Bhosale Rajesh S, Al Kobaisi Mohammad, Bhosale Sidhanath V, Bhargava Suresh, Bhosale Sheshanath V
RMIT-IICT Research Centre, CSIR-Indian Institute of Chemical Technology, Hyderabad- 500 007, Telangana, India.
School of Applied Sciences, RMIT University, GPO Box 2476, Melbourne, Vic. 3001, Australia.
Sci Rep. 2015 Sep 29;5:14609. doi: 10.1038/srep14609.
Diverse supramolecular assemblies ranging from nanometres to micrometers of small aromatic π-conjugated functional molecules have attracted enormous research interest in light of their applications in optoelectronics, chemosensors, nanotechnology, biotechnology and biomedicines. Here we study the mechanism of the formation of a flower-shaped supramolecular structure of phosphonic acid appended naphthalene diimide with melamine. The flower-shaped assembly formation was visualised by scanning electron microscope (SEM) and transmission electron microscopy (TEM) imaging, furthermore, XRD and DLS used to determined mode of aggregation. Characteristically, phosphonic acid-substituted at imide position of NDIs possess two important properties resulting in the formation of controlled flower-like nanostructures: (i) the aromatic core of the NDI which is designed to optimize the dispersive interactions (π-π stacking and van der Waals interactions) between the cores within a construct and (ii) phosphonic acid of NDI interact with malamine through molecular recognition i.e. strong hydrogen-bonding (H-bonding). We believe such arrangements prevent crystallization and favour the directional growth of flower-like nanostructure in 3D fashion. These works demonstrate that complex self-assembly can indeed be attained through hierarchical non-covalent interactions of two components. Furthermore, flower-like structures built from molecular recognition by these molecules indicate their potential in other fields if combined with other chemical entities.
从纳米到微米级的各种小芳香π共轭功能分子的超分子组装体,因其在光电子学、化学传感器、纳米技术、生物技术和生物医学中的应用而引起了巨大的研究兴趣。在此,我们研究了膦酸取代的萘二酰亚胺与三聚氰胺形成花状超分子结构的机制。通过扫描电子显微镜(SEM)和透射电子显微镜(TEM)成像观察到花状组装体的形成,此外,还使用XRD和DLS来确定聚集模式。具有特征性的是,在萘二酰亚胺的酰亚胺位置上取代的膦酸具有两个重要特性,导致形成可控的花状纳米结构:(i)萘二酰亚胺的芳香核旨在优化构建体内核之间的色散相互作用(π-π堆积和范德华相互作用);(ii)萘二酰亚胺的膦酸通过分子识别即强氢键(H键)与三聚氰胺相互作用。我们认为这种排列方式可防止结晶,并有利于花状纳米结构以三维方式定向生长。这些工作表明,通过两种组分的分级非共价相互作用确实可以实现复杂的自组装。此外,由这些分子通过分子识别构建的花状结构表明,如果与其他化学实体结合,它们在其他领域具有潜力。