双稳态[2]轮烷中的抗衡离子诱导平移异构现象。

Counterion-induced translational isomerism in a bistable [2]rotaxane.

作者信息

Laursen Bo W, Nygaard Sune, Jeppesen Jan O, Stoddart J Fraser

机构信息

California NanoSystems Institute and Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095-1569, USA.

出版信息

Org Lett. 2004 Nov 11;6(23):4167-70. doi: 10.1021/ol048518l.

DOI:10.1021/ol048518l

PMID:15524434

Abstract

Translational isomerization can be induced by changing the anions associated with a bistable rotaxane in which the tetracationic cyclophane (blue box), cyclobis(paraquat-p-phenylene), encircles a dumbbell component containing bispyrrolotetrathiafulvalene (green) and a dioxynaphthalene (red) recognition sites. The rotaxane was isolated as both its hexafluorophosphate and tris(tetrachlorobenzenediolato)phosphate(v) (TRISPHAT(-)) salts. Photophysical measurements and NMR spectroscopy carried out in acetone (CD(3)COCD(3)) and acetonitrile (CD(3)CN) solutions reveal that the much larger TRISPHAT(-) anion favors predominantly the encirclement of the green site by the blue box.

摘要

通过改变与双稳态轮烷相关的阴离子，可以诱导发生平移异构化。在该双稳态轮烷中，四价阳离子环番（蓝色框），即环双（百草枯 - 对亚苯基），环绕着一个哑铃型组分，该组分包含双吡咯并四硫富瓦烯（绿色）和二氧萘（红色）识别位点。轮烷以其六氟磷酸盐和磷酸（V）三（四氯苯二酚根）盐（TRISPHAT(-)）的形式被分离出来。在丙酮（CD(3)COCD(3)）和乙腈（CD(3)CN）溶液中进行的光物理测量和核磁共振光谱表明，大得多的TRISPHAT(-)阴离子主要有利于蓝色框对绿色位点的环绕。