Organic-metalloblock copolymers via photocontrolled living anionic ring-opening polymerization

Chabanne, Laurent; Matas, Inmaculada; Patra, Sanjib K.; Manners, Ian

doi:10.1039/c1py00298h

Cited by 25 publications

(60 citation statements)

References 67 publications

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“…57 Cleavage of the Fe-Z 1 -cyclopentadienyl bond in the photoexcited monomer affords a ring-opened species possessing a free silylsubstituted Cp anion that can propagate via attack on another ring-slipped monomer. [58][59][60][61][62][63][64] This reaction is therefore more tolerant of sensitive functional monomers; for example, it has allowed the preparation of PFSs with pendant alkynyl, 61 amino, 62 and fluoroalkyl groups. 57,58 This method contrasts with the previously reported living anionic ROP, which proceeds in the absence of UV irradiation and uses organolithium initiators to induce Si-Cp(ipso) bond cleavage.…”

Section: 242mentioning

confidence: 99%

“…After turning off the irradiation source, dimethylsila [1]ferrocenophane was added and the reaction mixture was irradiated again. 253 Firstly, PS was prepared using an alkyllithium initiator and the living anionic chain ends were capped with dichlorodimethylsilane. 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.…”

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

confidence: 99%

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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: 242mentioning

confidence: 99%

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

confidence: 99%

Polyferrocenylsilanes: synthesis, properties, and applications

et al. 2016

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“…81,82 However, ring-opening reactions with transition metal halides have not yet been reported. Initial investigations into the reactivity of sila [1]ferrocenophanes with chloro(trialkyl/arylphosphine)gold complexes 83,84 involved attempts to functionalise monomers which featured alkyne substituents at silicon, 85 with the aim of eventually synthesising poly(ferrocenylsilane)s with pendant gold groups (bimetallic polymers). However, the targeted ethynyl-gold complexes could not be isolated under basic conditions.…”

Section: Reactivity Of Sila[1]ferrocenophane 1 With Chloro(phosphine)mentioning

confidence: 99%

New reactivity at the silicon bridge in sila[1]ferrocenophanes

et al. 2018

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We describe two new types of reactivity involving silicon-bridged [1]ferrocenophanes. In an attempt to form a [1]ferrocenophane with a bridging silyl cation, the reaction of sila[1]ferrocenophane [Fe(η-CH)Si(H)TMP] (12) (TMP = 2,2,6,6-tetramethylpiperidyl) towards the hydride-abstraction reagent trityl tetrakis(pentafluorophenyl)borate ([CPh][B(CF)]) was explored. This yielded the unusual dinuclear species [Fe(η-CH)Si(TMP·H)(η-CH)Fe(η-CH)Si(H)TMP][B(CF)] [13][B(C6F5)4] in low yield. The formation of [13]+ is proposed to involve abstraction of hydride from the silicon bridge in 12 with subsequent C-H bond cleavage of a cyclopentadienyl group by the resulting electrophilic transient silyl cation intermediate. We also explored the reaction of dimethylsila[1]ferrocenophane [Fe(η-CH)SiMe] (1) with the Au(i) species AuCl(PMe). This was found to result in addition of the Au-Cl bond across the Cp-Si bond to yield the ring-opened species [1'-(chlorodimethylsilyl)-ferrocenyl](trimethylphosphine)gold(i), [Fe(CHSiMeCl){CHAu(PMe)}] (14). This represents the first example of ring-opening addition of a metallocenophane with a reagent possessing a transition metal-halogen bond.

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“…[58][59] Self-assembly of bimetallic BCPs is expected to be a promising and possible solution to direct and confine the metal precursors in one of the BCP domains and to obtain metallic NPs of low size dispersity after direct pyrolysis. [60][61][62] Up to now, the use of a single bimetallic BCP to synthesize FePt NPs has not been reported. Herein, we describe Green: FePt NPs embedded in a grey carbonaceous material).…”

Section: Introductionmentioning

confidence: 99%