Diffusion in weakly coordinating solvents
Diffusion in weakly coordinating solvents
Weakly coordinating solvents are of interest for the electrodeposition of p-block semiconductors for application in electronic devices. p-block complexes typically have weakly coordinated ligands that are easily displaced, making them incompatible with strongly Lewis basic solvents. In this work we use electrochemical measurements at microelectrodes to study diffusion in weakly coordinating solvents. Diffusion coefficients of the metallocenes decamethylferrocene, decamethylferrocenium hexafluorophosphate, cobaltocenium hexafluorophosphate, and the electrodeposition precursors tetrachloroantimonate(III) and tetrachlorobismuthate(III) were measured. The values are analyzed using the modified Stokes-Einstein equation and compared with the theoretical upper, D
max, and lower, D
min, bounds of the diffusion coefficients. This approach allows the interpretation of D values, whilst avoiding dealing with some of the uncertainties associated with molecular size in the Stokes-Einstein equation. The neutral decamethylferrocene was found to obey the Stokes-Einstein equation whereas the charged metallocene species had values which were less than the theoretical minimum, which was attributed to a larger than expected particle size caused by ion pairing. The importance of considering the modifications of the Stokes-Einstein equation is also highlighted.
Diffusion coefficients, Ion pairing, Microelectrodes, Weakly coordinating solvents
140720
Black, Alexander
d965eb9a-d173-4e3f-b317-389b09250c68
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Bartlett, Philip N.
d99446db-a59d-4f89-96eb-f64b5d8bb075
16 June 2022
Black, Alexander
d965eb9a-d173-4e3f-b317-389b09250c68
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Bartlett, Philip N.
d99446db-a59d-4f89-96eb-f64b5d8bb075
Black, Alexander, Zhang, Wenjian, Reid, Gillian and Bartlett, Philip N.
(2022)
Diffusion in weakly coordinating solvents.
Electrochimica Acta, 425, , [140720].
(doi:10.1016/j.electacta.2022.140720).
Abstract
Weakly coordinating solvents are of interest for the electrodeposition of p-block semiconductors for application in electronic devices. p-block complexes typically have weakly coordinated ligands that are easily displaced, making them incompatible with strongly Lewis basic solvents. In this work we use electrochemical measurements at microelectrodes to study diffusion in weakly coordinating solvents. Diffusion coefficients of the metallocenes decamethylferrocene, decamethylferrocenium hexafluorophosphate, cobaltocenium hexafluorophosphate, and the electrodeposition precursors tetrachloroantimonate(III) and tetrachlorobismuthate(III) were measured. The values are analyzed using the modified Stokes-Einstein equation and compared with the theoretical upper, D
max, and lower, D
min, bounds of the diffusion coefficients. This approach allows the interpretation of D values, whilst avoiding dealing with some of the uncertainties associated with molecular size in the Stokes-Einstein equation. The neutral decamethylferrocene was found to obey the Stokes-Einstein equation whereas the charged metallocene species had values which were less than the theoretical minimum, which was attributed to a larger than expected particle size caused by ion pairing. The importance of considering the modifications of the Stokes-Einstein equation is also highlighted.
Text
Diffusion in Weakly Coordinating Solvents
- Accepted Manuscript
Text
1-s2.0-S0013468622008799-main
- Version of Record
More information
Submitted date: 6 May 2022
Accepted/In Press date: 13 June 2022
Published date: 16 June 2022
Additional Information:
Funding Information:
This work was supported by the EPSRC through the Advanced Devices by Electroplating program grant (ADEPT; EP/N035437/1). All data supporting this study are openly available from the University of Southampton repository at https://doi.org/10.5258/SOTON/D2211.
Funding Information:
This work was supported by the EPSRC through the Advanced Devices by Electroplating program grant (ADEPT; EP/N035437/1). All data supporting this study are openly available from the University of Southampton repository at https://doi.org/10.5258/SOTON/D2211.
Publisher Copyright:
© 2022 The Author(s)
Keywords:
Diffusion coefficients, Ion pairing, Microelectrodes, Weakly coordinating solvents
Identifiers
Local EPrints ID: 468030
URI: http://eprints.soton.ac.uk/id/eprint/468030
ISSN: 0013-4686
PURE UUID: d34dc05a-db12-4f2d-b3fb-45e2f8f2b4a0
Catalogue record
Date deposited: 28 Jul 2022 16:42
Last modified: 06 Jun 2024 01:34
Export record
Altmetrics
Contributors
Author:
Alexander Black
Download statistics
Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.
View more statistics
