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When researchers linked ferrocene units directly into a ring, they created nanoscale molecules whose redox centers interact and exchange electrons rapidly. In a 2016 study, Michael S. Inkpen and colleagues reported rings containing five, six, seven, or nine ferrocene units, and measured distinct one-electron electrochemical transitions in solution. The work demonstrated a new molecular structure and its electrochemical behavior—not a working electronic device.
What does “bringing ferrocene full circle” mean?
Ferrocene is an organometallic compound with an iron atom positioned between two cyclopentadienyl rings. It can undergo oxidation and reduction, making it a redox-active building block. In this work, researchers joined modified ferrocene units to one another through direct carbon–carbon bonds between cyclopentadienyl groups. The links close into covalent rings rather than using spacer molecules between the ferrocene units.
The result is a family of cyclic oligomers: molecules made from a small number of repeating units arranged in a closed loop. The study’s authors described them as the first family of cyclic oligomers built from strongly interacting redox-active monomers. See the Nature Chemistry paper for the original report.
What ring sizes did the researchers make?
Inkpen and colleagues reported rings containing five, six, seven, and nine ferrocene units. Their paper describes the structures as nanorings approximately 1–2 nm in diameter. That size refers to the molecules reported in this 2016 study, not to a manufactured component or device.
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What did the electrochemistry show?
In solution voltammetry, the rings produced well-resolved, separated one-electron waves. Each wave corresponds to a distinguishable electron-transfer step as the molecule changes oxidation state. Rather than behaving as an undifferentiated cluster, the ring therefore showed multiple redox transitions that could be examined separately.
The researchers used the transition potentials and their spacing to investigate how ring size and charge relate to interactions among the redox centers. The paper reports that interaction free energies scale linearly with overall ring charge. It also reports intramolecular electron transfer at approximately 107 s−1. These measurements support the authors’ description of the molecules as uniformly charged nanorings; they do not establish performance in a circuit.
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Why is the six-ferrocene ring notable?
Ian Manners of the University of Bristol called the six-ferrocene macrocycle “a kind of organometallic analogue of benzene.” The comparison points to a ring of repeating units with distinctive electronic behavior. It is an analogy, not a claim that the organometallic ring is chemically identical to benzene.
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The 2016 Chemistry World feature discussed electronics and plasmonics as possible eventual applications. It also described host–guest chemistry and cyclic polymeric analogues as potential research directions. Those ideas were prospective: the cited reports establish synthesis and solution electrochemistry, not a functioning device, commercial application, or demonstrated host–guest system. Manners’s suggestions were conditional on improving yields while retaining solubility.
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The research team was investigating more efficient synthetic routes and further electrical and chemical properties. The work was published online on 27 June 2016 in Nature Chemistry, volume 8, pages 825–830 (DOI: 10.1038/nchem.2553). For the original feature and its expert commentary, see Chemistry World’s “Bringing ferrocene full circle”.
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