Oligomeric ferrocene rings
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Accepted version
Supporting information
Author(s)
Type
Journal Article
Abstract
Cyclic oligomers comprising strongly interacting redox-active monomer units represent an unknown, yet highly desirable class of nanoscale materials. Here we describe the synthesis and properties of the first family of molecules belonging to this compound category—differently sized rings comprising only 1,1′-disubstituted ferrocene units (cyclo[n], n = 5–7, 9). Due to the close proximity and connectivity of centres (covalent Cp–Cp linkages; Cp = cyclopentadienyl) solution voltammograms exhibit well-resolved, separated 1e– waves. Theoretical interrogations into correlations based on ring size and charge state are facilitated using values of the equilibrium potentials of these transitions, as well as their relative spacing. As the interaction free energies between the redox centres scale linearly with overall ring charge and in conjunction with fast intramolecular electron transfer (∼107 s−1), these molecules can be considered as uniformly charged nanorings (diameter ∼1–2 nm).
Date Issued
2016-06-27
Date Acceptance
2016-05-19
Citation
Nature Chemistry, 2016, 8, pp.825-830
ISSN
1755-4330
Publisher
Nature Publishing Group
Start Page
825
End Page
830
Journal / Book Title
Nature Chemistry
Volume
8
Copyright Statement
© 2016 Macmillan Publishers Limited. All rights reserved.
Sponsor
The Leverhulme Trust
Identifier
https://www.nature.com/articles/nchem.2553
Grant Number
RPG-2012-754
Subjects
Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
MIXED ULLMANN REACTIONS
1,1-OLIGOMERIC FERROCENES
RUTHENOCENE
BIS(FULVALENE)DIIRON
OLIGOMETALLOCENES
PURIFICATION
DERIVATIVES
BIFERROCENE
MONOCATION
SOLVENT
Organic Chemistry
03 Chemical Sciences
Publication Status
Published
Date Publish Online
2016-06-27