Main-Chain Ferrocene-Containing Polymers Prepared by Acyclic Diene Metathesis Polymerization: A Review

Abstract

Ferrocene, the crown of metallocene family, is widely studied as a functional unit in electrochemical and catalytic applications due to its sandwich structure. Ferrocene moieties can be embedded into the polymer backbone, leading to main-chain ferrocenecontaining polymers. These polymeric materials combine the unique functionalities of iron center with the processabilities of polymers. As one of the choice polymerization techniques, acyclic diene metathesis (ADMET) polymerization serves as a versatile method to prepare main-chain ferrocene-containing polymers under mild conditions using α,ω-dienes as monomers. This paper overviews main-chain ferrocene-containing polymers prepared by ADMET polymerization. Advances in the design, synthesis and applications of this class of organometallic monomers and polymers are detailed.

Forever young: the first seventy years of ferrocene

“…The steric strain, resulting in an increased reactivity, makes these molecules attractive starting materials for further synthesis, especially for the preparation of ferrocene-containing polymers by ring-opening polymerization. 52 The ferrocene units in the resulting polymers 53 are a part of the main chain and thus responsible for polymer propagation, as opposed to polymers where the ferrocene moieties are appended to the central polymer chain. 54…”

Copolymers of vinylferrocene and vinylimidazole for potential sensing applications

“…3 Studies with ferrocene within the polymer main-chain originally focused on on traditional polymer structures. 4 However, current approaches to including ferrocene in the main-chain have included metathesis polymerization, 5,6 ring opening polymerization, 7 and melt polymerization. 8 The large variety and scope of ferrocene containing polymers has led to extensive studies in their applications.…”

“…[17][18][19] One of the areas of interest in our lab is ferrocenecontaining polymers with electronic interactions with a neighboring moiety. Initial research with the polymer from 3-phenyl [5]ferrocenophane-1,5-dimethylene showed interactions between neighboring ferrocene/ ferrocenium moieties upon partial oxidation. 20 (Figure 2) This was evident by two redox waves in the cyclic voltammetry of the polymer and a broad absorption extending into the near-IR region of the Visible/Near-IR Spectrum.…”

“…20 (Figure 2) This was evident by two redox waves in the cyclic voltammetry of the polymer and a broad absorption extending into the near-IR region of the Visible/Near-IR Spectrum. Subsequent research studied copolymers of 3-phenyl [5] ferrocenophane-1,5-dimethylene or vinylferrocene with various N-substituted maleimides. 21 Cyclic voltammetry and UV-Vis spectra suggested interactions between the ferrocenyl and maleimide moieties.…”

Sequence-Controlled Metallopolymers: Synthesis and Properties

“…Numerous sequence-controlled polymerization methodologies based on chemical approaches have been established to prepare organic sequence-controlled polymers. − One of the most straightforward among these methods may be the direct transformation of tailor-made monomers with a built-in sequence into polymer products. Most of these polymerization strategies are anionic polymerizations and metathesis polymerizations, e.g., ring-opening metathesis polymerization (ROMP) − and acyclic diene metathesis (ADMET) polymerization, , which are also the methods of choice for the preparation of metallopolymers due to their good tolerance toward various functionalities. − …”