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富勒烯 (C60 /C70 )与N ,N ,N′ ,N′ 四 (对甲苯基 ) 4,4′ 二胺 1,1′ 二苯硒醚 (TPDASe)间在激光光诱导条件下 ,发生了分子间的电子转移过程 .在可见 -近红外区 ( 60 0~ 12 0 0nm) ,观测到了TPDASe阳离子自由基、富勒烯 (C60 /C70 )激发三线态和阴离子自由基 ,在苯腈溶液中 ,观测瞬态谱测定了电子从TPDASe转移到富勒烯 (C60 /C70 )激发三线态的量子转化产率(ΦTet)和电子转移常数 (Ket) . 相似文献
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M.Victoria Mart?&#x;nez-D?&#x;azSagrario Esperanza Andrés de la EscosuraMarinella Catellani Sami YunusSilvia Luzzati Tomás Torres 《Tetrahedron letters》2003,44(46):8475-8478
Two new donor-acceptor copolymers comprising a polythiophene backbone, and bearing phthalocyanine chromophores on the side chains have been prepared. Preliminary photophysical characterization of these materials by FTIR photoinduced absorption indicates that electron transfer from the polythiophene to the phthalocyanine units takes place. 相似文献
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Nikos G. Tsierkezos 《Journal of solution chemistry》2007,36(10):1301-1310
The reduction of benzophenone (Bzph) in 3-pentanone (PEN), acetone (ACE), N,N-dimethylacetamide (DMA), N,N-dimethylformamide (DMF), tetrahydrofuran (THF), acetonitrile (ACN) and dimethyl sulfoxide (DMSO) with n-tetrabutylammonium hexafluorophosphate (TBAPF6) as background electrolyte was studied using the technique of cyclic voltammetry at the temperature of 263.15 K. The half-wave
potentials (E
1/2) were extracted. The reduction of Bzph occurs in two successive one-electron steps to produce first the free radical anion
Bzph− and then the dianion Bzph2−. The results indicated that the radical anion Bzph− is reoxidized to Bzph in all investigated solvent media whereas the dianion Bzph2− is reoxidized to Bzph− only in THF. The heterogeneous electron-transfer rate constants (k
s
) were evaluated by employing the electrochemical rate equation proposed by Nicholson. The rate of electron transfer for the
Bzph/Bzph− couple was found to be relatively slow in all investigated solvent media. Consequently, the electron-transfer processes can
be recognized as quasi-reversible. The diffusion coefficients (D) of Bzph in the investigated solvent media have been calculated using the modified Randles-Sevcik equation. The effect of
the physical and chemical properties of the solvent medium on the electrochemical behavior of Bzph has been examined. 相似文献
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Pulse radiolysis technique has been used to characterise the transients formed by the reaction of sulphacetamide with eaq
- and subsequently study the electron transfer reactions from the transient to various electron acceptors such as thionine,
safranine-T and methyl viologen. The results indicate that the semi-reduced sulphacetamide species are highly reducing in nature as they
transfer electrons to various dyes with near diffusion controlled rates (k > 109dm3mol−1s−1) in alkaline and acidic solutions. The influence of oxygen on the decay behaviour of semi-reduced species has been investigated
and the results show that O2 reaction with SA− is very fast (k = 1.5 × l09dm3mol−1s−1) and leads to the formation of a permanent-coloured product. Reactions of H.atoms resulted in the formation of two transient
species whose spectral, kinetic and acid-base characteristics have also been investigated. 相似文献
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Aqueous-soluble monolayer-protected palladium nanoparticles were synthesized by hydrogen reduction of Pd(II) in a water solution. The particles were then further functionalized by incorporating multiple copies of mercapto derivatives of viologen into the particle protecting monolayers. The electrochemistry of the viologen moieties with the particles dissolved in solution or immobilized onto electrode surfaces was carefully studied using various electrochemical techniques. The particle molecular capacitance was evaluated by rotating-disk-electrode voltammetry and the electron-transfer rate constant of the particle-bound viologen moieties was estimated by impedance measurements. 相似文献
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Yoshihiro Tsuda Kohshin Takahashi Takahiro Yamaguchi Syuichi Matsui Teruhisa Komura 《Journal of molecular catalysis. A, Chemical》1998,130(3):244-295
When a viologen-linked Mn(III)porphyrin complex with a short methylene-chain, in which a viologen is covalently linked by the methylene-chain into one phenyl group of 5,10,15,20-tetraphenylporphyrinatomanganese(III)chloride (Mn(III)(tpp)Cl), was used as a catalyst for a monooxygenation of cyclohexene in an air-equilibrated acetonitrile solution containing insoluble zinc powder as a reductant, more cyclohexene oxide was obtained as a single product than when Mn(tpp)Cl was used as a catalyst. Benzoic acid as a cleaving reagent of the dioxygen double-bond and 1-methylimidazole as a ligand to Mn porphyrin were further contained in the reaction mixture. This result implies that the viologen moiety in the viologen-linked Mn(III)porphyrin acted effectively as a mediator for electron transfer from zinc powder to the Mn(III)porphyrin moiety in the epoxidation cycle activating molecular dioxygen reductively. Though Mn(tpp)Cl was remarkably demetallated by H+ ion from benzoic acid during the epoxidation reaction in the mixed system of Mn(III)(tpp)Cl and viologen, the demetallation of the viologen-linked Mn porphyrin with the short methylene-chain was partly prevented because the reduction of a Mn(II)porphyrin-dioxygen adduct was easily caused by fast intramolecular electron-transfer between the two moieties of the viologen and the Mn porphyrin, proceeding the epoxidation cycle smoothly. 相似文献
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Studies by the method of cyclic potential scanning from 0.2 to 1.9 V provided electroanalytical evidence that the reaction
of allyl dithiobenzoate with tetracyanoethylene (TCNE) in MeCN proceeds as the reaction of the TCNE.− radical anion with the PhSSAll.+ radical cation to form phenyl-substituted 2,2,3,3-tetracyano-7,8-dithiabicyclo[3.2.1]octane. When current is not applied,
the reaction does not proceed at 20°C for 3 days. However, this reaction in boiling MeCN occurs without electrochemical activation
and, apparently, involves intermediate formation of the above radical ions. It was established by semiempirical PM3 calculations
that allyl dithiobenzoate and TCNE form a stable charge-transfer complex that precedes chemical electron transfer.
Dedicated to the memory of Professor Viktor Nikolaevich Drozd.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 78–81, January, 1999. 相似文献
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