Terlecki Michał, Justyniak Iwona, Leszczyński Michał K, Lewiński Janusz
Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664, Warsaw, Poland.
Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224, Warsaw, Poland.
Commun Chem. 2021 Sep 20;4(1):133. doi: 10.1038/s42004-021-00574-3.
Metal-oxo clusters can serve as directional and rigid building units of coordination and noncovalent supramolecular assemblies. Therefore, an in-depth understanding of their multi-faceted chemistry is vital for the development of self-assembled solid-state structures of desired properties. Here we present a comprehensive comparative structural analysis of isostructural benzoate, benzamidate, and new benzamidinate zinc-oxo clusters incorporating the [O,O]-, [O,NH]- and [NH,NH]-anchoring donor centers, respectively. We demonstrated that the NH groups in the proximal secondary coordination sphere are prone to the formation of intermolecular hydrogen bonds, which affects the packing of clusters in the crystal structure. Coordination sphere engineering can lead to the rational design of new catalytic sites and novel molecular building units of supramolecular assemblies.
金属氧簇可作为配位和非共价超分子组装体的定向且刚性的构建单元。因此，深入了解其多方面的化学性质对于开发具有所需性质的自组装固态结构至关重要。在此，我们对分别包含[O,O]-、[O,NH]-和[NH,NH]-锚定供体中心的同构苯甲酸酯、苯甲酰胺酯和新型苯脒锌氧簇进行了全面的比较结构分析。我们证明，近端二级配位球中的NH基团易于形成分子间氢键，这会影响簇在晶体结构中的堆积。配位球工程可导致合理设计新的催化位点和超分子组装体的新型分子构建单元。
