Electron-induced inversion of helical chirality in copper complexes of N,N-dialkylmethionines
Electron-induced inversion of helical chirality in copper complexes of N,N-dialkylmethionines
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DOI：
10.1126/science.288.5470.1404
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发表时间：
2000-05-26
期刊：
影响因子：
56.9
通讯作者：
Canary, JW
中科院分区：
文献类型：
--
作者：
Zahn, S;Canary, JW
铜的立体动力学络合物被发现在氧化或还原时发生螺旋手性元素的反转。氨基酸甲硫氨酸通过两个生色团连接到氮原子上而衍生，得到的配体与铜-1和铜-11盐形成稳定的络合物。对于给定的绝对手性导数，该络合物提供了近乎镜像的圆二色光谱。光谱的变化源于含氮发色团的重新定向，这是由于羧酸盐与硫化物配体的交换所驱动的构象相互转换。电诱导的手性反转与偏振光的强相互作用是独一无二的，可能导致新型的手性分子器件。
Stereodynamic complexes of copper were found to undergo inversion of a helical chiral element upon oxidation or reduction. The amino acid methionine was derivatized by the attachment of two chromophores to the nitrogen atom, The resultant ligands formed stable complexes with Cu-1 and Cu-11 salts. For a derivative of a given absolute chirality, the complexes afford nearly mirror image circular dichroism spectra. The spectral changes originate from reorientation of the nitrogen-attached chromophores due to a conformation interconversion driven by the exchange of a carboxylate for a sulfide ligand. The electrically induced chirality inversion coupled with strong interactions with polarized light is unique and may Lead to novel chiral molecular devices.