Control of Metal Arrays Based on Heterometallics Masquerading in Heterochiral Aggregations of Chiral Clothespin-Shaped Complexes.
Control of Metal Arrays Based on Heterometallics Masquerading in Heterochiral Aggregations of Chiral Clothespin-Shaped Complexes.
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DOI：
10.1002/chem.201500996
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发表时间：
2015-09
期刊：
影响因子：
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通讯作者：
Masaya Naito;R. Inoue;Masayuki Iida;Yu Kuwajima;Soichiro Kawamorita;Naruyoshi Komiya;T. Naota
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文献类型：
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作者：
Masaya Naito;R. Inoue;Masayuki Iida;Yu Kuwajima;Soichiro Kawamorita;Naruyoshi Komiya;T. Naota
用手性衣夹形反式双（水杨醛缩）d8过渡金属配合物对有机液体进行自发和超声诱导凝胶化，得到了分子聚集中的异金属阵列。配合物1a （Pd）和1b （Pt）的杂金属混合物完全由于衣夹形状的有机壳结构而发生严格的杂手性聚集，而不受金属芯的影响。这种现象提供了一种前所未有的方法来产生高度控制的异金属排列，如交替序列[(+)- pd (-)- pt (+)- pd (-)- pt (-)- pt⋅⋅⋅⋅]以及各种富含单金属的阵列(例如，[(+)- pt (-)- pd (+)- pd (-)- pd (-)- pd (+)- pd (-)- pd⋅⋅⋅⋅]和[(+)- pd (-)- pt (+)- pt (+)- pt （-)- pt (-)- pt⋅⋅⋅⋅]）在异手性单金属序列中引入具有不同金属核心的光学活性伪装单元。本方法可用于形成具有光学活性Pd和Pt单元的各种新聚集体，以允许1)根据金属单元的不同听觉能力调整凝胶超声灵敏度；2)聚集诱导的异金属间手性转移；3)聚集诱导手性增强。基于单元的分子结构和聚集体的形态，提出了这些分子聚集的机械原理。
Heterometal arrays in molecular aggregations were obtained by the spontaneous and ultrasound-induced gelation of organic liquids containing the chiral, clothespin-shaped trans-bis(salicylaldiminato) d8 transition-metal complexes 1. Heterometallic mixtures of complexes 1 a (Pd) and 1 b (Pt) underwent strict heterochiral aggregation entirely due to the organic shell structure of the clothespin shape, with no effect of the metal cores. This phenomenon provides an unprecedented means of generating highly controlled heterometallic arrangements such as alternating sequences [(+)-Pd(-)-Pt(+)-Pd(-)-Pt⋅⋅⋅] as well as a variety of single metal-enriched arrays (e.g., [(+)-Pt(-)-Pd(+)-Pd(-)-Pd(+)-Pd(-)-Pd⋅⋅⋅] and [(+)-Pd(-)-Pt(+)-Pt(-)-Pt(+)-Pt(-)-Pt⋅⋅⋅]) upon the introduction of an optically active masquerading unit with a different metal core in the heterochiral single-metal sequence. The present method can be applied to form various new aggregates with optically active Pd and Pt units, to allow 1) tuning of the gelation ultrasound sensitivity based on the different hearing abilities of the metal units; 2) aggregation-induced chirality transfer between heterometallic species; and 3) aggregation-induced chirality enhancement. A mechanistic rationale is proposed for these molecular aggregations based on the molecular structures of the units and the morphologies of the aggregates.