A versatile synthesis of electroactive stilbenoprismands for effective binding of metal cations.
A versatile synthesis of electroactive stilbenoprismands for effective binding of metal cations.
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用于有效结合金属阳离子的电活性二苯乙烯棱柱体的多功能合成。
DOI：
10.1021/jo802579f
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发表时间：
2009
期刊：
影响因子：
--
通讯作者：
R. Rathore
中科院分区：
文献类型：
--
作者：
Paromita Debroy;S. Lindeman;R. Rathore
通过有效的分子内 McMurry 偶联反应，多功能合成了一类新型多芳香族受体（芪棱柱），其包含与 pi 棱柱类似的 Delta 形空腔以及紧密耦合的电活性芪类部分。通过 (1)H NMR 光谱探测，二苯乙烯棱柱中 Delta 形空腔的存在使得单个银阳离子能够有效结合。富含电子的二苯乙烯棱柱体容易氧化成其高度稳定的阳离子自由基盐和二价盐。代表性双二苯乙烯棱柱体的 X 射线结构测定表明，电荷主要集中在四芳基乙烯部分上，这导致烯键 C=C 键扭曲约 35 度。此外，通过光学方法简要探讨了各种二苯乙烯棱柱中二苯乙烯类化合物和π棱柱部分之间的电子耦合。
A versatile synthesis of a new class of polyaromatic receptors (stilbenoprismands) containing a Delta-shaped cavity similar to that of the pi-prismand together with an intimately coupled electroactive stilbenoid moiety was accomplished via an efficient intramolecular McMurry coupling reaction. The presence of the Delta-shaped cavity in stilbenoprismands allows an efficient binding of a single silver cation as probed by (1)H NMR spectroscopy. Electron-rich stilbenoprismands undergo a ready oxidation to their highly robust cation-radical and dicationic salts. X-ray structure determination of a representative dicationic stilbenoprismand showed that the charges were largely localized on the tetraarylethylene moiety, which results in a twisting of the ethylenic C=C bond by approximately 35 degrees. Moreover, the electronic coupling among the stilbenoid and pi-prismand moieties in various stilbenoprismands was briefly probed by optical methods.