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21.
Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η5-C5H5)Fe2+(η5-C5H4)-CH2-CH2-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe3+ at the expenses of Fe2+ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO− groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe3+ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing. 相似文献
22.
K. C. Kumara Swamy E. Balaraman M. Phani Pavan N. N. Bhuvan Kumar K. Praveen Kumar N. Satish Kumar 《Journal of Chemical Sciences》2006,118(6):495-501
The diversity of products in the reaction of diethyl azodicarboxylate (DEAD)/diisopropyl azodicarboxylate (DIAD) and activated
acetylenes with PIII compounds bearing oxygen or nitrogen substituents is discussed. New findings that are useful in understanding the nature
of intermediates involved in the Mitsunobu reaction are highlighted. X-ray structures of two new compounds (2-t-Bu-4-MeC6H3O)P (μ-N-t-Bu)2P+[(NH-t-Bu)N[(CO2]-i-Pr)(HNCO2-i-Pr)]](Cl-)(2-t-Bu-4-MeC6H3OH)(23)and [CH2(6-t-Bu-4-Me-C6H2O)2P(O)C(CO2Me)C-(CO2Me)CClNC(O)Cl] (33) are also reported. The structure of23 is close to one of the intermediates proposed in the Mitsunobu reaction. 相似文献
23.
Yuliya V. Rassukana Kateryna O. Davydova Anatolii D. Sinitsa 《Tetrahedron letters》2004,45(20):3899-3902
Hydrophosphoryl nucleophilic agents add to the CN bond of N-sulfonyltrichloroacetimidoylphosphonates to give unstable C,C-diphosphorylated adducts, which undergo competitive 1,2-C → N phosphorotropic rearrangement and dehydrochlorination with the formation of aza-Perkow reaction products, C,N-diphosphorylated dichlorovinylsulfonamides. This is the first reliably identified case of an aza-Perkow transformation for acid phosphites and their initial nucleophilic attack at the C atom of the azomethine bond in the aza-substrates. 相似文献
24.
Characterizations of Tb:Zn2SiO4 films on silicon wafer prepared by sol-gel dip-coating and solid-phase reaction 下载免费PDF全文
Terbium-doped Zn_2SiO_4 films were successfully prepared on Si wafers by a simple sol-gel dip-coating and solid-phase reaction method of ZnO and SiO_2. X-ray diffraction (XRD) and UV-Vis absorption results revealed that films processed below 850℃ were ZnO in wurzite structure, and films processed above 850℃ were Zn_2SiO_4 in wellimite structure. Photoluminescence measurements of the Tb-doped Zn_2SiO_4 films showed two strong emission bands at 490 and 545nm. The photoluminescence lifetime was 4.6ms. 相似文献
25.
Emmanuel DardennesÁrpád Kovács-Kulyassa Andrea RenzettiJanos Sapi Jean-Yves Laronze 《Tetrahedron letters》2003,44(2):221-223
Chiral pyrano- and pyrrolidino-fused tryptamines were prepared by a diasteroselective trimolecular condensation between indole, Garner's aldehyde and Meldrum's acid, followed by selective functional group transformations. 相似文献
26.
An intermolecular aldol reaction of 20S-camptothecin-7-aldehyde in the presence of strong bases affords an unusual dimeric compound, the structure and stereochemistry of which was assigned on the basis of NMR analysis and MM2 calculations. 相似文献
27.
Grindstone Chemistry--a greatly evolved version of Toda’s method of grinding solids together for solvent-free chemical reactions--has been described and its usefulness illustrated by the successful application of this technique to a simplified process for conducting the multi-component Biginelli reaction for the synthesis of physiologically active tetrahydropyrimidinones. 相似文献
28.
Luc Martinon Stéphane Azoulay E. Peter Kündig 《Journal of organometallic chemistry》2004,689(23):3831-3836
A Pd-catalyzed three-component assembling of highly functionalized 4-benzyl-(and allyl-)pyrrolidines was achieved based on a combination of allyl amines, gem-diactivated alkenes, and unsaturated halides (or triflate). 相似文献
29.
The Mannich-type reaction of imines with (1-methoxy-2-methylpropenyloxy)trimethylsilane and aza-Diels-Alder reaction of imines with Danishefsky's diene can be carried out in scCO2 in the presence of lithium heptadecafluorooctanesulfonate which offer a way to synthesize β-amino carbonyl compounds and nitrogen-containing six-membered ring compounds under environmentally benign conditions. 相似文献
30.
Mingbao Zhang Raymond Reeves Cheng Bi Robert Dally Gaetan Ladouceur William Bullock Jefferson Chin 《Tetrahedron letters》2004,45(27):5229-5231
Three novel, optically active, 6-substituted 2-(aminomethyl)chromans were synthesized from readily available chroman 2-carboxylic acid precursors. These chroman-containing primary amines are useful building blocks for the synthesis of chroman-derived pharmaceutical agents. 相似文献