Recent Trends in Metallopolymer Design: Redox‐Controlled Surfaces, Porous Membranes, and Switchable Optical Materials Using Ferrocene‐Containing Polymers

Abstract

Metallopolymers with metal functionalities are a unique class of functional materials. Their redox-mediated optoelectronic and catalytic switching capabilities, their outstanding structure formation and separation capabilities have been reported recently. Within this Minireview, the scope and limitations of intriguing ferrocene-containing systems will be discussed. In the first section recent advances in metallopolymer design will be given leading to a plethora of novel metallopolymer architectures. Discussed synthetic pathways comprise controlled and living polymerization protocols as well as surface immobilization strategies. In the following sections, we focus on recent advances and new applications for side-chain and main-chain ferrocene-containing polymers as (i) remote-switchable materials, (ii) smart surfaces, (iii) redox-responsive membranes, and some recent trends in (iv) photonic structures and (v) other optical applications.

Synthesis of Negative‐Charged Metal‐Containing Cyclomatrix Polyphosphazene Microspheres Based on Polyoxometalates and Application in Charge‐Selective Dye Adsorption

“…Metallopolymers are functional polymers with metal centers in their frameworks, which can integrate both the functions of metal elements and the properties of polymers . Many different metal‐containing building blocks and polymer topologies have been reported .…”

Electrochemically Triggered Interfacial Deposition/Assembly of Aqueous‐Suspended Colloids

“…With this method, high‐fidelity colloid micropatterns can be formed in seconds. This work expands the utility of ferrocene‐based redox‐controlled surfaces, which was pioneered by the Whitesides group and has since then seen quite exciting new development in the field of metallopolymers …”

Switchable Stimuli-Responsive Heterogeneous Catalysis

“…Elbert et al [41] reported that it is possible to reversibly modulate the catalytic activity of Grubbs Second Generation catalyst for the ROMP (ring-opening metathesis polymerization) reaction of nerbornene when it is immobilized on the surface of SiO 2 NPs functionalized with poly (vinylferrocene). In fact, when poly(vinylferrocene) is oxidized, it increases its hydrophilicity and the polymeric network swells [42] creating a thicker shell layer that hinders the diffusion of apolar molecules (such as nerbornene) toward the catalyst. As a consequence, after oxidation of the poly(vinylferrocene), the ROMP reaction can be not catalyzed by the immobilized Grubbs Second Generation catalysts, which are not accessible to norbonene monomers.…”