Supramolecular polymer networks metal complexation

Scheme 2 Popular metal complexation motifs used for supramolecular polymer-network formation. py pyridine, bpy bipyridine, tpy terpyridine, BTP 2,6-bis(l,2,3-triazol-4-yl)pyridine, BIP 2,6-bis(l-methylbenzimidazolyl)pyridine, DOPA dihydroxy-phenylalanine, PAA poly (acrylic acid)...

We also realized viscosity oscillations of a polymer solution based on different mechanisms [26]. It is known that a terpyridine ligand binds or dissociates with a Ru metal ion depending on the redox states of the Ru metal ion [29]. Generally, when the Ru metal ion is in the reduced Ru(II) state, the Ru(II) metal ion forms bis-complexes with terpyridine (Ru(terpy)2). However, when the Ru metal ion is in the oxidized Ru(III) state, the Ru(in) metal ion forms a monocomplex with terpyridine (Ru(terpy)) (Fig. 11.7). Therefore, supramolecular block copolymers have been made by using Ru(terpy)2 as a junction point [29], If the Ru-terpyridine complex acts as a catalyst of the BZ reaction, the redox oscillation may cause periodical binding/dissociation of the Ru-terpyridine complex. Recently, a theoretical computational simulation in the case that the Ru-terpyridine complex acts as a reversible crosslinking point of polymer network during the BZ reaction has been reported by Balazs et al. [30]. The... 

Methods based on the formation of complexes of CDAs with metal cations seem especially interesting for testing using PPAs, due both to the possibility of controlling the conformational equilibria at the pendants that will transmit further effects to the backbone, and to the potential role that metal ions could play in the establishment of supramolecular networks between the polymer chains (interchain bonding), giving birth to new types of nanostructures (i.e. helical polymer-metal complexes, HPMCs). 

The non-cross-linked poly(acrylamide) 79 bearing the triarylphosphino groups was prepared from the acrylamide monomer and diphenyl(styryl) phosphine. The metal-directed self-assembly process between the non-cross-linked polymer ligand 79 and the palladium species afforded the networked supramolecular complex 80 [106, 109]. The complex catalyzed the Suzuki-Miyaura coupling [106,109] and the same concept, a tungsten-based self-assembly complex, has also been developed for the catalytic oxidation process. 

---