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Diffusion in weakly coordinating solvents

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 analysed using the modified Stokes-Einstein equation and compared with the theoretical upper, Dmax, and lower, Dmin, 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.
0013-4686
140720
Black, Alexander W.
afede714-ea39-480d-b9e8-4d2af1d930c8
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Bartlett, Philip N.
d99446db-a59d-4f89-96eb-f64b5d8bb075
Black, Alexander W.
afede714-ea39-480d-b9e8-4d2af1d930c8
Zhang, Wenjian
1f80ac5e-d4c2-4720-b19e-be700cd411e7
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Bartlett, Philip N.
d99446db-a59d-4f89-96eb-f64b5d8bb075

Black, Alexander W., 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).

Record type: Article

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 analysed using the modified Stokes-Einstein equation and compared with the theoretical upper, Dmax, and lower, Dmin, 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.

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Submitted date: 6 May 2022
Accepted/In Press date: 13 June 2022
Published date: 16 June 2022

Identifiers

Local EPrints ID: 468030
URI: http://eprints.soton.ac.uk/id/eprint/468030
ISSN: 0013-4686
PURE UUID: d34dc05a-db12-4f2d-b3fb-45e2f8f2b4a0
ORCID for Alexander W. Black: ORCID iD orcid.org/0000-0003-3001-3083
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468
ORCID for Philip N. Bartlett: ORCID iD orcid.org/0000-0002-7300-6900

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Date deposited: 28 Jul 2022 16:42
Last modified: 06 Aug 2022 01:53

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Contributors

Author: Alexander W. Black ORCID iD
Author: Wenjian Zhang
Author: Gillian Reid ORCID iD

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