Self-assembly, structure, and dynamic interconversion of metallosupramolecular architectures generated by Pb(II) binding-induced unfolding of a helical ligand
Self-assembly, structure, and dynamic interconversion of metallosupramolecular architectures generated by Pb(II) binding-induced unfolding of a helical ligand
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DOI：
10.1021/ja0301929
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发表时间：
2003-08-27
影响因子：
15
通讯作者：
Lehn, JM
中科院分区：
文献类型：
--
作者：
Barboiu, M;Vaughan, G;Lehn, JM
铅（11）阳离子与螺旋配体1的三联吡啶型亚基的结合导致不同的纳米尺寸的多核金属超分子结构的自组装。生成三种不同的实体，并且可以作为金属/配体化学计量的函数相互转化：[4 × 4]-Pb-16（11）网格型阵列2、[4 × 4]Pb-12（11）双交叉物种4和中间络合物3。2和4的结构已通过X射线晶体学证实; 3的结构基于NMR光谱数据。这三个物种的相互转换产生动态多样性，并代表了宪法动态化学的表达。在离子结合的过程中，配体1的螺旋分子展开以产生在所产生的结构2-4中以垂直方式排列的完全延伸的链。该过程相当于分子在两个方向上的运动，这赋予本系统二维纳米机械装置的特性，能够进行2D收缩/伸展运动。三重功能的自组织，动态相互转换，和潜在的addressability所显示的过程中描述的跟踪自制造方法纳米科学和纳米技术。
The binding of lead(11) cations to the terpyridine-type subunits of the helical ligand 1 leads to the self-assembly of different polynuclear metallosupramolecular architectures of nanometric size. Three different entities are generated and may be interconverted as a function of metal/ligand stoichiometry: a [4 x 4]-Pb-16(11) grid-type array 2, a [4 # 4]Pb-12(11) double-cross species 4, and an intermediate complex 3. The structures of 2 and 4 have been confirmed by X-ray crystallography; that of 3 is based on NMR spectral data. The interconversion of the three species generates dynamic diversity and represents an expression of constitutional dynamic chemistry. In the course of ion binding, the helical molecules of ligand 1 unwrap to yield fully extended strands arranged in perpendicular fashion in the architectures 2-4 generated. This process amounts to molecular motions in two directions which confer to the present systems characteristics of two-dimensional nanomechanical devices, capable of performing 2D-contraction/extension motions. The triple features of self-organization, dynamic interconversion, and potential addressability displayed by the processes described trace a self-fabrication approach to nanoscience and nanotechnology.