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Comparative cation sensing properties of a newly designed urea linked ferrocene-benzimidazole dyad: a DFT study

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Abstract

Herein, our primary motivation was to elucidate the electronic and physicochemical properties of a novel molecular dyad consisting of ferrocene (Fc; electron donor), urea (u; linker), and amphoteric benzimidazole (BI; electron acceptor) entities. The sensor responses were investigated for various divalent transition metal cations (Mn2+, Fe2+, Co2+, Ni2+, Cu2+, and Zn2+) and the selectivity of this cationophore molecule (Fc-u-BI) to copper ion (Cu2+) was demonstrated by using B3LYP/LANL2DZ method. According to the thermochemical calculations, we justified that Fc-u-BI⋯Cu2+ reached to the lowest binding energy (∆E), enthalpy (∆H), and Gibbs free energy (∆G) changes. In the light of the calculated global descriptors, Fc-u-BI⋯Cu2+ was found to be the softer and thus the most reactive complex. The complex stabilities and their corresponding non-covalent interactions were also investigated by NBO and NCI analyses, respectively.

The mechanistic insight into metal cation sensing by the modeled cationophore dyad

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Notes

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    Electronic supplementary information (ESI†) is available comprising Cartesian coordinates, representative diagrams of the total dipole moments’ components, HOMO-LUMO counter plots including their orbital contributions.

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Acknowledgments

The numerical calculations reported in this paper were performed at TUBITAK ULAKBIM, High Performance, and Grid Computing Center (TRUBA resources).

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Correspondence to Fatma Sevin.

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Sarikavak, K., Kurtay, G. & Sevin, F. Comparative cation sensing properties of a newly designed urea linked ferrocene-benzimidazole dyad: a DFT study. J Mol Model 26, 50 (2020). https://doi.org/10.1007/s00894-020-4304-0

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Keywords

  • Cation sensing
  • Global descriptors
  • NBO analysis
  • NCI
  • DFT