The effects of the polymerization temperature and of voltammetric cycling on the chain length and the resistivity of polypyrrole films are investigated. The studies provide further proof for the existence of at least two different types of polypyrrole, the so-called PPy I and PPy II. As the electropolymerization of conjugated systems in contrast to normal polymerization reactions is a fully activated process, the generation of these different types of PPy depends on experimental parameters such as temperature or formation potentials. UV-vis measurements demonstrate that PPy II comprises significantly shorter chains than PPy I (8-12 vs 32-64 units); moreover, film conductivity is found to increase with the fraction of PPy II. This fraction is changed via the polymerization temperature as well as by cyclic voltammetry, both of which can induce a metal-insulator transition. The counter-intuitive relationship between resistivity and chain length is interpreted in terms of disorder-dominated transport, in which the shorter chains of PPy II support the formation of delocalized electronic states, thereby increasing the localization length. Thus, our results are in agreement with recent broadband reflectivity measurements.
The reaction O(,PJ) + (CH&SiH -products (1) has been investigated by the discharge/fast-flow method with mass spectrometric detection (DF-MS) over 298-773 K and by the flash photolysis/resonance fluorescence (FP-RF) technique over 293-549 K. The rate constants from both methods are in close accord and may be summarized by kl(T) = 5.6 X lo-" exp(-1005 K/7') cm3 molecule-' s-l for 290-770 K. There is reasonable agreement with previous room-temperature studies. kl is larger than k2 for 0 + SiH4 (2), similar to results for triethylsilane and triisopropylsilane [Buchta, Chr.; Stucken, D.-V.; Vollmer, J.-T.; Wagner, H. Gg. Z. Phys.Chem. Neue Folge, to be published], and tri-alkylation is seen to increase the reactivity of the Si-H bonds by similar amounts largely independent of the nature of the alkyl group. This silane activation occurs through lowering the energy barrier to abstraction to form O H + (CH3)3Si*. Ab initio analysis of this pathway at the MP2/6-31G*//HF/3-21G(*) level of theory gives relative energies for the transition states of reactions 1 and 2 that agree well with experiment.
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