Two-dimensional acetylenic scaffolding: extended donor-substituted perethynylated dehydroannulenes

被引:36
作者
Kivala, Milan
Mitzel, Frieder
Boudon, Corinne
Gisselbrecht, Jean-Paul
Seiler, Paul
Gross, Maurice
Diederich, Francois [1 ]
机构
[1] ETH, Dept Chem & Appl Biosci, Organ Chem Lab, HCI, CH-8093 Zurich, Switzerland
[2] Univ Strasbourg, Inst Phys, CNRS,UMR 7177 LC3, Lab Electrochim & Chim Phys Corps Solide, F-67000 Strasbourg, France
关键词
alkynes; charge transfer; conjugation; dehydroannulenes; electrochemistry;
D O I
10.1002/asia.200600131
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Starting from (Z)-bis(N,N-diisopropylanilino)-substituted tetraethynylethene (TEE), perethynylated octadehydro[12]- and dodecadehydro[18]annulenes were prepared by oxidative Hay coupling. The dodecadehydro[18]annulene with six peripheral N,N-diisopropylanilino substituents was characterized by X-ray crystallography. Elongation of the Z-bisdeprotected TEE by Cadiot-Chodkiewicz coupling with 1-bromo-2-(triisopropylsilyl)ethyne provided a Z-configured bis(butadiyne), which after alkyne deprotection afforded under Hay coupling conditions N,N-diisopropylanilino-substituted perethynylated hexadecadehydro[20]- and tetracosadehydro[30]annulenes. The diisopropylanilino substituents enhance the properties of these unprecedented all-carbon perimeters in several distinct ways. They ensure their solubility, increase their stability, and importantly, engage in strong intramolecular charge-transfer interactions with the electron-accepting all-carbon cores, resulting in intense, bathochromically shifted charge-transfer bands in the UV/Vis spectra. The charge-transfer character of these bands was confirmed by protonation-neutralization experiments. The redox properties of the new carbon-rich chromophores were investigated by cyclic voltammetry and rotating disk voltammetry, which indicated different redox behavior for aromatic (4n+2 pi electrons) and antiaromatic (4n pi electrons) dehydroannulenes.
引用
收藏
页码:479 / 489
页数:11
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