Liu Guofeng, Sheng Jianhui, Teo Wei Liang, Yang Guangbao, Wu Hongwei, Li Yongxin, Zhao Yanli
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences , Nanyang Technological University , 21 Nanyang Link , 637371 , Singapore.
School of Materials Science and Engineering , Nanyang Technological University , 50 Nanyang Avenue , 639798 , Singapore.
J Am Chem Soc. 2018 Nov 28;140(47):16275-16283. doi: 10.1021/jacs.8b10024. Epub 2018 Nov 14.
Precise control over helical chirality and dimensions of molecular self-assemblies, a remaining challenge for both chemists and materials scientists, is the key to manipulate the property and performance of supramolecular materials. Herein, we report that a cholesterol-azopyridine conjugate could self-assemble into organogels with photocontrollable dimensional transition from 2D microbelts to 1D nanotubes and finally to 0D nanoparticles. The E/ Z-Photoisomerization of the 4-azopyridine unit is the major driving force for the dimensional transformation. Furthermore, the self-assembled structures were observed to exhibit metal ion-mediated helicity inversion through the metal coordination. These observations were collectively confirmed by several techniques including scanning electron microscopy, atomic force microscopy, circular dichroism, and X-ray crystallography. The rational design of building blocks for the construction of dimension and chirality controllable self-assembly systems may lead to versatile applications in smart display, advanced optoelectronic device, and supramolecular asymmetric catalysis.
对分子自组装的螺旋手性和尺寸进行精确控制,这对化学家和材料科学家来说仍是一项挑战,却是操纵超分子材料性质和性能的关键。在此,我们报道一种胆固醇-偶氮吡啶共轭物可自组装成有机凝胶,其具有光控尺寸转变,从二维微带转变为一维纳米管,最终转变为零维纳米颗粒。4-偶氮吡啶单元的E/Z光异构化是尺寸转变的主要驱动力。此外,观察到自组装结构通过金属配位表现出金属离子介导的螺旋反转。这些观察结果通过扫描电子显微镜、原子力显微镜、圆二色性和X射线晶体学等多种技术得到了共同证实。用于构建尺寸和手性可控自组装系统的构建块的合理设计可能会在智能显示、先进光电器件和超分子不对称催化等方面带来广泛应用。