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
相关论文
共 90 条
  • [1] SIR97:: a new tool for crystal structure determination and refinement
    Altomare, A
    Burla, MC
    Camalli, M
    Cascarano, GL
    Giacovazzo, C
    Guagliardi, A
    Moliterni, AGG
    Polidori, G
    Spagna, R
    [J]. JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1999, 32 : 115 - 119
  • [2] Optical excitations in carbon architectures based on dodecadehydrotribenzo[18]annulene
    Anand, S
    Varnavski, O
    Marsden, JA
    Haley, MM
    Schlegel, HB
    Goodson, T
    [J]. JOURNAL OF PHYSICAL CHEMISTRY A, 2006, 110 (04) : 1305 - 1318
  • [3] STABLE [12]ANNULENES AND [18]ANNULENES DERIVED FROM TETRAETHYNYLETHENE
    ANTHONY, J
    KNOBLER, CB
    DIEDERICH, F
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1993, 32 (03): : 406 - 409
  • [4] TETRAETHYNYLETHENES - FULLY CROSS-CONJUGATED PI-ELECTRON CHROMOPHORES AND MOLECULAR SCAFFOLDS FOR ALL-CARBON NETWORKS AND CARBON-RICH NANOMATERIALS
    ANTHONY, J
    BOLDI, AM
    RUBIN, Y
    HOBI, M
    GRAMLICH, V
    KNOBLER, CB
    SEILER, P
    DIEDERICH, F
    [J]. HELVETICA CHIMICA ACTA, 1995, 78 (01) : 13 - 45
  • [5] MACROCYCLIC TETRAETHYNYLETHENE MOLECULAR SCAFFOLDING - PERETHYNYLATED AROMATIC DODECADEHYDRO[18]ANNULENES, ANTIAROMATIC OCTADEHYDRO[12]ANNULENES, AND EXPANDED RADIALENES
    ANTHONY, J
    BOLDI, AM
    BOUDON, C
    GISSELBRECHT, JP
    GROSS, M
    SEILER, P
    KNOBLER, CB
    DIEDERICH, F
    [J]. HELVETICA CHIMICA ACTA, 1995, 78 (04) : 797 - 817
  • [6] Anthony J., 1993, ANGEW CHEM INT EDIT, V105, P437
  • [7] STRUCTURE-PROPERTY PREDICTIONS FOR NEW PLANAR FORMS OF CARBON - LAYERED PHASES CONTAINING SP2 AND SP ATOMS
    BAUGHMAN, RH
    ECKHARDT, H
    KERTESZ, M
    [J]. JOURNAL OF CHEMICAL PHYSICS, 1987, 87 (11) : 6687 - 6699
  • [8] EXPANDED RADIALENES - A NOVEL CLASS OF CROSS-CONJUGATED MACROCYCLES
    BOLDI, AM
    DIEDERICH, F
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1994, 33 (04): : 468 - 471
  • [9] BOLDI AM, 1994, ANGEW CHEM, V106, P482
  • [10] ELECTROCHEMICAL PROPERTIES OF TETRAETHYNYLETHENES, FULLY CROSS-CONJUGATED PI-CHROMOPHORES, AND TETRAETHYNYLETHENE-BASED CARBON-RICH MOLECULAR RODS AND DEHYDROANNULENES
    BOUDON, C
    GISSELBRECHT, JP
    GROSS, M
    ANTHONY, J
    BOLDI, AM
    FAUST, R
    LANGE, T
    PHILP, D
    VANLOON, JD
    DIEDERICH, F
    [J]. JOURNAL OF ELECTROANALYTICAL CHEMISTRY, 1995, 394 (1-2): : 187 - 197