1653-16-3Relevant articles and documents
Preparation and electrochemistry properties of trifunctional 1,9-dithiophenalenylium salt and its neutral radical with benzene spacer
He, Guangrui,Hou, Yanhui,Sui, Dong,Wan, Xiangjian,Long, Guankui,Yun, Peng,Yu, Ao,Zhang, Mingtao,Chen, Yongsheng
, p. 6890 - 6896 (2013)
A trifunctional 1,9-dithiophenalenylium salt with benzene spacer has been prepared as the precursor for a phenalenyl-based high spin radical. Electrochemical studies show that this salt undergoes two three-electron reduction steps and generate its corresponding neutral radical, which has been studied by quantum chemical calculations. The investigation of the spin density distribution of the radical revealed that the spin and electronic properties of molecules based on phenalenyl systems are strongly influenced by intramolecular topology connection.
Ligand Free Palladium-Catalyzed Synthesis of α-Trifluoromethylacrylic Acids and Related Acrylates by Three-Component Reaction
Bouillon, Jean-Philippe,Couve-Bonnaire, Samuel,Pannecoucke, Xavier,Xiao, Pan
supporting information, p. 949 - 954 (2020/01/28)
Aryl iodides and 2-(trifluoromethyl)acrylic acid reacted together in ligand-free Mizoroki-Heck reaction furnishing a quick and efficient access to highly valuable α-trifluoromethylacrylic acids. The useful transformation was independent with regard to the electronic nature of the aryl group substituent. A three-component one-pot version was also developed to give diverse substituted acrylates. The versatility of α-trifluoromethylacrylic acids was demonstrated by quick access to 3-CF3-coumarins as well as fluorinated analogues of therapeutic or cosmetic agents. Finally, we proposed a catalytic cycle based on the silver carboxylate salt, identified as a key intermediate in the reaction. (Figure presented.).
Rapid Solution and Solid Phase Syntheses of Oligo(1,4-phenylene ethynylene)s with Thioester Termini: Molecular Scale Wires with Alligator Clips. Derivation of Iterative Reaction Efficiencies on a Polymer Support
Jones II, LeRoy,Schumm, Jeffry S.,Tour, James M.
, p. 1388 - 1410 (2007/10/03)
The syntheses of soluble oligo(2-alkyl-l,4-phenylene ethynylene)s via an iterative divergent/ convergent approach starting from 1-(diethyltriazyl)-3-alkyl-4-[(trimethylsilyl)ethynyl]benzenes are described. When the solublizing alkyl group is an ethyl substituent, the monomer, dimer, tetramer, and octamer can be synthesized. The octamer, however, is only minimally soluble. When the alkyl substituent is 3-ethylheptyl or dodecyl, the compounds are easily dissolved even at the 16-mer stage. The 16-mer is 128 A long in its near-linear extended conformation. At each stage in the iteration, the length of the framework doubles. Only three sets of reaction conditions are needed for the entire iterative synthetic sequence: an iodination, a protodesilylation, and a Pd/Cu-catalyzed cross coupling. Synthesis of the dodecyl-containing 16-mer was also achieved on Merrifield's resin using the iterative divergent/convergent approach. The oligomers were characterized spectroscopically and by mass spectrometry. The optical properties are presented which show that at the octamer stage, the optical absorbance maximum is nearly saturated. The size exclusion chromatography values for the number average weights, relative to polystyrene, illustrate the tremendous differences in the hydrodynamic volume of these rigid rod oligomers verses the random coils of polystyrene. These differences become quite apparent at the octamer stage. Equations were derived for assessing the efficiency of the polymer-supported reactions based on resin weight differences, molar concentration differences, and elemental analysis data. Each of these methods' limitations are discussed. Attachment of thiol end groups, protected as thioacetyl moieties, was achieved. These serve as binding sites for adhesion to gold surfaces. In some cases, one end of the oligomeric chains is capped with a thiol group so that the surface attachments to gold could be studied. In other cases, thiol groups are affixed to both ends of the molecular chains so that future conduction studies could be done between proximal metallic probes. The rigid rod conjugated oligomers may act as molecular wires in molecular scale electronic devices, and they also serve as useful models for understanding analogous bulk polymers.
