| Summary: | The synthesis and physical properties of the series of the ferrocenyl-containing sterically hindered phosphonium salts based on di(<i>tert</i>-butyl)ferrocenylphosphine is reported. Analysis of voltamogramms of the obtained compounds revealed some correlations between their structures and electrochemical properties. The elongation of the alkyl chain at the P atom as well as replacement of the Br<sup>−</sup> anion by [BF<sub>4</sub>]<sup>−</sup> shifts the ferrocene/ferrocenium transition of the resulting salts into the positive region. DFT results shows that in the former case, the Br<sup>−</sup> anion destabilizes the corresponding ion pair, making its oxidation easier due to increased highest occupied molecular orbital (HOMO) energy. Increased HOMO energy for ion pairs with the Br<sup>−</sup> ion compared to BF<sub>4</sub><sup>−</sup> are caused by contribution of bromide atomic orbitals to the HOMO. The observed correlations can be used for fine-tuning the properties of the salts making them attractive for applications in multicomponent batteries and capacitors.
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