Tuning Thiophene with phosphorus: Synthesis and electronic properties of benzobisthiaphospholes

Yunyan Qiu, Joshua C. Worch, Danielle N. Chirdon, Aman Kaur, Andrew B. Maurer, Samuel Amsterdam, Christopher R. Collins, Tomislav Pintauer, David Yaron, Stefan Bernhard, Kevin J.T. Noonan*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

35 Scopus citations

Abstract

1,4-Dimercapto-2,5-diphosphinobenzene and 3,6-bis(hexyloxy)-1,4-dimercapto- 2,5-diphosphinobenzene were synthesized and combined with various acid chlorides to obtain a series of benzobisthiaphospholes. Electrochemical and photophysical properties of the substituted benzobisthiaphospholes have been evaluated, and the observed reductions are more facile than the related benzothiaphospholes and 2,6-diphenylbenzobisthiazole. A benzobisthiaphosphole with C6H 4-p-CN substituents was reduced at E1/2=-1.08 V (vs. saturated calomel electrode (SCE)). X-ray diffraction data for several of these phosphorus heterocycles has been obtained, and DFT calculations at the B3LYP level have been performed. Fused-ring systems: Energetic tuning of conjugated building blocks can be achieved by atomic modulation of aromatic architectures. A phosphorus mimic of benzodithiophene and benzobisthiazole has been synthesized and structurally characterized (see figure). The UV/Vis spectrum of the phosphorus heterocycle is significantly redshifted compared to its organic counterparts. The redox properties of the benzobisthiaphospholes have been probed and revealed reversible reductions in THF.

Original languageEnglish (US)
Pages (from-to)7746-7751
Number of pages6
JournalChemistry - A European Journal
Volume20
Issue number25
DOIs
StatePublished - Jun 16 2014
Externally publishedYes

Keywords

  • fused-ring systems
  • heterocycles
  • n-type acceptors
  • organic electronics
  • phosphorus heterocycles

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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