Simple synthesis of P(Cbz-alt-TBT) and PCDTBT by combining direct arylation with suzuki polycondensation of heteroaryl chlorides

Macromol Rapid Commun. 2015 Jan;36(2):231-7. doi: 10.1002/marc.201400437. Epub 2014 Oct 21.

Abstract

Direct arylation (DA) of 2-chlorothiophene and 2-chloro-3-hexylthiophene with 4,7-dibromo-2,1,3-benzothiadiazole is used to synthesize 4,7-bis(5-chloro-2-thienyl)-2,1,3-benzothiadiazole (TBTCl2) and 4,7-bis(5-chloro-4-hexyl-2-thienyl)-2,1,3-benzothiadiazole (DH-TBTCl2) in one step. Suitable conditions of the Suzuki polycondensations (SPC) of TBTCl2 and DH-TBTCl2 with the carbazole comonomer CbzPBE2 are established, furnishing PCDTBT and P(Cbz-alt-TBT) with high molecular weight and yield. Compared with control samples made from the corresponding dibromides, high-temperature NMR and UV-vis spectroscopy indicate similar properties for PCDTBT but an increased content of Cbz-Cbz homocouplings for P(Cbz-alt-TBT).

Keywords: Suzuki polycondensation; conjugated polymers; direct arylation; heteroaryl chlorides; homocoupling.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Carbazoles / chemistry
  • Chlorides / chemistry*
  • Hydrocarbons, Aromatic / chemistry*
  • Magnetic Resonance Spectroscopy
  • Models, Chemical
  • Molecular Structure
  • Polymerization*
  • Polymers / chemical synthesis
  • Polymers / chemistry
  • Spectrophotometry
  • Thiadiazoles / chemical synthesis
  • Thiadiazoles / chemistry*
  • Thiophenes / chemistry

Substances

  • Carbazoles
  • Chlorides
  • Hydrocarbons, Aromatic
  • Polymers
  • Thiadiazoles
  • Thiophenes
  • carbazole
  • benzo-1,2,3-thiadiazole