Einelektronen-Redoxreaktionen von 4-(1-Pyridinio)phenolat-Betain: ESR/ENDOR-Charakterisierung seiner Radikalionen und ‘Batterie-Effekt’

One-Electron Redox Reactions of 4-(1-Pyridinio)phenolate Betaine: ESR/ENDOR Characterization of its Radical Ions and ‘Battery Effect’ Blue zwitterionic 2,6-Di(tert-butyl)-4-(2,4,6-triphenyl-1-pyridinio)phenolate 1a can be reduced to its blue-green radical anion ${\bf 1}^{- \atop \dot{}}$ using alkaline metals, and oxidized to its colorless radical cation 1 by Ag(OOCCF₃) or electrochemically. ESR/ENDOR spectra of their aprotic THF solutions indicate predominant spin population either in the pyridinium (${\bf 1a}^{- \atop \dot{}}$) or in the phenolate ring (${\bf 1a}^{+ \atop \dot{}}$). Reduction with other alkaline metals Li, Na, or Cs yields no changes in the ESR/ENDOR signal patterns, i.e. provides no indication of radical ion pair formation. The cyclovoltammetrically determined first reduction and oxidation potentials at ?1.11 V and +0.26 V, respectively, are both reversible and, in principle, allow to construct a molecular battery.     

Electrical properties of planar bimolecular surfactant membrane

Planar bimolecular film of the triple long-chain salt(dihexadecyldimethylammonium hexadecanesulfonate) was found to be formed in the electrolyte solutions was carried out at different temperatures by the transient D. C. method. In four electrolyte solutions of Li⁺, Na⁺, K⁺, and Cs⁺ chlorides, the resistance of the membrane was very high (up to 10⁷ ohm·cm²). From the temperature-dependence of conductivity, the activation energy of ion transfer through the film was calculated by the Arrhenius equation. The magnitude of the activation energy was related with the size of the crystallographic radius.The authors acknowledge financial support from the Swiss National Science Foundation.     

Synthesis and Characterization of ZnO Nanowires

Zinc oxide is a wide bandgap (3.37 eV) semiconductor with a hexagonal wurtzite crystal structure. ZnO prepared in nanowire form may be used as a nanosized ultraviolet light-emitting source. In this study, ZnO nanowires were prepared by vapor-phase transport of Zn vapor onto gold-coated silicon substrates in a tube furnace heated to 900 ?C. Gold serves as a catalyst to capture Zn vapor during nanowire growth. Size control of ZnO nanowires has been achieved by varying the gold film thickness…     

Ion/molecule reactions of isomeric bromobutene radical cations with ammonia

The ion/molecule reaction of the radical cations of three isomeric bromobutenes (2-bromobut-2-ene 1, 1-bromobut-2-ene 2, 4-bromobut-1-ene 3) with ammonia were studied by Fourier transform ion cyclotron resonance spectrometry to reveal the effect of a different position of the bromo substituent relative to the C-C double bond. Further, the reaction pathways of the ion/molecule reactions were analyzed by theoretical calculations at the level B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d). All three bromobutene radical cations 1(.+) to 3(.+) react efficiently with NH(3). The reactions of 1(.+) carrying the halogen substituent at the double bond follow the pattern observed earlier for other ionized vinylic halogenoalkenes. The major reaction corresponds to proton transfer to NH(3) as to be expected from the high acidity of but-2-ene radical cations exposing six acidic H atoms at allylic positions. The other, still important, reaction of 1(.+) is substitution of the Br substituent by NH(3). Although the radical cations 2(.+) and 3(.+) are expected to be as acidic as 1(.+), proton transfer is the minor reaction pathway of these radical cations. Instead, 2(.+) displays bomo substitution as the major reaction. It is suggested that the mechanism of this reaction is analogous to S(N)2' of nucleophilic allylic substitution. Substitution of Br is not efficient for the reactions of 3(.+)-the two major reactions correspond to C-C bond cleavage of the two possible beta-distonic ammonium ions which are generated by the addition of NH(3) to the ionized double bond of 3. This observation, as well as the results obtained for 1(.+) and 2(.+), emphasize the role of the fast and very exothermic addition of a nucleophile to the ionized double bond for the ion/molecule reactions of alkene radical cations. Clearly the energetically-excited distonic ion arising from the addition fragments unimolecularly by energetically accessible pathways. In the case of a halogene subsituent (except F) at the vinylic or allylic position, this is loss of thesubsituent. In the case of remote halogeno substituents, this is C-C bond cleavage adjacent to the radical site of the distonic ion.