Abstract
The synthesis and physical properties of the series of the ferrocenyl-containing sterically hindered phosphonium salts based on di(tert-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− anion by [BF4]− shifts the ferrocene/ferrocenium transition of the resulting salts into the positive region. DFT results shows that in the former case, the Br− 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− ion compared to BF4− 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.
Highlights
IntroductionMaterials that enable selective ion transport under a wide range of conditions (temperature, pH)play a key role for chemical separation processes and electrochemical batteries [1,2]
Materials that enable selective ion transport under a wide range of conditionsplay a key role for chemical separation processes and electrochemical batteries [1,2]
The starting di(tert-butyl)chlorophosphine has been obtained by the procedure described in [24], i.e., by the reaction of an excess of tert-butylmagnesium chloride with phosphorus trichloride with following separation of the product mixture by distillation under reduced pressure (Scheme 1)
Summary
Materials that enable selective ion transport under a wide range of conditions (temperature, pH)play a key role for chemical separation processes and electrochemical batteries [1,2]. Materials that enable selective ion transport under a wide range of conditions (temperature, pH). Introduction of the ferrocenyl (Fc) fragment into ILs leads to unique electrochemical properties [5] (Figure 1), that allows the Fc-containing phosphonium salts to be used for modification of the platinum electrodes surfaces [6,7,8,9,10]. The latter opens perspectives for using the Fc-based ILs as redox agents in electrolytes for lithium ion batteries [11]
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.