McSweeney, RL, Chamberlain, TW orcid.org/0000-0001-8100-6452, Baldoni, M et al. (4 more authors) (2016) Direct Measurement of Electron Transfer in Nanoscale Host-Guest Systems: Metallocenes in Carbon Nanotubes. Chemistry - A European Journal, 22 (38). pp. 13540-13549. ISSN 0947-6539
Abstract
Electron-transfer processes play a significant role in host–guest interactions and determine physicochemical phenomena emerging at the nanoscale that can be harnessed in electronic or optical devices, as well as biochemical and catalytic systems. A novel method for qualifying and quantifying the electronic doping of single walled carbon nanotubes (SWNTs) using electrochemistry has been developed that establishes a direct link between these experimental measurements and ab initio DFT calculations. Metallocenes such as cobaltocene and methylated ferrocene derivatives were encapsulated inside SWNTs (1.4 nm diameter) and cyclic voltammetry (CV) was performed on the resultant host–guest systems. The electron transfer between the guest molecules and the host SWNTs is measured as a function of shift in the redox potential (E1/2) of CoII/CoI, CoIII/CoII and FeIII/FeII. Furthermore, the shift in E1/2 is inversely proportional to the nanotube diameter. To quantify the amount of electron transfer from the guest molecules to the SWNTs, a novel method using coulometry was developed, allowing the mapping of the density of states and the Fermi level of the SWNTs. Correlated with theoretical calculations, coulometry provides an accurate indication of n/p-doping of the SWNTs.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. This is the peer reviewed version of the following article: McSweeney et al. (2016), Direct Measurement of Electron Transfer in Nanoscale Host–Guest Systems: Metallocenes in Carbon Nanotubes. Chem. Eur. J; which has been published in final form at https://dx.doi.org/10.1002/chem.201602116. This article may be used for non-commercial purposes in accordance with the Wiley Terms and Conditions for Self-Archiving. |
Keywords: | carbon nanotubes; charge transfer; electrochemistry; host–guest systems; metallocenes |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Inorganic Chemistry (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 21 Jun 2016 10:44 |
Last Modified: | 03 Aug 2017 00:35 |
Published Version: | https://dx.doi.org/10.1002/chem.201602116 |
Status: | Published |
Publisher: | Wiley |
Identification Number: | 10.1002/chem.201602116 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:100935 |