Iranian Journal of Chemistry

Iranian Journal of Chemistry

DFT-TDDFT study of a dinuclear Cobalt(II) complex with a 20-membered macrocyclic ligand

Document Type : Original Article

Authors
Hamid Rostami dana 1
Marjan Abedi 1
Amir Nasser Shamkhali 2
1 Department of chemistry, Faculty of Science, University of Mohaghegh Ardabili, Ardabil, Iran
2 Department of chemistry, Faculty of Science, University of Mohaghegh Ardabili, Ardabil, Iran.
10.22036/cr.2023.375535.1198
Abstract
n this research study, DFT-TDDFT calculations were used to analyze the electronic structure and simulation of the electronic absorption spectrum of the dinuclear cobalt(II) complex with II–II oxidation state of 20-membered N4, binucleating macrocycle derived by a cyclic [2 + 2] condensation of isophthaldialdehyde with 1,3-diaminopropane using CAM-B3LYP hybrid-DFT functional and 6-311+G(d,p) basis set. The structure of the [Co2LBr2OH]Br complex was optimized using density functional theory for all of the possible spin states of the complex. On the basis of the DFT results for spin 1, 3, 5, and 7 spin states, there is a clear thermodynamic preference for septet spin multiplicity even at 0 K, which exhibits two independent cobalt centers with tetrahedral coordination geometries, as can be concluded from their tau parameters. The TDDFT calculation demonstrates transitions from the β-spin HOMOs having mainly dxy, dxz character to the β-spin LUMOs with dominant Co dz2, dyz and dx2_y2 character.

Graphical Abstract

DFT-TDDFT study of a dinuclear Cobalt(II) complex with a 20-membered macrocyclic ligand
Keywords
Macrocycle
Dinuclear complex
Cobalt(II)
DFT/TDDFT

Subjects

  1. [1] G. Parkin, Chem. Rev. 104, 699 (2004).

    [2] B. Y. Lee, H. Y. Kwon, S. Y. Lee, S. J. Na, S. Han, H. Yun, H. Lee, Y. Park, J. Am. Chem. Soc 127, 3031 (2005).

    [3] J. Gao, J. H. Reibenspeis, R. A. Zingaro, F. R. Wooly, A. E. Martell, A, Inorg. Chem. 44, 232 (2005).

    [4] D. Kong, A. E. Martell, R. J. Motekaitis, Ind. Eng. Chem. Res. 39, 3429 (2000).

    [5] J. Huang, D. Fengli, Sh. Li, D. Yang, W. Sun, W. Tang, J. Inorg. Biochem. 98, 502 (2004).

    [6] F. B. Johansson, A. D. Bond, U. G. Nielsen, B. Moubaraki, K. S. Murray, K. J. Berry, J. A.

    Larrabee, C. J. McKenzie, Inorg. Chem. 47, 5079 (2008).

    [7] M. Abedi, R. J. Butcher, A. N. Shamkhali, V. Spasojevic, K. Al-Ameed, P. Abedi, inorganica

    Chim. Acta 520, 120310 (2021).

    [8] M. Abedi, K. Kirschbaum, A. N. Shamkhali, C. R. Brue, A. A. Khandar, Polyhedron, 109, 176 (2016).

    [9] M. Abedi, A. N. Shamkhali, R. J. Butcher, A. A. Khandar, P. Garczarek, G. Mahmoudi, S. A. Hosseini-Yazdi, Polyhedron 119, 98 (2016).

    [10] A. A. Khandar, K. Kirschbaum, M. Abedi, K. Mock, G. Tracy, New J. Chem. 39, 2822 (2015).

    [11]N. A. Bailey, D. E. Fenton, R. Moody, C. O. Rodriguez de Barbarin, I. N. Sciambarella, J. M.

    Latour, D. Limosin and V. McKee, J. Chem. Soc. Dalton Trans. 2519 (1987).

    [12]D. E. Polyansky, D. C. Grills, M. Z. Ertem, K. T. Ngo, E. Fujita, ACS Catal. 12, 1706 (2022).

    [13]Q. Wang, Sh. Zhang, P. Cui, A. B. Weberg, L. M. Thierer, B. C. Manor, M. R. Gau, P. J. Carroll, N.

    1. Tomson. Inorg. Chem. 59, 4200 (2019).

    [14] B. Ghanbari, L. Asadi Mofarrah, A. Jamjah, New J. Chem. 46, 20745 (2022).

    م. عابدی، ع. ا. خاندار (،١٣٩٢ بهمن ماه). ساختار کریستالی [14]

    لیگاند ماکروسیکلی بر پا یه ی (II (کمپلکس دوهسته ای کبالت

    با گروههای برمید. مقاله ارایه شده در ب یست و یکمین متا- زایلیل

    همایش بلورشناسی و کانی شناسی ا یران ، دانشگاه سیستان و

     بلوچستان. بازیابی شده در وب سایت

    https://civilica.com/doc/746472

    [15]M. Valiev, E. J. Bylaska, N. Govind, K. Kowalski, T. P. Straatsma, H. J. J. van Dam, D. Wang, J.

    Nieplocha, E. Apra, T. L. Windus, W. A. de Jong, Comput. Phys. Commun., 181, 1477 (2010).

    [16]T. Yanai, D. Tew, N. Handy, Chem. Phys. Lett., 393, 51 (2004).

  • Receive Date 13 December 2022
  • Revise Date 23 January 2023
  • Accept Date 24 January 2023