Donor-substituted perethynylated dehydroannulenes and radiaannulenes: Acetylenic carbon sheets featuring intense intramolecular charge transfer

被引:58
作者
Mitzel, F
Boudon, C
Gisselbrecht, JP
Seiler, P
Gross, M
Diederich, F [1 ]
机构
[1] ETH Honggerberg, Organ Chem Lab, CH-8093 Zurich, Switzerland
[2] Univ Strasbourg 1, CNRS, UMR 7512, Lab Electrochim & Chim Phys Corps Solide, F-6700 Strasbourg, France
关键词
D O I
10.1002/hlca.200490104
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
In this article, we report the preparation of unprecedented pi-conjugated macrocycles (Fig. 1) by acetylenic scaffolding using modular tetraethynylethene (TEE, 3,4-diethynylhex-3-ene-1,5-diyne) building blocks. A novel photochemical access to (Z)-bisdeprotected TEEs (Scheme 1) enabled the synthesis of the anilino-substituted perethynylated octadehydro[12]- (5) and dodecadehydro[ 18]annulenes (6) (Scheme 2). Following the serendipitous discovery of perethynylated radiaannulenes (Scheme 3) that can be viewed as hybrids between perethynylated dehydroannulenes and expanded radialenes, two series of monocyclic (7-9; Scheme 6) and bicyclic (10 and 11; Scheme 7) representatives were prepared. Substantial strain in the macrocyclic perimeter of radiaannulene 7 was revealed by X-ray crystal-structure analysis (Fig. 2). Nevertheless, mono- and bicyclic radiaannulenes are stable at room temperature in air for months. The opto-electronic properties of both dehydroannulenes and radiaannulenes are substantially enhanced by the introduction of the peripheral anilino donor groups that undergo strong intramolecular charge-transfer interactions with the electron-accepting all-C cores. As a result, the UV/VIS spectra feature intense, bathochromically shifted charge-transfer bands that disappear upon protonation of the anilino moieties and are fully recovered upon neutralization (Figs. 4- 9). A comparison between anilino-substituted perethynylated dehydroannulenes, expanded radialenes, and radiaannulenes revealed that the efficiency of the intramolecular charge-transfer interaction strongly depends on the structure of the electron-accepting all-C perimeter. Electrochemical investigations ( Table) demonstrated that the radiaannulenes are particularly powerful electron acceptors. Thus, bicyclic radiaannulene 11, which possesses eight peripheral 3,5-di(tert-butyl)phenyl substituents, is reversibly reduced at - 0.83 V in THF (vs. Fc(+/) Fc), making it a better electron acceptor than buckminsterfullerene C-60 under comparable conditions.
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页码:1130 / 1157
页数:28
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