Synthesis of Novel Ladder Polymer Electrolytes Bridged by Sulfonio and Imino Groups

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

“…However, the corresponding ladder polymers or oligomers could not be obtained by this method because of the inherent low conversion. On the other hand, we have demonstrated that a structurally related phenothiazinium salt and a triphenodithiazinium salt were quantitatively obtained by the superacid‐induced Swern condensation of aryl sulfoxides,1 which provided the synthetic route to the corresponding defect‐free ladder polymer electrolyte 1 . Our synthesis of the ladder‐like molecule hinged on the use of the polyaniline derivatives such as 3 , bearing methylsulfinyl groups at suitable positions.…”

“…Reasoning that Pd‐catalyzed polymerization might be disfavored because of the steric effect and/or the electron‐withdrawing nature of the sulfoxide group, we adopted the synthetic route involving three steps: (1) Pd‐catalyzed polymerization of (methylthio) anilines, (2) oxidation of methylthio to methylsulfinyl groups, and (3) the ring closure step. The retrosynthetic scheme provides the possible monomers, 4 , 6 with 7 , and 10 for this reaction, in addition to the previous monomer1 (Scheme ).…”

“…In our previous note,1 it was demonstrated that a ladder polymer 1 (see Scheme ) containing benzenetetrayl units linked by imino and methylsulfonio bonds could be prepared from poly(imino‐4,6‐bis(methylsulfinyl)‐1,3‐phenyleneimino‐1,3‐phenylene) ( 3 ) by the superacid‐induced intramolecular Swern condensation of pendant methylsulfinyl groups (Scheme ) 2. The prepolymer 3 was synthesized by the Pd‐catalyzed aryl amination of 1,3‐dibromo‐4,6‐di(methylthio)benzene with 1,3‐phenyenediamine followed by the oxidation with H 2 O 2 1 as shown in Scheme . Interestingly, polymer 1 with a planar π ‐conjugated structure does not have bulky substituents and yet they are soluble in polar organic solvents such as dimethyl sulfoxide (DMSO) by virtue of the ionic sulfonio groups.…”

“…The ladder polymer 1 was prepared according to the literature 1. Commercial reagents of 2‐(methylthio)aniline, 1,4‐phenylenediamine, thioanisole, N,N′ ‐diphenyl‐1,4‐phenylenediamine, acetyl chloride, acetic anhydride, lithium aluminum hydride (LiAlH 4 ), 4‐(dimethylamino)pyridine (DMAP), methyl iodide, sodium hydroxide, potassium hydroxide, iodine, bromine, triflic acid (TfOH), tris(dibenzylideneacetone)dipalladium(0) (Pd 2 (dba) 3 ), sodium tert ‐butoxide ( t ‐BuONa), 2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl (BINAP), triphenylphosphine (PPh 3 ), (+)‐( S )‐ N,N ‐dimethyl‐1‐[( R )‐2‐(diphenylphosphino)ferrocenyl]ethylamine (PPFA), tris(2‐methylphenyl)phosphine (P( o ‐tolyl) 3 ), sodium sulfite, and pyridine were used as received.…”

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.…”