., Naskar, S. (2017)., Cubane-like tetranuclear Cu(II) complexes bearing a Cu4O4 core: crystal structure, magnetic properties, DFT calculations and phenoxazinone synthase like activity., Dalton Trans., 46, 1249-1259.
  5. Paul, A., Mistri, S., Bertolasi, V. and Manna, S.C. (2019)., DNA/protein binding and molecular docking studies of two tetranuclear Cu(II) complexes with double-open-cubane core like structure., Inorg. Chim. Acta, 495, 119005, https://doi.org/10.1016/j.ica.2019.119005.
  6. Ardizzoia, G.A. and Brenna, S. (2016)., Hydroxo-bridged copper(II) cubane complexes., Coord. Chem. Rev., 311, 53-74. https://doi.org/10.1016/j.ccr.2015.11.013.
  7. Vafazadeh, R. and Willis, A.C. (2015)., Tetra(μ3-hydroxo) Bridged Copper(II) Tetranuclear Cubane Complexes: Synthesis, Crystal Structure, and DNA Binding Studies., J. Coord. Chem., 68(13), 2240-2252.
  8. Mehrani, A., Sorolla, M.G., Makarenko, T. and Jacobson, A.J. (2021)., A New 1-1-4 Pattern of Magnetic Exchange Interactions in A Cubane Core Tetranuclear Copper (II) Complex., Polyhedron, 199, 115088.
  9. Thakurta, S., Roy, P.P., Butcher, R.J., Fallah, M.S., Tercero, J., Garribba, E. and Mitra, S. (2009)., Ferromagnetic Coupling in a New Copper(II) Schiff Base Complex with Cubane Core: Structure, Magnetic Properties, DFT Study and Catalytic Activity., Eur. J. Inorg. Chem., 29, 4385-4395. https://doi.org/10.1002/ ejic.200900493
  10. Asadi, Z., Zarei, L., Golchin, M., Skorepova, E., Eigner, V. and Amirghofran, Z. (2020)., A Novel Cu(II) Distorted Cubane Complex Containing Cu4O4 Core as the First Tetranuclear Catalyst for Temperature Dependent Oxidation of 3,5-Di-Tert-Butyl Catechol and in Interaction with DNA & Protein (BSA)., Spectrochim Acta A Mol Biomol Spectrosc. 227, 117593. https://doi.org/10.1016 /j.saa.2019.117593
  11. Jiang, X., Li., J., Yang., B., Wei., X., Dong, B., Kao, Y., Huang, M., Tung, C. and Wu, L. (2018)., A Bio-inspired Cu4O4Cubane: Effective Molecular Catalysts for Electrocatalytic Water Oxidation in Aqueous Solution., Angew. Chem. Int. Ed., 57, 7850–7854. https://doi.org/10.1002/anie.201803944
  12. Gao, W., Wang, J., Shi, N., Chen, C., Fan, Y. and Wang, W. (2019)., Electrocatalytic Water Oxidation Studies of a Tetranuclear Cu(II) Complex with Cubane-like Core Cu4(μ3-O)4., New J. Chem., 43, 4640-4647. https://doi.org/10.1039/ C8NJ06263C
  13. Karmakar, A., Oliver, C.L., Roy, S. and Öhrström L. (2015)., The Synthesis, Structure, Topology and Catalytic Application of a Novel Cubane-Based Copper(II) Metal–Organic Framework Derived From a Flexible Amido Tripodal Acid., Dalton Trans., 44, 10156-10165. https://doi.org/ 10.1039/ C4DT03087G
  14. Sletten, J., Sørensen, A., Julve, M., and Journaux, Y. (1990)., A Hydroxybridged Tetranuclear Copper(II) Cluster of the Cubane Type. Preparation and Structural and Magnetic Characterization of tetrakis [2,2’-bipyridyl) hydroxocopper(ii)] hexafluorophosphate., Inorg. Chem., 29, 5054-5058. Https://doi.org/10.1021/ic00350a010
  15. Zheng, Y. and Lin, J. (2002)., Hydroxo-bridged Tetranuclear CuII Complexes :{[Cu(bpy)(OH)]4Cl2]Cl2. 6H2O and {[Cu(phen)(OH)]4(H2O)2]Cl4.4H2O., Z. Anorg. Allg. Chem., 628, 203-208. https://doi.org/10.1002/ zaac.200300003
  16. Carballo, R., Covelo, B., Vazquez-Lopeza, E.M., Garcıa-Martınez, E. and Castineiras, A. (2002)., A New Preparative Route of the Stepped-Cubane Tetranuclear Copper(II) Compound, [Cu4(μ2-OH)2(μ3-OH)2Cl2(bipy)4] Cl2•6H2O., Z. Anorg. Allg. Chem., 628, 907-908.