Doping iodine

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... 

Liu, G., Chen, Z., Dong, C., Zhao, Y., H, F Lu, G.Q., and Cheng, H.M. (2006) Visible light photocatalyst iodine-doped mesoporous titania with a bicrystalline framework. Journal of Physical Chemistry B, 110 (42), 20823-20828. 

In TGA studies on the decomposition of iodine-doped polyacetylene, at high heating rates (30°C/min), decomposition becomes explosive at the m.p. of iodine, 113°C. This was attributed to exothermic reaction of liquid iodine with polyacety-lene. 

F. Huang, A.G. MacDiarmid, and B.R. Hsieh, An iodine-doped polymer light-emitting diode, Appl. Phys. Lett., 71 2415-2417 (1997). 

Y. Zhao, J. Wei, R. Vajtai, P. M. Ajayan, E. V. Barrera, Iodine doped carbon nanotube cables exceeding specific electrical conductivity of metals, Scientific Reports 1 83, 2011. 

Construction of LB films having lateral d.c. conductivities is a burgeoning activity. Results of published work are summarized in Table 9 [726-772]. The first formation of a conducting LB film was reported by French workers in 1985 [726]. Non-conducting LB films were formed from N-docosylpyridinium TCNQ. Subsequent exposure to iodine vapor resulted, however, in the lateral conductivities in the order of 0.1 S cm-1 [726]. The initially formed LB film was shown to consist of (TCNQ. )2 dimers whose molecular planes were almost parallel to the substrate. Iodination resulted in the development of a brown-purple color, the partial oxidization erf the radical anions to TCNQ° and, most importantly, a dramatic rearrangement of the LB film. In iodine-doped films, the TCNQ molecules have been shown to assume a position almost perpendicular to the substrate [721, 773],... 

LB films prepared from N-docosylpyridinium (TCNQ)2 and transferred to substrates Absorption and infrared spectra Lateral d.c. conductivity was determined to be 10"2 Scm"1, even without iodine doping 739, 740... 

Lateral d.c. conductivity of iodine-doped 762 film was about 1 x 10 4 S cm 1... 

Several attempts to induce orientation by mechanical treatment have been reviewed 6). Trans-polyacetylene is not easily drawn but the m-rich material can be drawn to a draw ratio of above 3, with an increase in density to about 70% of the close-packed value. More recently Lugli et al. 377) reported a version of Shirakawa polyacetylene which can be drawn to a draw ratio of up to 8. The initial polymer is a m-rich material produced on a Ti-based catalyst of undisclosed composition and having an initial density of 0.9 g cm-3. On stretching, the density rises to 1.1 g cm-3 and optical and ir measurements show very high levels of dichroism. The (110) X-ray diffraction peak showed an azimuthal width of 11°. The unoriented material yields at 50 MPa while the oriented film breaks at a stress of 150 MPa. The oriented material, when iodine-doped, was 10 times as conductive (2000 S cm-1) as the unstretched film. By drawing polyacetylene as polymerized from solution in silicone oil, Basescu et al.15,16) were able to induce very high levels of orientation and a room temperature conductivity, after doping with iodine, of up to 1.5 x 10s S cm-1. 

In their studies of effects of oxidation of polyacetylene on its dopability, Pochan et al.545 reported that iodine-doped polymer loses its conductivity in vacuum and concluded that the I3 counter-ions are able to react with the polymer chain, leading to iodination. Huq and Farrington 5561 found that bromine- and iodine-doped polyacetylenes lose conductivity rapidly at temperatures below 60 °C, whereas samples doped with AsFs are very much more stable. 

Druy et al.562) showed that iodine- and perchlorate-doped samples lose conductivity quite rapidly in vacuum, due to reaction of the polymer with the counter-ion. Yang and Chien 56l) also observed the instability of these doped polymers and showed that the reaction of polyacetylene with perchlorate counter-ions can be explosive. They showed that doped samples are much more stable to oxygen than is the undoped material. Muller et al.565) also observed that the stability of polyacetylene in air depends on the extent of doping, as did Ohtsuka et al.566). Aldissi 5671 has suggested that iodine doped polyacetylene can be stabilized by phenolic antioxidants, although the effect was modest. 

As discussed earlier, substitution onto the polyacetylene chain invariably has a deleterious effect on dopability and conduction properties. At the same time the stability tends to improve. Masuda et al.583) studied a large range of substituted polyacetylenes and found that stability increased with the number and bulkiness of the substituents, so that the polymers of aromatic disubstituted acetylenes were very stable, showing no reaction with air after 20 h at 160 °C. Unfortunately, none of these polymers is conducting. Deitz et al.584) studied copolymers of acetylene and phenylacetylene they found that poly(phenylacetylene) degrades even more rapidly than does polyacetylene and that the behaviour of copolymers is intermediate. Encapsulation of the iodine-doped polymers had little effect on the degradation, which is presumably at least in part due to iodination of the chain. 

The electrochemical behavior of poly(ferrocenylsilanes) has been studied at three levels—in solution by cyclic voltammetry, as films deposited on electrodes, and in the solid state via iodine doping. Solution cyclic voltammetric oxidation and reduction has shown that the polymer, where R/R is Me/Me, reversibly oxidizes in methylene chloride in two stages, apparently with the first oxidation being on alternating iron atoms along the chain.29 Films cast on electrodes behave in a similar way and also show an electrochromic response to oxidation and reduction.30... 

Iodine-doped hematite has also been studied. The iodine-doped thin films of iron oxide were obtained by spray pyrolysis. The condition for the preparation was not described in detail, apart that a mixture of an 80% ethanolic solution of 0.01 M iodine and 0.1 M FeCl3 was used. Undoped films of 50 nm film thickness showed a maximum photocurrent density of 1.1 mA/cm2, while a 100 nm thick iodine-doped films had a maximum photocurrent density of 5 mA/cm2 at 0.82 V vs. NHE at pH 13 [37]. These measurements were performed with a xenon lamp with a light irradiation of only 150 mW/cm2. At the same condition, it was suggested by model calculation that an optimized stack of five iodine-doped hematite electrodes was expected to yield a photocurrent density of 15 mA/cm2. 

Shibayama, Y., H. Sato, T. Enoki, X. X. Bi, M. S. Dresselhaus, and M. Endo. 2000. Novel electronic properties of a nano-graphite disordered network and their iodine doping effects../. Phys. Soc. Jpn. 69 754-767. 

Simple admixture of arylamines to polysilanes also serves to increase the conductivity upon iodine doping. Addition of 30 wt% of AWW. iV -tetrakisO-methylphenyl)-1,3-diaminobenzene to (PhSiMe)n increased the conductivity of this polymer to 3 x 10"4 Scm-1. 

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