Self-Assembly of a Nanoscopic Pt12Fe12 Heterometallic Open Molecular Box Containing Six Porphyrin Walls
Self-Assembly of a Nanoscopic Pt12Fe12 Heterometallic Open Molecular Box Containing Six Porphyrin Walls
复制标题
DOI：
10.1002/anie.200803543
复制
发表时间：
2008-01-01
影响因子：
16.6
通讯作者：
Mukherjee, Partha Sarathi
中科院分区：
文献类型：
--
作者：
Bar, Arun Kumar;Chakrabarty, Rajesh;Mukherjee, Partha Sarathi
如文献中所反映的，配位驱动的自组装已被证明是合成有限形状和尺寸的大超分子的有效方法。[1-2]正方形平面PdII和PtII中心长期以来一直是用于此目的的最佳选择之一，因为它们具有严格的协调环境。通过使用这些金属离子与合适的多吡啶基连接剂结合，已经制备了几种3D封闭结构，如球体、十二面体、棱柱和三角双锥。[3]分子的性质取决于存在的官能团。因此，将官能团并入纳米结构中可能是引导所得组装体的性质的有效方式。卟啉衍生物在生物系统中对于氧运输、能量转换和电子转移是重要的。因此，基于卟啉的离散组装体的构建是设计自组装领域中一个很有前途的方法。令人惊讶的是，将卟啉功能引入到PdII/PtII中心的离散纳米级结构中的开发要少得多。[4]此外，在报道的几种3D离散组件中，分子盒是鲜为人知的架构之一。[4a-b使用四位体单元是设计这种系统的正确选择。然而，所有前面的分子盒的例子都包含三个或四个被四配位体单元占据的面，而包含六个这样的面的大离散开放盒的例子还不知道。本文报道了第一个Pt_（12）Fe_（12）异金属六方开口盒（1）的设计和合成（方案1），该六方开口盒（1）含有六个被六个5，10，15，20-四（4-吡啶基）卟啉（L）连接体占据的六个面。
Coordination-driven self-assembly has proven to be an efficient approach towards the synthesis of large supramolecules of finite shapes and sizes, as reflected in the literature.[1–2] Square-planar PdII and PtII centers have long been among the favorite choices for this purpose because of their rigid coordination environments. Several 3D closed architectures such as spheres, dodecahedrons, prisms, and trigonal bipyramids, have been prepared by using these metal ions in conjunction with suitable polypyridyl linkers.[3] The properties of a molecule depend on the functional group (s) present. Thus, incorporation of functional groups into nanostructures may be an efficient way to guide the properties of the resulting assemblies. Porphyrin derivatives are important in biological systems for oxygen transport, energy conversion, and electron transfer. Thus, the construction of porphyrinbased discrete assemblies is a promising approach in the field of designed self-assembly. Surprisingly, the introduction of porphyrin functionality into discrete nanoscopic architectures of PdII/PtII centers is much less developed.[4] Moreover, among the several 3D discrete assemblies reported, a molecular box is one of the much less known architectures.[4a–b, 5] The use of a tetratopic unit is the right choice for designing such a system. However, all the preceding examples of molecular boxes contain either three or four faces occupied by the tetratopic unit, whereas an example of a large discrete open box containing six such faces is not yet known. Herein we report the design and synthesis (Scheme 1) of the first Pt12Fe12 heterometallic open hexagonal box (1) containing six faces occupied by six 5, 10, 15, 20-tetrakis (4-pyridyl) porphyrin (L) linkers.