Synthesis and structural analysis of two constitutional isomeric libraries of AB2-based monodendrons and supramolecular dendrimers
Synthesis and structural analysis of two constitutional isomeric libraries of AB2-based monodendrons and supramolecular dendrimers
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DOI：
10.1021/ja0037771
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发表时间：
2001-02-21
影响因子：
15
通讯作者：
Yeardley, DJP
中科院分区：
文献类型：
--
作者：
Percec, V;Cho, WD;Yeardley, DJP
本文报道了基于3,4-和3,5-二取代苄基醚内部重复单元的自组装AB(2)单枝化合物两个构象文库的合成和结构分析，这些文库含有4种不同的第一代单枝化合物，即3,4,5-三（n-十二烷-1-基氧基）苄基醚、3,4-二（n-十二烷-1-基氧基）苄基醚、3,4,5-三[对-（n-十二烷-1-基氧基）苯氧基]苄基醚和3,4-二[对-（n-十二烷-1-基氧基）苯氧基]苄基醚。无论其外围的重复单元如何，前三代或第四代3,4-二取代单枝树系列自组装成球形超分子树状大分子，自组织成Pm(3)超过barn的三维立方体晶格，而同代的3,5-二取代单枝树系列自组装成圆柱形超分子树状大分子，自组织成p6mm的六边形柱状二维晶格。单树突的内部重复单元决定了超分子树突的形状。然而，对于一个特定的内部重复单元，其外围的结构决定了单枝的大小，自组装成超分子树突的单枝的数量，单枝的立体角，以及超分子树突的大小与代数的依赖关系。由于所有的单枝树最终都必须达到一个球体的形状，因此由这些构件组成的圆柱形和球形超分子树状大分子的直径被限制在100埃以下。3,5-二取代单枝植物的文库还提供了前五个超分子树状大分子的例子，这些树状大分子在其焦点处的温度和功能诱导下发生可逆的形状变化。此外，在同一文库中还发现了一种基于3,5-二取代重复单元的球形超分子树状大分子，该结构可自组装成Im (3) over barm三维立方晶格。由这两个AB(2)和先前报道的准等效单树树AB(3)文库生成的结构信息提供了构建块，使外部调节的功能超分子、大分子和单分子纳米系统能够在可预测的晶格中自组织。
The synthesis and structural analysis of two constitutional isomeric libraries of self-assembling AB(2) monodendrons based on 3,4- and 3,5-disubstituted benzyl ether internal repeat units containing four different first generation monodendrons, i.e., 3,4,5-tris(n-dodecan-1-yloxy)benzyl ether, 3,4-bis(n-dodecan-1-yloxy)benzyl ether, 3,4,5-tris [p-(n-dodecan-1-yloxy)benzyloxy]benzyl ether, and 3,4-bis[p-(n-dodecan-1-yloxy)benzyloxy]benzyl ether, on their periphery are described. Regardless of the repeat unit on their periphery, the first three or four generations of the 3,4-disubstituted series of monodendrons self-assemble into spherical supramolecular dendrimers that self-organize into a Pm (3) over barn 3-D cubic lattice while the same generations of the 3,5-disubstituted series of monodendrons self-assemble into cylindrical supramolecular dendrimers that self-organize into a p6mm hexagonal columnar 2-D lattice. The internal repeat unit of the monodendrons determines the shape of the supramolecular dendrimers. However, for a particular internal repeat unit, the architecture from its periphery determines the size of the monodendron, the number of monodendrons that self-assemble into a supramolecular dendrimer, the solid angle of the monodendron, and the dependence of the size of the supramolecular dendrimer on generation number. Since ultimately all monodendrons must reach the shape of a single sphere, the diameter of cylindrical and spherical supramolecular dendrimers constructed from these building blocks is Limited to less than 100 Angstrom. The library of 3,5-disubstituted monodendrons also provided the first five examples of supramolecular dendrimers that undergo reversible shape changes induced by temperature and functionality at their focal point. In addition, a spherical supramolecular dendrimer based on a 3,5-disubstituted repeat unit that self-assembles in an Im (3) over barm 3-D cubic lattice was discovered in the same library. The structural information generated by these two AB(2) and the previously reported AB(3) libraries of quasi-equivalent monodendrons provides building blocks that enable the construction of externally regulated functional supramolecular, macromolecular, and single-molecule-based nanosystems self-organizable in predictable lattices.