Metal coordination polymers phthalocyanines

Scheme 6 represents coordinate polymers. A low-molecular-weight compound with multidentate groups on both ends of the molecule grows into a linear polymer with metal ions, and the polymer chain is composed of coordinate bonds. The parquetlike polymer complexes, poly(metal-phthalocyanine) and poly(metal-tetracyano-ethylene), are classified into Scheme 7. They are formed by inserting metal ions into planar-network polymers or by causing a low-molecular-weight ligand derivative to react with a metal salt and a condensation reagent.

Recently, Shirai and Hojo25) have reported the synthesis of the soluble coordinate polymers containing metal-phthalocyanines in the main chain according to Scheme 2 (Eq. 7). The polymers obtained by polycondensation of metal-phthalocyanines bearing peripheral carboxy groups attached to various aromatics, -QH4-, -CsHr-CHz-CgH, exhibit higher conductivities (10-11 10-6 Q cm-1) than the corresponding monomer complexes. 

The synthesis and characterization of coordination polymers was supported by the U.S. Air Force in a search for materials that exhibited high thermal stabilities. However, attempts to prepare stable, tractable coordination polymers that simulate the exceptional thermal and/or chemical stability of model monomeric coordination compounds such as copper(II) ethylenediaminobisacetylacetonate or phthalocyanine have been disappointing ". Typically, only short chains are formed, and the thermally stable monomers lose most of their stability when linked by the metals into polymeric units. The principles in designing coordination polymers are ... 

SiPcs axially substituted with 3- or 4-pyridyloxy moieties have been nsed as bnilding blocks in the formation of alternating coordination polymers when mixed with zinc(n) octathiobutoxy (R = nBu) or octathiophenoxy phthalocyanine (R = Ph) (Figure 9)P The fairly low binding constant, about 300-400 M , between the two Pc-based supramolecular monomers, SiPc and ZnPc, shows how weak the metal-ligand interaction between a pyridine... 

This chapter describes the synthesis and properties of a number of classes of polymers containing metal coordination complexes in their structures. These polymers are prepared by polymerization reactions of metal-containing monomers and through metal coordination reactions. Schiff base-containing polymers (5) were one of the earUest classes of coordination polymers examined. Polymers incorporating macro-cycUc porphyrins and phthalocyanines (7) in their backbones and sidechains are known to exhibit interesting optical and electrical properties. The best-studied classes of metal-containing polymers contain bipyridyl and other related units coordinated to metal ions (8). 

The phthalocyanine moiety (LXa), where M represents a coordinated metal, has been incorporated into polymer structures. LXa is abbreviated by structure LXb. One reaction... 

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