Solid-State Synthesis and Morphology of Poly(ferrocenyldimethylsilane)

Rasburn, J.; Petersen, Ruth; Jahr, T.; Rulkens, Ron; Manners, Ian; Vancso, Gyula J.

doi:10.1021/cm00053a010

Cited by 79 publications

(77 citation statements)

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“…In this case, only the characteristic reflection at 2q = 13.988 (d = 0.63 nm), which corresponds to the crystalline PFDMS domains, was found. [44] This rather broad reflection was also detected for the vesicles. However, the signals at 2q = 7.3 and 12.158 cannot be assigned to linear PFDMS, PEO, or the [PEO 50 -b-PFDMS 35 ] 4 diblock copolymer prior to vesicle formation.…”

Section: Resultsmentioning

confidence: 63%

“…The properties of PFS homopolymers depend strongly on the substituents present at silicon: Symmetrically substituted materials are, in general, semicrystalline [24,44,45] whereas PFSs with two different substituents are amorphous. [46] The polymerization of the organometallic monomer was carried out for 72 h and, after two-fold reprecipitation of the resulting orange materials to remove any unreacted PEO star macroinitiator, a four-arm star-block copolymer with a moderate PDI was obtained.…”

Section: Resultsmentioning

confidence: 99%

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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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Section: Resultsmentioning

confidence: 63%

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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“…Thus, the preference for these bulky substituents to minimize steric interactions with one another might provide an additional driving force for ROP. Thirdly, we have previously shown that a trans zigzag conformation is likely for the high polymer 2 (R = R' = Me) in ordered regions in the solid state (20). The presence of bulky trimethylsilyl substituents might be expected to impart unusual conformational properties to the macromolecules both in the solid state and solution which would influence the interactions between the transition metal centers that dominate the electrochemical behaviour (4).…”

Section: [Traduit Par La Rbdaction]mentioning

confidence: 99%

The synthesis and polymerization behaviour of silicon-bridged [1]- and [2]ferrocenophanes with sterically demanding trimethylsilyl substituents attached to the cyclopentadienyl rings

Peckham¹,

Foucher²,

Lough³

et al. 1995

Can. J. Chem.

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The silicon-bridged [llferrocenophane Fe(q-C,H3SiMe,),(SiMe2) (5) was synthesized via the reaction of Li,[Fe(q-C,H,SiMe,),].tmeda (tmeda = tetramethylethylenediamine) with Me2SiC1, in hexanes. The disilane-bridged [2]ferrocenophane Fe(q-C5H3SiMe,),(Si2Me4) (7) was prepared using a similar route from the disilane C1Me2SiSiMe2C1. Despite the presence of sterically demanding SiMe, substituents on the cyclopentadienyl rings, compound 5 was found to undergo thermal ring-opening polymerization at 170°C to produce very soluble, high molecular weight poly(ferrocenylsi1ane) 6 with Mw = 1.4 x lo5, M , = 8.4 x lo4.However, the [2]ferrocenophane 7 was found to be resistant to thermal ring-opening polymerization even at 350°C and decomposed above 380°C. A single-crystal X-ray diffraction study of 7 revealed that the steric interactions between the bulky SiMe, groups are relieved by a significant twisting of the disilane bridge with respect to the plane defined by the centroids of the cyclopentadienyl ligands and the metal atom. The angle between the planes of the cyclopentadienyl rings in 7 was found to be 5.4(6)", slightly greater than that in the non-silylated analogue Fe(q-C5H4),(Si2Me4) (4a) (4.19(2)"), and dramatically less than the corresponding tilt angle of the strained, polymerizable, silicon-bridged ,(SiMe2) (1) (20.8(5)"). The length of the Si-Si bond in 7 (2.342(3) A) was found to be close to the sum of the covalent radii (2.34 A). Crystals of 7 are monoclinic, space group C'lc, with a = 23.689(3) A, b = 11.174(1) A, c = 31.027(3) A, p = 109.16(1)", V = 7758(2) A3, and Z = 12.Key words: ring-opening polymerization, ferrocenophane, organometallic polymers.Rksumk : On a synthCtist le [I]ferroctnophane pontC par un silicium, Fe(q-C5H3SiMe3),(SiMe2) (5), par une rkaction du Li,[Fe(q-C5H3SiMe3),].tmeda (tmeda = tCtramtthyltthylknediamine) avec du Me2SiC12 dans de l'hexane. On a prCparC le [2]ferroctnophane pontt par deux silanes, Fe(q-C5H3SiMe3),(Si2Me4) (7). faisant appel ti une voie sernblable i partir du disilane C1Me2SiSiMe2C1. MalgrC la prksence sur les noyaux cyclopentadiCnyles de substituants SiMe, ayant une demande stCrique irnportante, on a trouvC que le compose 5 subit une polymCrisation therrnique par ouverture de cycle 2 170°C qui conduit au poly(ferrocCnylsi1ane) 6 trks soluble et de poids rnolCculaire ClevC avec Mw = 1,4 x lo5, M,, = 8,4 x lo4. Toutefois, on a trouvC que le[2]ferrocCnophane 7 est resistant une polyrnCrisation therrnique par ouverture de cycle, rn&rne a 350°C, et qu'il se dCcornpose i 380°C. Une ttude de diffraction des rayons X par un cristal unique du composC 7 rnontre que les interactions stCriques entre les groupes SiMe, sttriquernent encombrants sont apaisCes par une dtforrnation irnportante du pont disilane par rapport au plan dtfini par les centro~des des coordinats cyclopentadienyles et de l'atome de metal. On a trouvC que l'angle entre les plans des noyaux cyclopentadienyles du composC 7 est de 5,4(6)", ce qui est 1Cgkrernent supCrieur $ i la valeur de 4,19(2)" observke...

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“…It was reported that as the dose of initiating radiation rose, the weight average molar mass increased, indicating a greater degree of polymerisation. 42 Higher radiation rates are expected to yield more reaction centres, which typically, and contrary to that observed, would be expected to afford lower molar mass polymers. poly(ferrocenylmethylphenylsilane)), in a topotactic process based on NMR analysis.…”

Section: Rop Induced By γ-Irradiation and Cationic Initiatorsmentioning

confidence: 94%

Synthesis and Solution Self‐Assembly of Polyisoprene‐block‐poly(ferrocenylmethylsilane): A Diblock Copolymer with an Atactic but Semicrystalline Core‐Forming Metalloblock

Qiu

Winnik

et al. 2016

Macro Chemistry & Physics

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Solid-State Synthesis and Morphology of Poly(ferrocenyldimethylsilane)

Cited by 79 publications

References 0 publications

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

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

The synthesis and polymerization behaviour of silicon-bridged [1]- and [2]ferrocenophanes with sterically demanding trimethylsilyl substituents attached to the cyclopentadienyl rings

Synthesis and Solution Self‐Assembly of Polyisoprene‐block‐poly(ferrocenylmethylsilane): A Diblock Copolymer with an Atactic but Semicrystalline Core‐Forming Metalloblock

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