Polyferrocenylsilane block copolymers synthesis

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. 

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.)...

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). 

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 16.15 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. 

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