Tuning the interactions between electron spins in fullerene-based triad systems

A series of six fullerene-linker-fullerene triads have been prepared by the stepwise addition of the fullerene cages to bridging moieties thus allowing the systematic variation of fullerene cage (C60 or C70) and linker (oxalate or terephthalate) and enabling precise control over the inter-fullerene...

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Main Authors: Lebedeva, Maria A., Chamberlain, Thomas W., Davies, E. Stephen, Thomas, Bradley E., Schröder, Martin, Khlobystov, Andrei N.
Format: Article
Published: Beilstein-Institut 2014
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Online Access:https://eprints.nottingham.ac.uk/29706/
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author Lebedeva, Maria A.
Chamberlain, Thomas W.
Davies, E. Stephen
Thomas, Bradley E.
Schröder, Martin
Khlobystov, Andrei N.
author_facet Lebedeva, Maria A.
Chamberlain, Thomas W.
Davies, E. Stephen
Thomas, Bradley E.
Schröder, Martin
Khlobystov, Andrei N.
author_sort Lebedeva, Maria A.
building Nottingham Research Data Repository
collection Online Access
description A series of six fullerene-linker-fullerene triads have been prepared by the stepwise addition of the fullerene cages to bridging moieties thus allowing the systematic variation of fullerene cage (C60 or C70) and linker (oxalate or terephthalate) and enabling precise control over the inter-fullerene separation. The fullerene triads exhibit good solubility in common organic solvents, have linear geometries and are diastereomerically pure. Cyclic voltammetric measurements demonstrate the excellent electron accepting capacity of all triads, with up to 6 electrons taken up per molecule in the potential range between -2.3 and 0.2 V (vs. Fc+/Fc). No significant electronic interactions between fullerene cages are observed in the ground state indicating that the individual properties of each C60 or C70 cage are retained within the triads. The electron-electron interactions in the electrochemically generated dianions of these triads, with one electron per fullerene cage were studied by EPR spectroscopy. The nature of electron-electron coupling observed at 77 K can be described as an equilibrium between a doublet and triplet state biradical which depends on the interfullerene spacing. The shorter oxalate-bridged triads exhibit stronger spin-spin coupling with triplet character, while in the longer terephthalate-bridged triads the intramolecular spin-spin coupling is significantly reduced.
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spelling nottingham-297062020-05-04T16:43:23Z https://eprints.nottingham.ac.uk/29706/ Tuning the interactions between electron spins in fullerene-based triad systems Lebedeva, Maria A. Chamberlain, Thomas W. Davies, E. Stephen Thomas, Bradley E. Schröder, Martin Khlobystov, Andrei N. A series of six fullerene-linker-fullerene triads have been prepared by the stepwise addition of the fullerene cages to bridging moieties thus allowing the systematic variation of fullerene cage (C60 or C70) and linker (oxalate or terephthalate) and enabling precise control over the inter-fullerene separation. The fullerene triads exhibit good solubility in common organic solvents, have linear geometries and are diastereomerically pure. Cyclic voltammetric measurements demonstrate the excellent electron accepting capacity of all triads, with up to 6 electrons taken up per molecule in the potential range between -2.3 and 0.2 V (vs. Fc+/Fc). No significant electronic interactions between fullerene cages are observed in the ground state indicating that the individual properties of each C60 or C70 cage are retained within the triads. The electron-electron interactions in the electrochemically generated dianions of these triads, with one electron per fullerene cage were studied by EPR spectroscopy. The nature of electron-electron coupling observed at 77 K can be described as an equilibrium between a doublet and triplet state biradical which depends on the interfullerene spacing. The shorter oxalate-bridged triads exhibit stronger spin-spin coupling with triplet character, while in the longer terephthalate-bridged triads the intramolecular spin-spin coupling is significantly reduced. Beilstein-Institut 2014-02-05 Article PeerReviewed Lebedeva, Maria A., Chamberlain, Thomas W., Davies, E. Stephen, Thomas, Bradley E., Schröder, Martin and Khlobystov, Andrei N. (2014) Tuning the interactions between electron spins in fullerene-based triad systems. Beilstein Journal of Organic Chemistry, 10 . pp. 332-343. ISSN 1860-5397 Fullerene dimers fullerene triads electrochemistry EPR spin-spin interactions http://www.beilstein-journals.org/bjoc/single/articleFullText.htm?publicId=1860-5397-10-31 doi:10.3762/bjoc.10.31 doi:10.3762/bjoc.10.31
spellingShingle Fullerene dimers
fullerene triads
electrochemistry
EPR
spin-spin interactions
Lebedeva, Maria A.
Chamberlain, Thomas W.
Davies, E. Stephen
Thomas, Bradley E.
Schröder, Martin
Khlobystov, Andrei N.
Tuning the interactions between electron spins in fullerene-based triad systems
title Tuning the interactions between electron spins in fullerene-based triad systems
title_full Tuning the interactions between electron spins in fullerene-based triad systems
title_fullStr Tuning the interactions between electron spins in fullerene-based triad systems
title_full_unstemmed Tuning the interactions between electron spins in fullerene-based triad systems
title_short Tuning the interactions between electron spins in fullerene-based triad systems
title_sort tuning the interactions between electron spins in fullerene-based triad systems
topic Fullerene dimers
fullerene triads
electrochemistry
EPR
spin-spin interactions
url https://eprints.nottingham.ac.uk/29706/
https://eprints.nottingham.ac.uk/29706/
https://eprints.nottingham.ac.uk/29706/