Add time:09/05/2019         Source:sciencedirect.com

The impact of solvent basicity on the solvatochromism of pentacyanoferrate(II) complexes has scarcely been discussed. In this work a study of the influence of solvent basicity on the local effects occurring in binary solvent mixtures consisting of an amide and water or an alcohol and water is reported. The author argues that the reason of the underestimation of the impact of solvent basicity on the solvatochromism of pentacyanoferrate(II) complexes is the use of empirical indicator-centric solvent basicity parameters for the description of solvatochromic shifts. The model of Inomata and coworkers [J. Phys. Chem. B 119 (2015) 14738–14,749] was utilized as a means to determine local, solute-centric basicity in three cases of binary solvent mixtures involving a pentacyanoferrate(II) complex as s'olute. Solute- and indicator-centric excess basicities were compared. It was found that the solute-centric properties markedly differed from the corresponding published indicator-centric properties. The contribution of the basicity was determined for each case of solvent mixture with the use of suitable linear solvation energy relationships (LSERs) involving terms expressing Lewis acidity, dipolarity, and the basicity of the medium. Additionally, a modified Redlich–Kister (CNIBS/R–K) equation, was employed for the algebraic description of the solute-centric solvent polarity parameters.

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