Subcomponent Self-Assembly of a Cyclic Tetranuclear FeII Helicate in a Highly Diastereoselective Self-Sorting Manner
Subcomponent Self-Assembly of a Cyclic Tetranuclear FeII Helicate in a Highly Diastereoselective Self-Sorting Manner
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DOI：
10.1002/chem.201903164
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发表时间：
2019-08-28
影响因子：
4.3
通讯作者：
Luetzen, Arne
中科院分区：
文献类型：
--
作者：
Anhaeuser, Jana;Puttreddy, Rakesh;Luetzen, Arne
基于4，15-双官能化[2.2]对环芳烷骨架和2-甲酰基吡啶的对映体纯的二胺在与铁（II）离子混合后在非对映选择性子组分自组装过程中自组装成光学纯的环状金属超分子Fe 4L 6螺旋酸盐。环状组装的结果，从空间应变，防止形成一个较小的线性双核三链螺旋，因此，导致较大的无应变组装，满足最大占有率规则。有趣的是，使用外消旋二胺还导致纯手性环状螺旋酸酯的外消旋混合物以高度非对映选择性自恋手性自分选方式作为主要产物，因为该组装含有十个立体元素，其原则上可以产生149种不同的非对映异构体。金属超分子聚集体可以通过NMR、UV/维斯和CD光谱、质谱和X射线晶体学来表征。
An enantiomerically pure diamine based on the 4,15-difunctionalized [2.2]paracyclophane scaffold and 2-formylpyridine self-assemble into an optically pure cyclic metallosupramolecular Fe4L6 helicate upon mixing with iron(II) ions in a diastereoselective subcomponent self-assembly process. The cyclic assembly results from steric strain that prevents the formation of a smaller linear dinuclear triple-stranded helicate, and hence, leads to the larger strain-free assembly that fulfils the maximum occupancy rule. Interestingly, use of the racemic diamine also leads to a racemic mixture of the homochiral cyclic helicates as the major product in a highly diastereoselective narcissistic chiral self-sorting manner given the fact that the assembly contains ten stereogenic elements, which can in principle give rise to 149 different diastereomers. The metallosupramolecular aggregates could be characterized by NMR, UV/Vis and CD spectroscopy, mass spectrometry, and X-ray crystallography.