Synthesis and Properties of Terthiophene and Bithiophene Derivatives Functionalized by BF2 Chelation: A New Type of Electron Acceptor Based on Quadrupolar Structures
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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DOI：
10.1002/chem.201001185
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发表时间：
2010-01-01
影响因子：
4.3
通讯作者：
Yamashita, Yoshiro
中科院分区：
文献类型：
--
作者：
Ono, Katsuhiko;Nakashima, Akihiro;Yamashita, Yoshiro
合成了三噻吩和联噻吩衍生物作为新型电子受体，并与联呋喃和联苯衍生物进行了性能比较。这些新化合物的特点是四极结构，由于共振贡献者产生的BF 2螯合。与联呋喃和联苯衍生物相比，联噻吩衍生物具有较强的四极特性，因为它们的水解分析表明，联噻吩部分具有比其它部分更大的原位库仑排斥。由于噻吩间隔基的加入，三噻吩衍生物具有比联噻吩衍生物更小的原位库仑排斥。这些BF2配合物表现出长波长的吸收，并根据电离势和吸收边的测量，他们有积极的低洼HOMO和LUMO。该联噻吩衍生物的晶体结构为人字形，具有短的F中心点S和F中心点C接触，提供致密的晶体堆积。在基于这些BF 2配合物的有机场效应晶体管中观察到n型半导体行为。
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 center dot center dot center dot S and F center dot center dot center dot C contacts affording dense crystal packing. n-Type semiconducting behaviour was observed in organic field-effect transistors based on these BF2 complexes.