Polyferrocenylsilanes synthesis

Electric arcs, in metal vapor synthesis, 1, 224 Electric-field-induced second harmonic generation Group 8 metallocenes, 12, 109 for hyperpolarizability measurement, 12, 107 Electrochemical cell assembly, in cyclic voltammetry, 1, 283 Electrochemical irreversibility, in cyclic voltammetry, 1, 282 Electrochemical oxidation, arene chromium carbonyls, 5, 258 Electrochemical properties, polyferrocenylsilanes, 12, 332 Electrochemical reduction, bis-Cp Zr(III) and (IV) compounds, 4, 745 Electrochemical sensors biomolecule—ferrocene conjugates... 

Vandermeulen, G.W.M., Kim, K.T., Wang, Z., and Manners, I. "Metallopolymer-peptide conjugates synthesis and self-assembly of polyferrocenylsilane graft and block copolymers containing a beta-sheet forming Gly-Ala-Gly-Ala tetrapeptide segment". Biomacromolecules 7(4), 1005-1010 (2006). 

Wang Z, Masson G, Peiris PC et al. (2007) Living photolytic ring-opening polymerization of amino-functionalizEd [l]ferrocenophanes synthesis and layer-by-layer self-assembly of weU-deflned water-soluble polyferrocenylsilane polyelectrolytes. Chem -A Eur J 13 9372-9383... 

Synthesis of polyferrocenylsilane-poly(aminoalkylmethacrylate)-block co-polymers 479... 

Synthesis of high molecular weight unsymmetrically substituted polyferrocenylsilanes 502... 

This chapter focuses on polyferrocenylsilanes (PFSs) where iron and silicon are in the main chain. Subsequently, PFS block copolymers will be reviewed. These materials represent an area of rapidly growing interest as a result of their self-assembly into phase-separated metal-rich nanodomain structures in thin films and micelles in block-selective solvents. The resulting nanostructured materials have a wealth of potential applications and recent breakthroughs in this area are discussed. The subject matter of the chapter is divided up into subsections covering PFS homopolymer and block copolymer synthesis, solution and solid-state self-assembly and applications of the latter, which have been extensively developed by ourselves and our collaborators and also by other research groups. 

Scheme 16.6 Synthesis of polyferrocenyldimethylsilane-Z -polydimethylaminoethylmethacylate. (Reproduced with permission from X.S. Wang, M.A. Winnik and I. Manners, Synthesis and aqueous self-assembly of a polyferrocenylsilane-block-poly(aminoalkyl methacrylate) diblock copolymer, Macromolecular Rapid Communications, 2002,23, 210. Wiley-VCH Verlag GmbH Co. KGaA.).

Figure 16.11 TEM image in dark-field mode for shell-crosslinked cylinders of PFS53- -Pl32o block copolymers encapsulated with Ag nanoparticles. (Reprinted with permission from H. Wang, X. Wang, M.A. Winnik and I. Manners, Redox-mediated synthesis and encapsulation of inorganic nanoparticles in shell-cross-linked cylindrical polyferrocenylsilane block copolymer micelles, Journal of the American Chemical Society, 130, 12921, 2008. 2008 American Chemical Society.)...

Figure 16.15 TEM images for bulk state morphologies of PS- -PFS (a-c), PFS- -PMMA (d) and PMMA- -PFS-Z -PS-Z -PFS- -PMMA (e-f) (PFS = poly(ferrocenylethylmethylsilane) in (a)-(c) and the dimethyl analog in (d)-(f). ((a)-(c) Reprinted with permission from D.A Rider, K.A. Cavicchi, K.N. Power-Billard et al, Diblock copolymers with amorphous atactic polyferrocenylsilane blocks Synthesis, characterization, and self-assembly of polystyrene-block-poly(ferrocenylethylmethylsilane) in the bulk state, Macromolecules, 38, 6931, 2005. 2005 American Chemical Society, (d) Reprinted with permission from C. Kloninger and M. Rehahn, Bicontinuous gyroidic morphologies in ferrocenyldi-methylsilane-b-methyl methacrylate diblock copolymer blends, Macromolecules, 37, 8319, 2004. 2004 American Chemical Society, (e)-(f) Reproduced with permission from U. Datta and M. Rehahn, Synthesis and self-assembly of styrene-[l]dimethylsilaferrocenophane-methyl methacrylate penta-block copolymers, Molecular Rapid Communications, 2004,25,1615. Wiley-VCH Verlag GmbH Co. KGaA.)...

Rider, D.A., Cavicchi, K.A., Power-BiUard, K.N. et al. (2005) Diblock copolymers with ammphous atactic polyferrocenylsilane blocks synthesis, characterization, and self-assembly of polystyrene-block-poly(ferrocenylethyl-methylsilane) in the bulk state. Macromolecules, 38,6931. 

Wang, X.S., Winnik, M.A., and Maimers, 1. (2002a) Synthesis and solution self-assembly of coil-crystalline-coil polyferrocenylphosphine-b-polyferrocenylsilane-b-polysiloxane triblock copolymers. Macrorrwlecules, 35,9146. 

A number of studies have focused on the synthesis of polymers with functionalized sidechains. For example, long-chain alkyl, chloroalkyl, chloro, and alkoxy substitutes polyferrocenylsilanes have been reported. Polymers with... 

Kulbaba K, Cheng A, Bartole A, Greenberg S, Resendes R, Coombs N, Safa-Sefat A, Greedan JE, Stover HDH, Ozin GA, Manners I (2002) Polyferrocenylsilane microspheres synthesis, mechanism of formation, size and charge tunability, electrostatic self-assembly, and pyrolysis to spherical magnetic ceramic particles. J Am Chem Soc 124 12522-12534... 

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