Synthesis and Properties of Terthiophene and Bithiophene Derivatives Functionalized by BF2 Chelation: A New Type of Electron Acceptor Based on Quadrupolar Structures

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Synthesis and Properties of Terthiophene and Bithiophene Derivatives Functionalized by BF2 Chelation: A New Type of Electron Acceptor Based on Quadrupolar Structures

Abstract

Terthiophene and bithiophene derivatives functionalized by BF₂ chelation were synthesized as a new type of electron acceptor, and their properties were compared to those of bifuran and biphenyl derivatives. These new compounds are characterized by quadrupolar structures due to resonance contributors generated by BF₂ chelation. The bithiophene derivative has a strong quadrupolar character compared with the bifuran and biphenyl derivatives because their hydrolytic analyses indicated that the bithiophene moiety has a larger on-site Coulomb repulsion than the others. The terthiophene derivative has a smaller on-site Coulomb repulsion than the bithiophene derivative due to the addition of a thiophene spacer. These BF₂ complexes exhibit long-wavelength absorptions and according to measurements of ionization potentials and absorption edges they have energetically low-lying HOMOs and LUMOs. The crystal structure of the bithiophene derivative is of the herringbone type, with short F⋅⋅⋅S and F⋅⋅⋅C contacts affording dense crystal packing. n-Type semiconducting behaviour was observed in organic field-effect transistors based on these BF₂ complexes.

Boron functionalization: Terthiophene and bithiophene derivatives functionalized by coordination of BF₂ groups were synthesized as a new type of electron acceptor that has quadrupolar character due to resonance contributors generated by BF₂ chelation (see picture), as well as energetically low-lying HOMOs and LUMOs. The bithiophene derivatives exhibit n-type semiconducting behaviour in organic field-effect transistors.

B.O.