Polyferrocenylsilane‐Based Polymer Systems

Abstract

The study of metallopolymers has blossomed into a mature field over the last few decades. Especially, polyferrocenylsilane (PFS) chemistry has taken a tremendous leap and continues to raise intense interest. Since the discovery of thermal ring-opening polymerization (ROP) of sila[1]ferrocenophanes, PFSs have been also accessed by anionic, cationic, transition-metal-catalyzed, and photolytic anionic ROP methodologies. A plethora of synthetic strategies have been devised, enabling access to a wide variety of copolymers, polyelectrolytes, and nanostructured materials. The distinctive physical properties and functions of many PFS-based polymers have been explored, leading to their apt exploitation in technical applications. Therefore, it is conceivable that PFS-related platforms might be indispensable nano-objects in the near future, as they stand on the verge of a new generation of sophisticated materials.

Equilibrium Melting Temperature of Poly(ferrocenyl dimethylsilane) in Homopolymers and Lamellar Diblock Copolymers with Polystyrene

“…[1][2][3][4][5][6][7] Moreover, it counts among the very few metallopolymers accessible by living chain-growth protocols which give access not only to products of defined molar mass and narrow polydispersity but also to a broad variety of copolymer architectures: plenty of PFDMS block copolymers with, e.g., polystyrene (PS), [8][9][10][11] polyisoprene (PI), [12] poly(dimethyl siloxane) (PDMS), [8,12,13] poly(ethylene oxide) (PEO), [14] poly(methyl methacrylate) (PMMA), [15][16][17][18][19][20][21] and poly(2-vinylpyridine) [22] have been synthesized, and they have been shown to develop fascinating morphologies at the nanometer to micrometer scale. [2,7,23] Another important feature of PFDMS is its ability to crystallize. [24] It exhibits a T g of around 30 8C and-depending on molecular mass and thermal history-a melting temperature (T m ) in the range from 110 to 142 8C.…”

Self‐Assembled Nanoscale Ring Arrays from a Polystyrene‐b‐polyferrocenylsilane‐b‐poly(2‐vinylpyridine)Triblock Terpolymer Thin Film

“…[28,29] PFS has also been incorporated into multiblock copolymers with a variety of organic and inorganic coblocks. [28][29][30][31][32][33][34] These block copolymers microphase-separate to give ordered arrays of iron and silicon containing nanostructures, which have already been used in lithographic applications. [35][36][37] PFS possesses interesting properties including resistance to oxygen reactive ion etching, [35][36][37][38] which makes PFS-containing block copolymers useful in nanolithographic applications.…”

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

“…A carbanionic mechanism appears unlikely however, because the ROP of monomers bearing Si-Cl substituents results in high molecular weight polymers. 5 Radicals also do not appear to be involved, and the most likely mechanism appears to be a nucleophilically-assisted process. 30, 31…”

“…PFS materials are readily processed from solution or the melt (see Figure 1) and studies of their properties and applications by numerous workers over the past 25 years have created a field that continues to flourish. 5,6 Developments concerning PFS homopolymers and/or block copolymers and their properties and applications have been previously reviewed. [4][5][6][7] This article, while aiming to be comprehensive, has a particular focus on more recent developments over the past decade although key work from earlier is also discussed.…”