A direct route to polythiophenes displaying lateral substituents: Easy one‐step synthesis and polymerization of thiophene monomers substituted by a dimethylenecarboxylate (CH₂CH₂COOR) appendage on the 3‐position

Abstract

Thiophene monomers displaying a dimethylenecarboxylate (CH 2 CH 2 COOR) substituent on the 3-position of the aromatic ring can be easily obtained and in one step from the electrochemically induced reaction of 3-bromothiophene with the corresponding acrylate (CH 2 ¼ ¼CHCOOR). The synthesis of the ethyl ester monomer, of related 2,5-dihalogenothiophenes, and their polymerization are reported. Despite the surprisingly low solubilities displayed by the polymers, a full spectroscopic characterization could be performed and the data fully analyzed. Oxidative polymerizations (FeCl 3 or electropolymerization) yield a regioirregular polythiophene, with 60-70% of head-to-tail diads. Both experimental and theoretical results suggest that the nonconjugated ester plays a very minor roleif any-in the polymerizations under oxidative conditions, but has a significant influence on the polymer properties. Preliminary attempts to polymerize the dihalogenothiophenes under reductive conditions were hampered by the even lower solubilities exhibited by the regioregular oligomers. V C 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: 900-911, 2012

Reactive polythiophenes with zincke salt structure: Synthesis, polymer reactions, and chemical properties

“…Poly(thiophene‐2,5‐diyl)s (PThs) have been extensively studied because of their interesting chemical properties and practical applications 1–4. PRThs with substituents (R) on the thiophene ring have attracted considerable attention because they exhibit high solubility in organic solvents and have unique solid‐state structures 5–35. For example, regioregular PRThs (where R is a long alkyl chain) cause π‐stacking between the polymer chains to form ordered structures in the solid state or in films, which results in high electric conductivity and carrier ion mobility 32, 33.…”

Ru-Complex-Catalyzed Synthesis of Telechelic Oligobenzimidazoles and Their Chemical Properties, Reactivity, and Structures

“…Well-defined rigid rod oligomers have attracted considerable attention because they can be used to understand the chemical and physical properties of related polymeric materials as well as to investigate structure–property correlations. − The OBIs with reactive NH, CN, and OH groups can be modified by N- and O-alkylation reactions, and alkylated OBI-Rs will self-assemble into ordered structures in the solid state. It has been reported that rigid rod polymers and oligomers with long alkyl side chains often self-assemble into ordered structures in the solid state. − The investigation of the structure–property correlations of such modified OBI-Rs can provide useful information for the development of new functional materials. To date, there have been no reports on telechelic OBIs, their applications as macromonomers, or OBI-Rs with self-assembled ordered structures.…”

Optical and electrochemical properties of oligo(1,5‐dialkoxynaphthalene‐2,6‐diyl)s with self‐assembled ordered structures in solid state

“…π‐Conjugated polymers have attracted considerable attention owing to their interesting chemical properties and practical applications . The molecular self‐assembly of π‐conjugated polymers into ordered structures in the solid state considerably affects their chemical properties . It has been reported that π‐conjugated polymers consisted of a rigid main chain with long alkyl side chains often self‐assemble into ordered structures in the solid state …”