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Structure, DFT based investigations on vibrational and nonlinear optical behavior of a new guanidinium cobalt thiocyanate complex

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Abstract

This paper reports the crystal growth and structure of a newly synthesized hybrid organic-inorganic compound (CH6N3)2[Co (NCS)4].H2O by means of a joint experimental and theoretical study. Single-crystal X-ray diffraction reveals that this compound crystallizes in the noncentrosymmetric P21212 space group. The 3D framework of the crystal structure is formed by hydrogen-bonded cations of (CH6N3)+, [Co (NCS)4]2− anions and water molecules. UV-Visible reveals an indirect allowed optical transition with energy gap Eg = 3.41 eV. The optimized molecular structure, harmonic vibrational frequencies, static and frequency-dependent nonlinear optical (NLO) parameters were calculated by density functional theory with and without dispersion corrections. A good consistency for the structure, as well as IR and Raman spectra, is found between the calculated and experimental results. A detailed interpretation of the vibrational modes was carried out and a total assignment was performed on the basis of the potential energy distribution (PED) contribution. Moreover, the inter-ionic interaction energy was evaluated and a decomposition analysis was performed by localized molecular orbital energy decomposition analysis (LMO-EDA) method. The calculated NLO parameters compared to urea as a reference show that the title compound can be a good candidate for NLO applications.

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Acknowledgments

The authors gratefully acknowledge the support of the Tunisian Ministry of Higher Education and Scientific Research for LR11ES46 and the Center for Scientific Computing in Aarhus (CSCAA).

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Correspondence to H. Triki.

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Triki, H., Nagy, B., Overgaard, J. et al. Structure, DFT based investigations on vibrational and nonlinear optical behavior of a new guanidinium cobalt thiocyanate complex. Struct Chem 31, 103–114 (2020). https://doi.org/10.1007/s11224-019-01380-3

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Keywords

  • Crystal structure
  • Vibrational frequency
  • EDA
  • Interaction energies
  • LMO-EDA
  • Dispersion correction
  • DFT calculations