Coordination complexes homopolymers

Compared to block copolymers, there have been relatively fewer examples of using homopolymers for nanofabrication. Nevertheless, some polymers with amphiphilic properties were also used in the fabrication of nanostructures with various metal salts/complexes. For example, polyaniline (PANI) emeraldine base formed self-organized mesomorphic structures when mixed with Zn(DBS)2 by the coordination between Zn2+ and the imine nitrogen atoms on the polymer main chain.100 The resulting supramolecule PANI[Zn(DBS)2]0.5 had a comb-shaped... 

The simplest way to turn these molecular complexes into polymers is to prepare the polymer backbones containing pure ligand, such as polybipyridine homopolymers. These tend to be rather intractable, hence, the emphasis in the succeeding sections on mixed polymer chains. Nevertheless, interesting examples of this approach include polybenzimidazoles 14, which can coordinate to Ru centers [43], Despite complications in the emission spectra from the formation of aggregates, LEDs prepared from this material exhibited 0.1% external quantum efficiency. 

Similar Ru-O coordination has been observed in both the crystal structure of an r -methyl vinyl ketone complex [34] and in the DFT calculations of a ruthenium ester carbene by Parker, Sampson, and co-workers [35]. The stability of the ester carbene intermediate led to the inactivity of a 1-substituted cyclobutene ester in the formation of homopolymers via ROMP (ring-opening metathesis polymerization) (Scheme 7.2) [36]. 

Fig. 19 (a) Formation of a complex coacervate core microemulsion (C3 — pE) droplet. The core comprises anionic homopolymer green, hp ), cationic homopolymer purple, hp ), and cationic block red, dp ) of diblock copolymer. The corona consists of the electroneutial hydrophilic blocks blue) of the diblock copolymer, (b) Formation of C3-(iE containing coordination polymers. Adapted from [81]. Reprinted with permission from the Royal Chemical Society... 

Kros et al. reported a polymer-peptide conjugate prepared via nickel-mediated NCA polymerization and a subsequent polymerization of an isocyanide, again using the nickel complex as initiator [111]. The active catalyst is attacked by the more electrophilic isocyanide and the coordinated amine reacts with the isocyanide to yield a carbene-like initiator for the isocyanide polymerization (see Fig. 14). The product can be purified from free residual homopolymers by selective solvent... 

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