Center of Micro and Nanochemistry and Engineering, Organische Chemie I, Universität Siegen, Adolf-Reichwein-Strasse 2, D-57068 Siegen, Germany.
Inorg Chem. 2013 Jun 17;52(12):6975-84. doi: 10.1021/ic400328d. Epub 2013 Jun 5.
A simple approach toward preparation of heteroleptic two-dimensional (2D) rectangles and three-dimensional (3D) triangular prisms is described utilizing the HETPYP (HETeroleptic PYridyl and Phenanthroline metal complexes) concept. By mixing metal-loaded linear bisphenanthrolines of varying lengths with diverse (multi)pyridine (py) ligands in a proper ratio, six different self-assembled architectures arise cleanly and spontaneously in the absence of any template. They are characterized by (1)H and DOSY NMR, ESI-FT-ICR mass spectrometry as well as by Job plots and UV-vis titrations. Density functional theory (DFT) computations provide information about each structure. A stoichiometry-controlled supramolecule-to-supramolecule interconversion based on the relative amounts of metal bisphenanthroline and bipyridine forces the rectangular assembly to reorganize to a rack architecture and back to the rectangle, as clearly supported by variable temperature and DOSY NMR as well as dynamic light scattering data. The highly dynamic nature of the assemblies represents a promising starting point for constitutional dynamic materials.
一种简单的方法来制备杂化二维（2D）矩形和三维（3D）三角棱柱是描述利用 HETPYP（杂化吡啶和菲咯啉金属配合物）的概念。通过混合金属负载的线性双菲咯啉的不同长度与不同的（多）吡啶（PY）配体在一个适当的比例，六个不同的自组装架构在没有任何模板的情况下干净和自发地出现。它们的特点是（1）H 和 DOSY NMR，ESI-FT-ICR 质谱以及作业图和紫外 - 可见滴定。密度泛函理论（DFT）计算提供了关于每个结构的信息。基于金属双菲咯啉和联吡啶的相对量的化学计量控制的超分子 - 超分子的转化迫使矩形组装重新组织成一个机架结构，然后再回到矩形，这一点得到了变温和 DOSY NMR 以及动态光散射数据的明确支持。组装体的高度动态性质代表了组成动态材料的一个有希望的起点。
