Jansze Suzanne M, Wise Matthew D, Vologzhanina Anna V, Scopelliti Rosario, Severin Kay
Institut des Sciences et Ingénierie Chimiques , Ecole Polytechnique Fédérale de Lausanne (EPFL) , 1015 Lausanne , Switzerland . Email:
Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences , 119991 Moscow , Russia.
Chem Sci. 2017 Mar 1;8(3):1901-1908. doi: 10.1039/c6sc04732g. Epub 2016 Nov 18.
The utilization of large ligands in coordination-based self-assembly represents an attractive strategy for the construction of supramolecular assemblies more than two nanometers in size. However, the implementation of this strategy is hampered by the fact that the preparation of such ligands often requires substantial synthetic effort. Herein, we describe a simple one-step protocol, which allows large bipyridyl ligands with a bent shape to be synthesized from easily accessible and/or commercially available starting materials. The ligands were used to construct PdL-type coordination cages of unprecedented size. Furthermore, we provide evidence that these cages may be stabilized by close intramolecular packing of lipophilic ligand side chains. Packing effects of this kind are frequently encountered in protein assemblies, but they are seldom used as a design element in metallasupramolecular chemistry.
在基于配位的自组装中使用大配体是构建尺寸超过两纳米的超分子组装体的一种有吸引力的策略。然而，这一策略的实施受到阻碍，因为制备此类配体通常需要大量的合成工作。在此，我们描述了一种简单的一步法方案，该方案可使具有弯曲形状的大二吡啶配体由易于获得和/或市售的起始原料合成。这些配体被用于构建前所未有的尺寸的PdL型配位笼。此外，我们提供证据表明，这些笼子可能通过亲脂性配体侧链的紧密分子内堆积而稳定。这种堆积效应在蛋白质组装体中经常遇到，但在金属超分子化学中很少用作设计元素。
