Photocontrolled Ring‐Opening Polymerization of Strained Dicarba[2]Ferrocenophanes: A Route to Well‐Defined Polyferrocenylethylene Homopolymers and Block Copolymers

Herbert, David E.; Mayer, Ulrich F. J.; Gilroy, Joe B.; López-Gómez, María J.; Lough, Alan J.; Charmant, Jonathan P. H.; Manners, Ian

doi:10.1002/chem.200901311

Cited by 33 publications

(35 citation statements)

References 81 publications

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“…248 Initially, an acetylide-substituted monomer in THF was irradiated with UV light in the presence of Na[C 5 H 5 ] initiator to yield living PFS with pendant acetylide groups. This method has also allowed the formation of a range of BCPs, including PFE-b-PFDMS (PFE: polyferrocenylethylene), 249 Organic-organometallic PS-b-PFS BCPs have been prepared by a combination of conventional and photocontrolled anionic polymerisation. The acetylide PFS-b-PFDMS was isolated after addition of methanol to quench the reaction giving BCPs with predictable molecular weights (based on the monomer to M[C 5 H 5 ] ratio) and low polydispersities.…”

Section: ''Photocontrolled'' Living Anionic Rop Involving Fe-cp Bond mentioning

confidence: 99%

Polyferrocenylsilanes: synthesis, properties, and applications

et al. 2016

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This in-depth review covers progress in the area of polyferrocenylsilanes (PFS), a well-established, readily accessible class of main chain organosilicon metallopolymer consisting of alternating ferrocene and organosilane units. Soluble, high molar mass samples of these materials were first prepared in the early 1990s by ring-opening polymerisation (ROP) of silicon-bridged [1]ferrocenophanes (sila[1]ferrocenophanes). Thermal, transition metal-catalysed, and also two different living anionic ROP methodologies have been developed: the latter permit access to controlled polymer architectures, such as monodisperse PFS homopolymers and block copolymers. Depending on the substituents, PFS homopolymers can be amorphous or crystalline, and soluble in organic solvents or aqueous media. PFS materials have attracted widespread attention as high refractive index materials, electroactuated redox-active gels, fibres, films, and nanoporous membranes, as precursors to nanostructured magnetic ceramics, and as etch resists to plasmas and other radiation. PFS block copolymers form phase-separated iron-rich, redox-active and preceramic nanodomains in the solid state with applications in nanolithography, nanotemplating, and nanocatalysis. In selective solvents functional micelles with core-shell structures are formed. Block copolymers with a crystallisable PFS core-forming block were the first to be found to undergo "living crystallisation-driven self-assembly" in solution, a controlled method of assembling block copolymers into 1D or 2D structures that resembles a living covalent polymerisation, but on a longer length scale of 10 nm-10 μm.

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Section: ''Photocontrolled'' Living Anionic Rop Involving Fe-cp Bond mentioning

confidence: 99%

Polyferrocenylsilanes: synthesis, properties, and applications

et al. 2016

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“…[14] An alternative procedure, living photocontrolled ROP in the presence of cyclopentadienide anion initiators, [15] involves photoactivation and subsequent cleavage of the Fe-Cp bond. These living ROP routes have been extended to prepare block copolymers from several [1]-and [2]ferrocenophanes containing various bridges (1, M= Fe, E x R y = GeR 2 , [16] PR, [17] or C 2 R 4 [18] ); however, their use for analogous materials containing metals other than iron is unexplored. Here, we demonstrate the synthesis of PFS diblock copolymers with a poly(cobaltoceniumethylene) ([PCE] + ) coblock derived from the dicarba[2]cobaltococenophane 3.…”

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Main‐Chain Heterobimetallic Block Copolymers: Synthesis and Self‐Assembly of Polyferrocenylsilane‐b‐Poly(cobaltoceniumethylene)

et al. 2011

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Metal-containing polymers are attracting growing attention as functional materials as a result of the useful physical and catalytic properties that arise from the presence of metal centers. [1] For example, metallopolymers with reversible redox properties are of interest for applications in electrocatalysis [2] and sensing, [3] as responsive surfaces [4] and capsules, [5] and as the active components of photonic crystal displays. [6] Block copolymers containing metal centers present additional features of considerable interest as a result of their ability to undergo self-assembly in the solid state or solution. Studies of such materials have led to applications as nanotemplates in lithography [7] and as precursors to patterned magnetic nanostructures [8] and nanocatalysts for carbon nanotube growth. [9] However, the synthesis of materials containing metalloblocks by living polymerization protocols presents substantial challenges as a result of undesirable side reactions of many metal centers with ionic and radical propagating sites. Herein, we describe our initial results on the synthesis and properties of unusual main-chain heterobimetallic diblock copolymers with different redox-active centers in each metalloblock.The ring-opening polymerization (ROP) of strained metallocenophanes 1 provides a well-studied route to functional metallopolymers 2. [10][11][12] In particular, the ROP of 18electron sila[1]ferrocenophanes (1, M= Fe, E x R y = SiR 2 ) represents a useful route to polyferrocenylsilanes (PFSs, 2, M = Fe, E x R y = SiR 2 ) which exhibit many interesting characteristics. [13] Living anionic polymerization of sila[1]ferrocenophanes (1, M = Fe, E x R y = SiR 2 ) using organolithium initia-[*] Dr.

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“…This is consistent with electrochemical studies of ferrocenophanes, which show that their redox potential is similar to that of ferrocene 23. 17c RuCp 2 likewise has a marked preference for the non‐bent structure with α =0°. In contrast, RuCp 2 + barely increases in energy upon tilting, until α >20°, so that the cation lies lower in energy relative to the neutral species as the angle increases (Figure S9).…”

Section: Resultsmentioning

confidence: 99%

Influence of Cyclopentadienyl Ring‐Tilt on Electron‐Transfer Reactions: Redox‐Induced Reactivity of Strained [2] and [3]Ruthenocenophanes

Russell

Gilroy

Lam

et al. 2014

Chemistry A European J

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In contrast to ruthenocene [Ru(η(5) -C5 H5 )2 ] and dimethylruthenocene [Ru(η(5) -C5 H4 Me)2 ] (7), chemical oxidation of highly strained, ring-tilted [2]ruthenocenophane [Ru(η(5) -C5 H4 )2 (CH2 )2 ] (5) and slightly strained [3]ruthenocenophane [Ru(η(5) -C5 H4 )2 (CH2 )3 ] (6) with cationic oxidants containing the non-coordinating [B(C6 F5 )4 ](-) anion was found to afford stable and isolable metalmetal bonded dicationic dimer salts [Ru(η(5) -C5 H4 )2 (CH2 )2 ]2 [B(C6 F5 )4 ]2 (8) and [Ru(η(5) -C5 H4 )2 (CH2 )3 ]2 [B(C6 F5 )4 ]2 (17), respectively. Cyclic voltammetry and DFT studies indicated that the oxidation potential, propensity for dimerization, and strength of the resulting RuRu bond is strongly dependent on the degree of tilt present in 5 and 6 and thereby degree of exposure of the Ru center. Cleavage of the RuRu bond in 8 was achieved through reaction with the radical source [(CH3 )2 NC(S)SSC(S)N(CH3 )2 ] (thiram), affording unusual dimer [(CH3 )2 NCS2 Ru(η(5) -C5 H4 )(η(3) -C5 H4 )C2 H4 ]2 [B(C6 F5 )4 ]2 (9) through a haptotropic η(5) -η(3) ring-slippage followed by an apparent [2+2] cyclodimerization of the cyclopentadienyl ligand. Analogs of possible intermediates in the reaction pathway [C6 H5 ERu(η(5) -C5 H4 )2 C2 H4 ][B(C6 F5 )4 ] [E=S (15) or Se (16)] were synthesized through reaction of 8 with C6 H5 EEC6 H5 (E=S or Se).

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Photocontrolled Ring‐Opening Polymerization of Strained Dicarba[2]Ferrocenophanes: A Route to Well‐Defined Polyferrocenylethylene Homopolymers and Block Copolymers

Cited by 33 publications

References 81 publications

Polyferrocenylsilanes: synthesis, properties, and applications

Polyferrocenylsilanes: synthesis, properties, and applications

Main‐Chain Heterobimetallic Block Copolymers: Synthesis and Self‐Assembly of Polyferrocenylsilane‐b‐Poly(cobaltoceniumethylene)

Influence of Cyclopentadienyl Ring‐Tilt on Electron‐Transfer Reactions: Redox‐Induced Reactivity of Strained [2] and [3]Ruthenocenophanes

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