Self-organization in coordination-driven self-assembly.
Self-organization in coordination-driven self-assembly.
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在协调驱动的自组装中进行自组织。
DOI：
10.1021/ar900077c
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发表时间：
2009-10-20
影响因子：
18.3
通讯作者：
Stang, Peter J.
中科院分区：
文献类型：
--
作者：
Northrop, Brian H.;Zheng, Yao-Rong;Chi, Ki-Whan;Stang, Peter J.
自组装允许从相对简单的起始材料制备高度复杂的分子和超分子系统。通常，自组装超分子通过组合两个高度对称的分子组分的互补对来构建，从而限制形成不需要的副产物的机会。在一个复杂的混合物中组合不对称的分子组分或多个互补的分子组可以产生无数不同的有序和无序的超分子组装体。或者，自发的自组织现象可以促进特定产品的形成，而这些产品是多种可能性的集合。自组织过程在自然界中很常见，在生物系统中尤其常见。最近，研究人员研究了纯合成系统中的自组织自组装。这个帐户描述了我们的调查自组织在协调驱动的自组装铂（II）为基础的金属超分子。协调驱动的自组装方法的模块化使我们能够系统地研究各种不同的因素，可以控制超分子自组织的程度。特别是，我们评估了两齿供体亚基的对称性和极性的影响、Pt（II）基受体和有机供体的几何参数（例如尺寸、棱角和维度）差异的影响、温度和溶剂的影响以及分子间空间相互作用和疏水性相互作用对自组织的影响。我们的研究表明，在二维多边形和三维多面体的坐标驱动的自组装中，自组织的程度从无组织（多个产品的统计混合）到放大组织（其中特定产品或产品比其他产品更受欢迎），一直到离散超分子组装的绝对自组织。在许多情况下，输入，如偶极相互作用，空间相互作用，以及亚基的几何参数的差异，单独使用或作为多个因素，可以实现绝对的离散超分子的自组织。我们还观察到，自组织不是绝对的，它与统计结果的偏差各不相同。空间相互作用是驱动这种放大自组织的特别有用的控制因素，因为它们可以通过微小的结构变化进行微妙的调整。有能力充分理解和控制复杂混合物的自组织成特定的合成超分子可以提供更好地理解生物系统中的类似过程。此外，自组织可以允许简单地混合更简单、明智地设计的单个分子组分的集合来容易地合成复杂的多功能、多组分系统。
Self-assembly allows for the preparation of highly complex molecular and supramolecular systems from relatively simple starting materials. Typically, self-assembled supramolecules are constructed by combining complementary pairs of two highly symmetric molecular components, thus limiting the chances of forming unwanted side products. Combining asymmetric molecular components or multiple complementary sets of molecules in one complex mixture can produce myriad different ordered and disordered supramolecular assemblies. Alternatively, spontaneous self-organization phenomena can promote the formation of specific product(s) out of a collection of multiple possibilities. Self-organization processes are common throughout much of nature and are especially common in biological systems. Recently, researchers have studied self-organized self-assembly in purely synthetic systems. This Account describes our investigations of self-organization in the coordination-driven self-assembly of platinum(II)-based metallosupramolecules. The modularity of the coordination-driven approach to self-assembly has allowed us to systematically study a wide variety of different factors that can control the extent of supramolecular self-organization. In particular, we have evaluated the effects of the symmetry and polarity of ambidentate donor subunits, differences in geometrical parameters (e.g. the size, angularity, and dimensionality) of Pt(II)-based acceptors and organic donors, the influence of temperature and solvent, and the effects of intermolecular steric interactions and hydrophobic interactions on self-organization. Our studies have shown that the extent of self-organization in the coordination-driven self-assembly of both 2D polygons and 3D polyhedra ranges from no organization (a statistical mixture of multiple products), to amplified organization (wherein a particular product or products are favored over others), and all the way to the absolute self-organization of discrete supramolecular assemblies. In many cases, inputs such as dipolar interactions, steric interactions, and differences in the geometric parameters of subunits—used either alone or as multiple factors simultaneously—can achieve absolute self-organization of discrete supramolecules. We have also observed instances where self-organization is not absolute and varies in its deviation from statistical results. Steric interactions are particularly useful control factors for driving such amplified self-organization because they can be subtly tuned through small structural variations. Having the ability to fully understand and control the self-organization of complex mixtures into specific synthetic supramolecules can provide a better understanding of analogous processes in biological systems. Furthermore, self-organization may allow for the facile synthesis of complex multifunctional, multicomponent systems from simply mixing a collection of much simpler, judiciously designed individual molecular components.
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