Conjugated systems metal coordination polymers

Compared to the silole-containing polymers, phosphole has received little attention as a building block for extended -conjugated systems, despite its unique characteristics and numerous applications in organic and metal coordination chemistry. The first practically applicable synthesis was independently presented in 1959 by two groups. The first successful synthesis of phosphole-containing 7i-conjugated polymers was established by Tilley and... 

As surmized in a recent review article there are literally hundreds of polymeric systems featuring organometallic complexes within a conjugated organic backbone. Given recent reviews of these systems, here we shall restrict discussion to the various polymeric species and ceramic materials derived from diyne complexes and from coordination of metal fragments to polymers featuring C=CC=C repeat units. 

The optical and PL spectroscopies have been undertaken to understand the structure-property correlations of this important family of triplet-emitting polymers. The red shift in the absorption features upon coordination of the metal groups is consistent with there being an increase in conjugation length over the molecule through the metal center. The trade-olf relationship between the phosphorescence parameters (such as emission wavelength, quantum yield, rates of radiative and nonradiative decay) and the optical gap will be formulated. For systems with third-row transition metal chromophores in which the ISC efficiency is close to 100%,76-78 the phosphorescence radiative (kr)y, and nonradiative (/cm)p decay rates are related to the measured lifetime of triplet emission (tp) and the phosphorescence quantum yield ([Pg.300]

This chapter describes the coordination polymerization of acyclic and cyclic vinylic monomers, conjugated dienes, and polar vinylic monomers with the most important catalytic systems known in this area. A chronological classitication for the development of the main coordination catalyst types is outlined, as well as polymerization kinetics and mechanisms and applications of polymers obtained through different metallic complexes. 

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