(1,1'-Ferrocenediyl)ferrocenyl(methyl)silane, Its Thermally Ring-Opened Polymer, and Oligomer Models

Pannell, Keith H.; Dementiev, Vyacheslav V.; Li, Hong; Cervantes‐Lee, Francisco; Nguyên, My T.; Diaz, A. F.

doi:10.1021/om00021a043

Cited by 104 publications

(84 citation statements)

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“…[91][92][93] The diffraction pattern of the pentamer was found to display a broad peak with a similar d-spacing to that of high molecular weight PFDMS, thus providing evidence of a close relationship between the two structures. Molecular mechanics calculations of the possible conformations of well-defined oligomeric species, both as isolated molecules and in the solid state, have been compared to single crystal X-ray diffraction data.…”

Section: Morphology In the Solid State: Crystalline And Amorphous Matmentioning

confidence: 81%

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: Morphology In the Solid State: Crystalline And Amorphous Matmentioning

confidence: 81%

Polyferrocenylsilanes: synthesis, properties, and applications

et al. 2016

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“…The d spacing (1.21 nm) of the most intense reflection at 2q = 7.38 is approximately twice the distance reported for the Fe-Fe vector in a linear pentamer model of PFDMS. [55] For com- parison, we also performed WAXS analysis on the starshaped block copolymer in the bulk, prior to self-assembly (line 2, Figure 7). In this case, only the characteristic reflection at 2q = 13.988 (d = 0.63 nm), which corresponds to the crystalline PFDMS domains, was found.…”

Section: Resultsmentioning

confidence: 99%

Responsive Vesicles from the Self‐Assembly of Crystalline‐Coil Polyferrocenylsilane‐block‐Poly(ethylene Oxide) Star‐Block Copolymers

Schacher¹,

Elbert²,

Patra³

et al. 2011

Chemistry A European J

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We demonstrate the synthesis and characterization of star-shaped crystalline-coil block copolymers with four arms consisting of an inner block of poly(ethylene oxide) and an outer semicrystalline compartment of poly(ferrocenyldimethylsilane), [PEO(50) -b-PFDMS(35)](4). The materials were synthesized by transition-metal-catalyzed ring-opening polymerization of dimethylsila[1]ferrocenophane in the presence of silane-functionalized four-arm PEO stars as macroinitiators and they exhibited a moderate polydispersity (PDI≅1.4). Self-assembly in mixtures of THF and different alcohols as selective solvents for the PEO block resulted in the formation of semicrystalline vesicles (ethanol, 1-butanol) or large, rather ill-defined, spherical structures (methanol). Further, both the rate of addition of the selective co-solvent and the overall solvent/non-solvent ratio drastically affected the size and stability of the self-assembled particles. We could also show that a photoacid generator, as a model for an active substance, can be encapsulated and the UV-induced generation of HCl resulted in a straightforward degradation of the organometallic vesicles.

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“…For CoA, CoB and FeC, both of the torsion angles are very close to 1808, presumably indicating that their conformation is dominated instead by the steric bulk of the Cp* group. Close contacts between Fe atoms and Cp rings to which the metal is not directly bound have been distinguished in the crystal structures of trimetallic [Fe(FcEMe 2 C 5 H 4 ) 2 ] (E= C, [27] Si [28] ) and pentametallic [Fe(FcSiMe 2 fcSiMe 2 C 5 H 4 ) 2 ] (fc = 1,1'-ferrocenediyl [29] ); for these both intra-and intermolecular contacts are seen and the molecules stack in layers with their arrangement determined by non-bonded Fe-Cp electrostatic interactions, the magnitude of which presumably surpasses any unfavourable intramolecular conformations. The packings of CoA, CoB and FeC show similar motifs, although with these bimetallics only intermolecular close contact is possible; this causes the molecules to arrange themselves in chains, giving a herringbone-like pattern in one plane which is stacked perpendicular to this (see Figure …”

Section: Resultsmentioning

confidence: 99%

Electronic Coupling in Mixed‐Valence Dinuclear Ferrocenes and Cobaltocenes with Saturated Bridging Groups

Jones

Barlow

O’Hare

2005

Chemistry A European J

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We have synthesised a series of new dinuclear metallocenes [{M(Cp*)(C5H4)}2X] (Cp* = eta5-pentamethylcyclopentadienyl; M = Fe, Co, X = CMe2, SiMe2, GeMe2; M = Fe, X = Si2Me4). For the neutral dicobalt complexes, magnetic susceptibility measurements reveal intramolecular antiferromagnetic interactions of -21 and -14 cm(-1) for SiMe2- and GeMe2-bridged species, respectively, but negligible interaction for the CMe2-bridged compound. In contrast, intervalence charge-transfer (IVCT) data for the mixed-valence monocations of both Fe and Co complexes show electronic coupling to decrease in the order CMe2 > SiMe2 > GeMe2. This suggests that electronic coupling is principally through-space in contrast to results found from previous studies. The IVCT data also show much stronger coupling in the dicobalt species versus their diiron analogues.

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(1,1'-Ferrocenediyl)ferrocenyl(methyl)silane, Its Thermally Ring-Opened Polymer, and Oligomer Models

Cited by 104 publications

References 0 publications

Polyferrocenylsilanes: synthesis, properties, and applications

Polyferrocenylsilanes: synthesis, properties, and applications

Responsive Vesicles from the Self‐Assembly of Crystalline‐Coil Polyferrocenylsilane‐block‐Poly(ethylene Oxide) Star‐Block Copolymers

Electronic Coupling in Mixed‐Valence Dinuclear Ferrocenes and Cobaltocenes with Saturated Bridging Groups

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