Palladium-catalyzed synthesis of oligo(methylthio)aniline and conversion to polyacene-type electrolytes bearing phenothiazinium repeating units

Abstract

The synthetic routes to ladder polymers which consist of benzenetetrayl subunits with imino and methylsulfonio linkages are described. As the key intermediate, oligo‐ and polyaniline derivatives having pendant methylthio groups are prepared by the Pd‐catalyzed aryl amination from various monomers. The oxidation of the polymers with H2O2 in the presence of CH3COOH effects the high yielding conversion of methylthio to methylsulfinyl groups without the formation of the undesired methylsulfonyl groups. The superacid‐induced condensation of the resulting polymers under dilution conditions induced the polymer‐analogous intramolecular electrophilic ring closure reaction of the hydroxy(methyl)(phenyl)sulfonium cation onto the adjacent benzene ring to yield the required ladder polymers which have proved to be semiconductors with intrinsic electric conductivities of ca. 10−5 S · cm−1.

Creation of persistent charge-transfer interactions in TCNQ polyester

“…[2][3][4][5] For example, the addition of p-type doping reagents, such as tetracyanoethylene, 7,7,8,8-tetracyanoquinodimethane (TCNQ) and their derivatives, to electron-rich polymers produces open-shell polymers because of the charge-transfer (CT) complexation. [6][7][8][9][10] However, a similar approach using the combination of n-type doping reagents and electrondeficient polymers is rare, probably because of the difficulty of preparing precursor polymers, namely electron-deficient conjugated polymers, and the limited chemical stability of the n-doped polymers at room temperature.…”

Heteropolyacene with Thianthrenium Ring Systems ProvingπElectron Delocalization over S Atoms

“…6) containing benzenetetrayl units bridged by imino and methylsulfonio groups, an analogue of 5 containing imino groups in place of the sulfido linkages, were prepared. [22,23] However, the optical band gap estimated from the tailing edge of the absorption spectrum (520 nm, 2.4 eV) indicated that the p-electron conjugation did not extend throughout the polymer chain. The localized intramolecular donor -acceptor interaction between the imino and methylsulfonio moieties was also considered to play a role in the visible absorption.…”

“…The localized intramolecular donor -acceptor interaction between the imino and methylsulfonio moieties was also considered to play a role in the visible absorption. [16,22] A heteropolyacene 6 having phenoxathiinium-type repeating units was also prepared. [21] Taking into account the lack of such donor -acceptor interaction between oxo and methylsulfonio linkages, one could ascribe the smaller band gap in 6 only to the p-electron delocalization through the polymer backbone.…”

Effect of morphology of polyaniline nanomaterials on cure kinetics and properties of liquid crystalline epoxy nanocomposite

“…Recently, there has been a consid-erable interest on the synthesis of PANI nanomaterials owing to their potential applications, such as antistatic coating, corrosion protection, batteries and energy storage, catalysts, and chemical sensors. [14][15][16][17][18][19][20][21][22][23] It is possible to prepare novel electrically conducting composites through the combination of complementary properties of LCE and PANI nanomaterials. The combination of advantageous properties of LCE and PANI nanomaterials can offer an attractive route not only to reinforce LCE matrix but also to introduce new electrical properties based on the enhanced electronic interaction.…”