Correlation between 195Pt chemical shifts and the electronic transitions among d orbitals in pincer NCN Pt(II) complexes: A theoretical study and application of Ramsey’s equation

•Correlation between spectral parameters and 195Pt chemical shifts in pincer NCN Pt(II) complexes.•Correlation between chemical potentials and 195Pt chemical shifts in pincer NCN Pt(II) complexes.•The contribution of paramagnetic part of shielding in the 195Pt chemical shifts.•DFT was used to obtain two indices for deriving structure property relationships.

The chemical potentials for two series of [PtCl(NCN-Z-4)] (NCN = 2,6-bis[(dimethylamino)methyl]phenyl, Z = H, CHO, COOH, NH2, OH, NO2, SiMe3, I, t-Bu) and [PtCl(NCN-4-CHN-C6H4-Z′-4′)] (Z′ = NMe2, Me, H, Cl, CN) were calculated. The energies of platinum d orbitals were calculated by NBO analysis. Good correlations were obtained between 195Pt chemical shifts and the spectral parameters obtained from the energies of electronic transitions between Pt d orbitals in these complexes. The correlations between 195Pt chemical shifts and the chemical potentials were also good. The correlations were discussed based on Ramsey’s equation.

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