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Abstract: Chemical and topographic surface patterning of inorganic polymer‐functionalized nanoparticles (NPs) and their self‐assembly in nanostructures with controllable architectures enable the design of new NP‐based materials. Capping of NPs with inorganic polymer ligands, such as metallopolymers, can lead to new synergetic properties of individual NPs or their assemblies, and enhance NP processing in functional materials. Here, for gold NPs functionalized with polyferrocenylsilane, two distinct triggers are used to induce attraction between the polymer ligands and achieve NP self‐assembly or topographic surface patterning of individual polymer‐capped NPs. Control of polymer–solvent interactions is achieved by either changing the solvent composition or by the electrooxidation of polyferrocenylsilane ligands. These results expand the range of polymer ligands used for NP assembly and patterning, and can be used to explore new self‐assembly modalities. The utilization of electrochemical polymer oxidation stimuli at easily accessible potentials broadens the range of stimuli leading to NP self‐assembly and patterning. [ABSTRACT FROM AUTHOR]

The incorporation of metal atoms into synthetic polymer chains leads to desirable properties and generates a new and versatile class of functional materials with enhanced processability. New creative approaches have led to macromolecular structures in which metals are not only incorporated via the use of traditional covalent bonds but also by potentially reversible coordination interactions. Metallopolymers with precisely controlled chain length are therefore attracting rapidly expanding attention as a result of their properties and potential applications. This article focuses on polyferrocenylsilanes and polyferrocenylsilane block copolymers where iron and silicon are present in the main chain of the organometallic segment. These materials also represent an area of rapidly growing interest as a result of their self-assembly. The resulting nanostructured materials have a wealth of potential applications and recent breakthroughs in this area are discussed. The subject matter of the article is divided up into subsections covering polyferrocenylsilane homopolymer and block copolymer synthesis, solution and solid state self-assembly, and applications. [ABSTRACT FROM AUTHOR]

Mixed micelles formed by co‐assembly of pairs of block copolymers (BCPs) can develop novel morphologies and generate useful properties not accessible from homomicelles. For micelles consisting of two different polymers in the corona, identifying the location of the corona chains is a critical part of morphology characterization. Coronal segregation in mixed micelle is often characterized by transmission electron microscopy in combination with selective staining of individual polymers. In this study, Karstedt's catalyst is used for selective Pt(0)‐olefin coordination staining of polyisoprene (PI) and poly(methylvinylsiloxane) (PMVS) corona chains in the presence of poly(dimethylsiloxane) (PDMS) corona chains in cylindrical mixed micelles with a crystalline poly(ferrocenyldimethylsilane) (PFS) core. Previous experiments using OsO4 as a stain did not enable visualization of nanoscale coronal segregation in mixed micelles obtained from co‐assembly of PFS‐b‐PI and PFS‐b‐PDMS, as well as PFS‐b‐PMVS and PFS‐b‐PDMS. Karstedt's catalyst can be used as a staining agent for visualizing nanoscale coronal segregation in core‐crystalline comicelles through Pt(0)‐olefin coordination. [ABSTRACT FROM AUTHOR]