University of Bonn, Kekulé-Institute of Organic Chemistry and Biochemistry, Gerhard-Domagk-Str. 1, 53121, Bonn, Germany.
University of Bonn, Institute of Inorganic Chemistry, Gerhard-Domagk-Str. 1, 53121, Bonn, Germany.
Chempluschem. 2020 Jul;85(7):1455-1464. doi: 10.1002/cplu.202000387.
Five ligands with either nitrile or isonitrile metal binding motifs have been synthesized based on the 2,8- or 3,9-disubstituted Tröger's base scaffold, respectively. These ligands self-assemble into dinuclear cyclic metallosupramolecular aggregates upon coordination to [(dppp)Pd(OTf) ] in a highly diastereoselective manner, by heterochiral self-sorting in a chiral self-discriminating manner as shown by ESI mass spectrometry, NMR spectroscopy, and single crystal XRD analysis. This observation is in contrast to earlier studies with ligands derived from Tröger's base that have larger metal binding motifs and bis(nitrile) and bis(isonitrile) ligands based on other rigid dissymmetric cores such as [2.2]paracyclophanes. Thus, the combination of these slim metal binding motifs with the rigid v-shaped 2,8- or 3,9-disubstituted Tröger's base scaffolds seems to be especially well preorganized to ensure high-fidelity social self-sorting behavior.
基于 2,8-或 3,9-取代的特罗格碱骨架，分别合成了具有腈或异腈金属配位基序的五种配体。这些配体在与 [(dppp)Pd(OTf) ]配位时，通过手性自识别的异手性自分类，以高度非对映选择性的方式自组装成双核环状金属超分子聚集体，如电喷雾质谱、NMR 光谱和单晶 XRD 分析所示。这一观察结果与之前使用衍生自特罗格碱的配体的研究结果形成对比，这些配体具有更大的金属结合基序和基于其他刚性不对称核的双(腈)和双(异腈)配体，如[2.2]对环芳烷。因此，这些细长的金属结合基序与刚性 V 形 2,8-或 3,9-取代的特罗格碱骨架的组合似乎特别预先组织，以确保高保真的社交自分类行为。
