Representative Metallopolymers

The aim of these pages is not only to hopefully pick up most meaningful examples among the materials proposed for analytical scope, but also to identify those that, for pecufiar characteristic behavior, seem to be particularly appealing in respect to an appfication in electroanalysis. 

The metal centers are chosen from those that typically exhibit, in the frame of the complexes, reversible redox behavior, being stable in two oxidation states. Such a feature is required in order to sustain electrical conduction, either purely redox in character or somehow hybridized with the electronic one, proper of the a -electron chain fragments. Moreover, it also constitutes an evident necessity whenever one partner of the redox couple is called to play the role of redox mediator in 

---

Platinum polyynes represent one of the most interesting and well-studied classes of linear metallopolymers. Dendritic analogs of these materials have been prepared via a variety of methodologies. One example is the nonametallic dendrimer 248 that was prepared via a convergent route as illustrated in Equation (92). Dendrimers based on ruthenium polyyne architectures have also been prepared and promising NLO properties have been identified. ... 

Unsaturated nitriles, in principle, have two centers of coordination an unshared pair of electrons on the nitrogen atoms and the n-electrons of double and triple bonds, sometimes, both Ji- and -electrons take part in coordination with MX simultaneously. There are representatives of all types of the complexes, but for the synthesis of metallopolymers the nv-type MCM complexes are of greatest interest. For instance, acrylonitrile and methacrylonitrile are widely used ligands for the synthesis of this type of MCM, as is acrylamide (AAm). The existence of the double bond in AAm markedly... 

At present, several thousand metallopolymers have been described, although the part of those obtained by polymerization and l lopolymerisation of metal-containing monomers is not great. Nevertheless, the procedures of synthesis of over 200 metallomonomers are given in the monograph [124]. In this book we restrict ourselves to preparative methods of synthesis only of some main representatives of metal-containing monomers and their polymers. 

In Ref. [109], a particularly significant example is found of the potentiality of metallopolymers in detecting selectively different metal ions bipy hgand is inserted inside an oligothienyl chain. Bipy reversibly captures Zn(ll) or Cu(ll)/Cu(I) metal ion and the coordination is completed by a rotaxane macrocycle two additional N atoms satisfy the tetracoordination tendency of both metals. Figure 3.23 represents the structural tuiits of the two different systems. 

Peculiar metallopolymers, seemingly representative of situations intermediate between type 2 and 3 metallopolymers, present the metal co-ordinated to a ligand that is part of the jr-electron chain and completes the co-ordination set with additional external ligands. Similar metallopolymers have been synthesized and characterized, in which the Ru metal is co-ordinated to bipy belonging to the ICP backbone, consisting of bipy and Th basic structural units in a co-polymeric chain [68] (see Fig. 3.24) ... 

Thus rmit variability in metallopolymers can be represented in a simplified form by scheme 32, which takes into account the change in the metal valence state, ligand environment, nuclearity and the elimination of a metal-containing group. 

---