Coordination polymers electrical conductivity

The polymerization of acetylene (alkyne) monomers has received attention in terms of the potential for producing conjugated polymers with electrical conductivity. Simple alkynes such as phenylacetylene do undergo radical polymerization but the molecular weights are low (X <25) [Amdur et al., 1978]. Ionic and coordination polymerizations of alkynes result in high-molecular-weight polymers (Secs. 5-7d and 8-6c). 

There are two classes of materials which may be used as electrolytes in all-solid-state cells polymer electrolytes, materials in which metal salts are dissolved in high molar mass coordinating macromolecules or are incorporated in a polymer gel, and ceramic crystalline or vitreous phases which have an electrical conductance wholly due to ionic motion within a lattice structure. The former were described in Chapter 7 in this... 

Much work has been undertaken to modify electrode surfaces with films which are themselves conducting. The most promising approaches involve organic charge transfer and radical ion polymers. Coordination chemistry has, to date, played little part in this work (a good recent review is available),67 but one example relating to ferrocene chemistry can be quoted. In this example a well known electron acceptor, 7,7, 8,8 -tetracyanoquinodimethane (TCNQ 27), is modified and incorporated into polymer (28) in which the iron(II) of the ferrocene unit is the electron donor. The electrical conductivity of such a film will depend on partial electron transfer between ion and TCNQ centres as well as on the stacking of the polymer chains. The chemistry of other materials, based on coordination compounds, which have enhanced electrical conductivity is covered in Chapter 61. 

Figure 3.16 Ionic electrical conductivity for solutions of lithium triflate in solid poly[fc (methoxyethoxyethoxy)phosphazene] ( MEEP ) is believed to occur following coordination of the etheric side groups to Li+ ions, cation-anion separation, ion transfer from one polymer to another as the polymer and side groups undergo extensive thermal motions. From Shriver and Farrington, Chem. Eng. News, 1985, 42-57 (May 20). Reprinted by permission of the American Chemical Society.

Conjugated polymers may be made by a variety of techniques, including cationic, anionic, radical chain growth, coordination polymerisation, step growth polymerisation or electrochemical polymerisation. Electrochemical polymerisation occurs by suitable monomers which are electrochemically oxidised to create an active monomeric and dimeric species which react to form a conjugated polymer backbone. The main problem with electrically conductive... 

Table 1. Electrical conductivities of some linear coordination polymers of the type...

This reaction seems to be specific for monomers containing amide groups (acrylamide or methacrylamide), but once these monomers are present in the electrolytic medium, other monomers, e. g., acrylonitrile, can be polymerized. The authors attribute the polymerization initiation to the electrogenerated metal ions only, but it is possible that even the perchlorate ion plays a role in the formation of the initiating species. The polyacrylamide thus obtained has an electrical conductivity 3 to 4 times higher than that of polymers obtained by the usual methods. This is due to the presence of metallic cations coordinatively bound in the polymer bulk. The presence of these cations increases the thermal stability of the polymer by 20—40%. 

The donors face to each other to assume a dimeric structure, with close intradimeric S-—S conducts of 3.43-3.52 A. Consistent with the absence of significant interdimeric S—-S interactions, the two compounds exhibit low electric conductivity. The diversity of copper halide frameworks, affected by several elements such as the metal ions, coordination of the halogen atoms, and the stereofactors of the ligand, makes it possible to design two- and three-dimensional coordination polymers. 

Earlandite structure, 849 Electrical conductivity metal complexes, 133 tetracyanoplatinates anion-deficient salts, 136 Electrical properties metal complexes, 133-154 Electrocatalysis, 28 Electrochemical cells, 1 Electrochemistry, 1-33 hydrogen or oxygen production from water coordination complex catalysts, 532 mineral processing, 831 reduction, 831 Electrodeposi (ion of metals, 1-15 mineral processing difficulty, 831 Electrodes clay modified, 23 ferrocene modified, 20 nation coated, 15 polymers on, 16 polyvinylferrocene coated, 19 poly(4-vinylpyridine) coated, 17 redox centres, 17 Prussian blue modified, 21 surface modified, 15-31 Electrolysis... 

Often these polymers are insoluble, although in several cases this can be overcome by adding bulky substituents. Several coordination polymers are stable only in the solid crystalline state. Properties so far described are electrical conductivity, photoactivity, non-linear optical behavior, liquid crystallinity and the formation of porous networks. 

Coordination polymers of transition metal ions with different tetrathiolates such as tetrathiooxalate [54], tetrathiosquarate [55], tetrathiofulvalene tetrathiolate [56,57], benzene- or naphthalenetetrathiolates [58,59]. Such polymers exhibit electrical conductivities up to 30 S cm (for the investigation of the electronic structure see [60]). 

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