Synthesis and characteristics of a nonaggregating tris(tetrathiafulvaleno)dodecadehydro[18]annulene

被引:41
作者
Andersson, Asbjorn Sune
Kilsa, Kristine
Hassenkam, Tue
Gisselbrecht, Jean-Paul
Boudon, Corinne
Gross, Maurice
Nielsen, Mogens Brondsted
Diederich, Francois
机构
[1] Univ Copenhagen, Dept Chem, DK-2100 Copenhagen O, Denmark
[2] ETH, HCI, Organ Chem Lab, CH-8093 Zurich, Switzerland
[3] Univ Copenhagen, NanoSci Ctr, DK-2100 Copenhagen O, Denmark
[4] Univ Strasbourg 1, Lab Electrochim & Chim Phys Corps Solide, UMR 7177, CNRS, F-67000 Strasbourg, France
关键词
aggregation; alkynes; cyclization; dehydroannulenes; tetrathiafulvalenes;
D O I
10.1002/chem.200600986
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A new tris(tetrathiafulvaleno)dodecadchydro[18]annulene with six peripheral n-hexyl substituents was prepared by oxidative Glaser-Hay cyclization of a corresponding diethynylated tetrathiafulvalene (TTF) precursor. The electronic properties of the neutral and oxidized species were studied by both UV/Vis absorption spectroscopy and electrochemistry. From these studies, it transpires that the strongly violet-colored macrocycle does not aggregate in solution to any significant degree, which was confirmed by (HNMR)-H-1 spectroscopy. This reluctance towards aggregation contrasts that observed for related TTF-annulenes containing other peripheral substitutents. Oxidation of the TTF-annulene occurs in two three-electron steps as inferred from both the peak amplitudes and the spectroelectrochemical study. We find that the tris(TTF)-fused dehydro[18]annulene is more difficult to oxidize (by +0.20V) than the silyl-protected diethynylated mono-TTF precursor. In contrast, the first vertical ionization energy calculated at the B3LYP/6-311+G(2d,p) level for the parent tris(TTF)-fused dehydro[18]annulene devoid of peripheral hexyl substituents is in fact lower (by 0.44 eV). Moreover, the surface morphology of 1d drop-cast on a mica substrate was investigated by atomic force microscopy (AFM). Crystalline domains with slightly different orientations were observed. The thickness of individual layers seen in the crystalline domains and the thickness of a monolayer obtained from a very dilute solution were determined to 1.8-1.9 nm. This thickness corresponds to the diameter of the macrocycle and the layers seen in the film are apparently formed when the molecules stack in the horizontal direction relative to the substrate.
引用
收藏
页码:8451 / 8459
页数:9
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