Inorganic complexes, highly conducting

Fig. 1. Electrolytic cell used for the electrochemical syntheses of highly conducting inorganic complexes.

The silver(I) complexes with the tetrakis(methylthio)tetrathiafulvalene ligand have been reported, the nitrate salt presents a 3D structure with an unprecedented 4.16-net porous inorganic layer of silver nitrate,1160 the triflate salt presents a two interwoven polymeric chain structure.1161 The latter behaves as a semiconductor when doped with iodine. With a similar ligand, 2,5-bis-(5,5,-bis(methylthio)-l,3,-dithiol-2 -ylidene)-l,3,4,6-tetrathiapentalene, a 3D supramolecular network is constructed via coordination bonds and S"-S contacts. The iodine-doped compound is highly conductive.1162 (Methylthio)methyl-substituted calix[4]arenes have been used as silver-selective chemically modified field effect transistors and as potential extractants for Ag1.1163,1164... 

Acetonitrile. Acetonitrile is resistant to both oxidation and reduction, is transparent in the region 200-2000 nm, and is an excellent solvent for many polar organic compounds and some inorganic salts. Its dielectric constant of 37 permits reasonably high conductivities, although there is evidence of some association (see Table 7.8). It is less basic than dimethylformamide and dimethyl sulfoxide, and therefore does not solvate alkali metal cations as strongly. However, acetonitrile forms stable complexes with Ag(I) and Cu(I) ions. 

The following is a case history of the one-dimensional inorganic complex, K o.5lr(CO)2Cl2, which exhibits high conductivity at room temperature. This complex exhibits a variety of unusual properties which indicate a columnar structure and a partially oxidized character in spite of the original proposals for its structure. This material serves as an instructive example to point out several features which make the complex worthy of detailed study. To date, the detailed study of its electrical, magnetic, and optical properties has not been reported. 

The chemical and physical properties of inorganic complexes which exhibit a columnar structure are discussed below. Section II. A discusses highly conducting one-dimensional inorganic materials which may be described in terms of a partially occupied electron energy band. Section II.B describes those complexes which exhibit a columnar structure and generally low conductivity. Several less well characterized materials which may exhibit columnar structure are introduced in Section II. C. Section II. D selectively surveys inorganic polymers, with emphasis on poly(sulfurnitride). 

Partial oxidation is the only method successful so far in achieving onedimensional highly conducting systems, but partial oxidation is not sufficient for high conductivity. All partially oxidized inorganic complexes characterized to date are nonstoichiometric. The determination of these nonstoichiometric ratios is the most direct way to determine the degree of partial oxidation. However, the errors associated with routine elemental analyses may be too large to allow the accurate determination of the constancy of the nonstoichiometric composition. 

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