Organometallic polymers polymer chain incorporation

Metal-containing polymers may be produced by various methods, such as chemical reactions of precursors— in particular, reactions of metal salts in polymer solutions, the treatment of polymers with metal vapors, or the polymerization of various metal-monomer systems [1-4], Depending on the metal nature and the polymer structure, these processes lead to organometallic units incorporated into polymer chains, metal-polymer complexes, or metal clusters and nanoparticles physically connected with polymer matrix. Of special interest are syntheses with the use of metal vapors. In this case, metal atoms or clusters are not protected by complexones or solvate envelopes and consequently have specific high reactivity. It should be noted that the apparatus and principles of metal vapor synthesis techniques are closely related to many industrial processes with participation of atomic and molecular species [5]—for example, manufacturing devices for microelectronic from different metals and metal containing precursors [6]. Vapor synthesis methods employ varying metals and... 

On the basis of the fact that metallacycles such as metallacyclopentadiene derivatives have unique and versatile reactivity,incorporation of these units into the backbone of the polymers are quite attractive to realize mainchain reactive materials (Fig. 2). Besides, these materials are potentially attractive as novel functional materials if the unique geometry of the organometallic systems reflects the character of the polymers and/or each metal center included in the polymer chains interacts by appropriate macromolecular design. 

Organometallic polyurethanes containing backbone polyether units have been reported.184,185 The incorporation of ferrocenyl segments into the backbone of polyurethanes enhanced thermal stability.186 There have been a number of studies on the incorporation of ferrocenyl units into the backbone of polyesters 101.187-191 A number of polymers of this class exhibited liquid crystalline properties.189-192 The thermal stability and glass transition temperatures of these polymers decreased with an increase in the length of the alkyl chains. 

Ferrocene is an attractive and convenient organometallic species to incorporate into conjugated polymers—it is stable, easy to functionalize, has reversible electrochemistry, and its derivatives (both monomeric and polymeric) can be easily characterized [e.g., by nuclear magnetic resonance (NMR) spectroscopy]. Ferrocene has been incorporated into the backbone and side chains of polythiophene 45 In 1999, both Higgins and Wolf independently reported the synthesis of polythiophenes with ferrocene in the backbone.46,47 Electropolymerization of ferrocene substituted... 

Ferrocene was the starting point for organometallic chemistry nearly four decades ago and is still today one of the most studied and versatile organometallic building blocks. Ferrocene has been incorporated in polymeric systems to alter bulk properties of the material. Ferrocene possesses excellent thermal and photochemical stability and can also protect polymeric systems from photodegradation. In addition, the ferrocene building block has been used in conducting polymers and in main chain liquid crystalline polyesters. ... 

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