Department of Chemistry, Graduate School of Science, Osaka City University, Sugimoto, Osaka 558-8585, Japan.
Chem Soc Rev. 2012 Nov 7;41(21):6977-91. doi: 10.1039/c2cs35192g. Epub 2012 Aug 1.
'Chirality switching' is one of the most important chemical processes controlling many biological systems. DNAs and proteins often work as time-programmed functional helices, in which specific external stimuli alter the helical direction and tune the time scale of subsequent events. Although a variety of organic foldamers and their hybrids with natural helices have been developed, we highlight coordination chemistry strategies for development of structurally and functionally defined metal helicates. These metal helicates have characteristic coordination geometries, redox reactivities and spectroscopic/magnetic properties as well as complex chiralities. Several kinds of inert metal helicates maintain rigid helical structures and their stereoisomers are separable by optical resolution techniques, while labile metal helicates offer dynamic inversion of their helical structures via non-covalent interactions with external chemical signals. The latter particularly have dynamically ordered helical structures, which are controlled by the combinations of metal centres and chiral ligands. They further function as time-programmable switches of chirality-derived dynamic rotations, translations, stretching and shape flipping, which are useful applications in nanoscience and related technology.
手性转变是控制许多生物系统的最重要的化学过程之一。DNA 和蛋白质通常作为时间编程的功能螺旋发挥作用,其中特定的外部刺激会改变螺旋方向,并调整后续事件的时间尺度。尽管已经开发出了各种有机折叠体及其与天然螺旋体的混合物,但我们强调了用于开发结构和功能定义明确的金属螺旋体的配位化学策略。这些金属螺旋体具有特征的配位几何形状、氧化还原反应性和光谱/磁性特性以及复杂的手性。几种惰性金属螺旋体保持刚性螺旋结构,其对映异构体可以通过光学拆分技术分离,而不稳定的金属螺旋体则可以通过与外部化学信号的非共价相互作用动态反转其螺旋结构。后者特别具有动态有序的螺旋结构,这些结构受金属中心和手性配体的组合控制。它们进一步用作手性衍生动态旋转、平移、拉伸和形状翻转的可编程开关,这在纳米科学和相关技术中有广泛的应用。