Metal‐Containing Polymers: Building Blocks for Functional (Nano)Materials

Abstract

The incorporation of metallic units into polymer chains has emerged as a promising route towards functional metal-containing (nano)materials. The resulting polymers possess rich functions derived from their metallic elements, such as redox, optical, catalytic and magnetic properties. In addition, the directional and dynamic nature of metal coordination interactions provides further variables for the exploration of novel materials with designed nanostructures. These types of polymers can be synthesized through direct metal-ligand coordination or chain polymerization of metal containing monomers. Depending on the polymerization techniques and starting components, the resulting polymers, akin to their organic counterparts, can be produced in the form of insoluble networks, processible chain structures, gels or colloids. Research into this rising multidisciplinary subject has benefited from recent progress in several related areas such as supramolecular chemistry, colloidal chemistry etc., with the combination of the relative merits of each ensuring further developments in each individual discipline. For example, as a result of studies into organometallic block copolymers self-assembly behavior, living supramolecular polymerization has been unprecedentedly realized for the architectural design of micelles (see image on the right). Nevertheless, the field is still in a developmental stage and offers ample opportunities for fundamental research, as well as material exploration. In this Feature Article, we intend to overview the field with a brief survey of recent literature.

A synthetic route to ultralight hierarchically micro/mesoporous Al(III)-carboxylate metal-organic aerogels

“…Unfortunately, the design of the aerogel is still rudimentary owing to a large disorder present in the structure and the insufficient prediction of gelation behaviour20. Nevertheless, metal coordination is emerging as an effective force when used to drive gelation, offering metal-organic gels (MOGs) as a novel class of functional soft materials212223 in which the scaffolding framework is fabricated by metal–ligand coordination in conjunction with other supramolecular interactions (for example, hydrogen bonding, π-π stacking).…”

Porous Carbons – Hyperbranched Polymers – Polymer Solvation

“…An AB 2 -type monomer (1-13, Scheme 8), was synthesized by Yamanaka et al [133] starting from 3,5-dimethoxyphenol via a polyamic acid methyl ester precursor. The aromatic hb-PIs were prepared by chemical imidization in the presence of acetic anhydride and pyridine.…”

“…However, classical covalent linkages are not necessarily required in order to impart redox sensitivity to polymers [132]. Polymers with suitable ligands can bind redox-active metals by "inorganic" complexation [133]. This coordination concept is even used in a supramolecular sense [134,135].…”

Synthesis of Prussian Blue Coordination Polymer Nanocubes via Confinement of the Polymerization Field Using Miniemulsion Periphery Polymerization (MEPP)

“…[1][2][3][4] A number of NMCP preparative methods have been reported, with various morphologies and functions discussed. However, many of these successes have been predominately as a result of serendipity rather than design, with minimal knowhow available currently in predicting morphological outcomes of such systems.…”