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Assembly of Chiral Cluster-Based Metal–Organic Frameworks and the Chirality Memory Effect during their Disassembly
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-06-28 , DOI: 10.1021/jacs.1c03251 Guocheng Deng 1 , Boon K Teo 1 , Nanfeng Zheng 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-06-28 , DOI: 10.1021/jacs.1c03251 Guocheng Deng 1 , Boon K Teo 1 , Nanfeng Zheng 1
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Many metal clusters are intrinsically chiral but are often synthesized as a racemic mixture. By taking chiral Ag14(SPh(CF3)2)12(PPh3)4(DMF)4 (Ag14) clusters with bulky thiolate ligands as an example, we demonstrate herein an interesting assembly disassembly (ASDS) strategy to obtain the corresponding, optically pure crystals of both homochiral enantiomers, R-Ag14m and S-Ag14m. The ASDS strategy makes use of two bidentate linkers with different chiral configurations, namely, (1R,2R,N1E,N2E)-N1,N2-bis(pyridin-3-ylmethylene)cyclohexane-1,2-diamine (LR) and the corresponding chiral analogue LS. For comparison, we also use the racemic mixture of equimolar of LR and LS (LRS). Three three-dimensional (3D) Ag14-based metal–organic frameworks (MOFs) were characterized by X-ray crystallography to be [Ag14(SPh(CF3)2)12(PPh3)4(LR)2]n (Ag14-LR), [Ag14(SPh(CF3)2)12(PPh3)4(LS)2]n (Ag14-LS), and [Ag14(SPh(CF3)2)12(PPh3)4(LRS)2]n (Ag14-LRS), respectively. As expected, the building blocks in Ag14-LR or Ag14-LS are homochiral R-Ag14 or S-Ag14, respectively. In contrast, Ag14-LRS is achiral and crystallizes with a diamond-like structure containing alternate R-Ag14 and S-Ag14 clusters. During the assembly process, the racemic Ag14 clusters were converted to homochiral building blocks, namely, R-Ag14 for Ag14-LR and S-Ag14 for Ag14-LS. Subsequently, the chiral linkers were removed from the crystals of Ag14-LR and Ag14-LS via hydrolysis with water, and from the disassembled solid material Ag14-DR and Ag14-DS, optically pure enantiomers R-Ag14m and S-Ag14m were obtained. It is hoped that this simple assembly strategy can be used to construct cluster-based chiral assemblage materials and that the subsequent disassembly protocol can be used to obtain optically pure chiral cluster molecules from as-prepared racemic mixtures.
中文翻译：
基于手性簇的金属-有机框架的组装及其拆卸过程中的手性记忆效应
许多金属簇本质上是手性的，但通常合成为外消旋混合物。通过以具有庞大硫醇盐配体的手性 Ag 14 (SPh(CF 3 ) 2 ) 12 (PPh 3 ) 4 (DMF) 4 ( Ag 14 ) 簇为例，我们在此展示了一种有趣的组装拆卸 (ASDS) 策略，以获得两种同手性对映体R-Ag 14m和S-Ag 14m 的相应光学纯晶体。ASDS 策略利用两个具有不同手性构型的双齿接头，即 (1 R ,2 R ,N 1 E , N 2 E ) -N 1 , N 2 -双(吡啶-3-基亚甲基)环己烷-1,2-二胺( LR )和相应的手性类似物LS。为了进行比较，我们还使用等摩尔LR和LS ( LRS )的外消旋混合物。三种三维 (3D) Ag 14基金属有机骨架 (MOF) 通过 X 射线晶体学表征为 [Ag 14 (SPh(CF 3 ) 2 ) 12 (PPh 3 ) 4 (LR) 2] n ( Ag 14 -LR )、[Ag 14 (SPh(CF 3 ) 2 ) 12 (PPh 3 ) 4 (LS) 2 ] n ( Ag 14 -LS ) 和 [Ag 14 (SPh(CF 3 ) 2 ) ) 12 (PPh 3 ) 4 (LRS) 2 ] n ( Ag 14 -LRS )。正如预期的那样，Ag 14 -LR或Ag 中的构建块14 -LS分别是同手性的R-Ag 14或S-Ag 14。相比之下， Ag 14 -LRS是非手性的，并以包含交替R-Ag 14和S-Ag 14簇的类金刚石结构结晶。在组装过程中，外消旋的Ag 14团簇转化为纯手性结构单元，即， R-银14为银14 -LR和S-银14为银14 -LS. 随后，通过用水水解从Ag 14 -LR和Ag 14 -LS晶体中去除手性连接体，并从分解的固体材料Ag 14 -DR和Ag 14 -DS 中去除光学纯对映异构体R-Ag 14m和S获得-Ag 14m。希望这种简单的组装策略可用于构建基于簇的手性组装材料，随后的拆卸协议可用于从制备的外消旋混合物中获得光学纯的手性簇分子。
更新日期：2021-07-14
中文翻译：
基于手性簇的金属-有机框架的组装及其拆卸过程中的手性记忆效应
许多金属簇本质上是手性的，但通常合成为外消旋混合物。通过以具有庞大硫醇盐配体的手性 Ag 14 (SPh(CF 3 ) 2 ) 12 (PPh 3 ) 4 (DMF) 4 ( Ag 14 ) 簇为例，我们在此展示了一种有趣的组装拆卸 (ASDS) 策略，以获得两种同手性对映体R-Ag 14m和S-Ag 14m 的相应光学纯晶体。ASDS 策略利用两个具有不同手性构型的双齿接头，即 (1 R ,2 R ,N 1 E , N 2 E ) -N 1 , N 2 -双(吡啶-3-基亚甲基)环己烷-1,2-二胺( LR )和相应的手性类似物LS。为了进行比较，我们还使用等摩尔LR和LS ( LRS )的外消旋混合物。三种三维 (3D) Ag 14基金属有机骨架 (MOF) 通过 X 射线晶体学表征为 [Ag 14 (SPh(CF 3 ) 2 ) 12 (PPh 3 ) 4 (LR) 2] n ( Ag 14 -LR )、[Ag 14 (SPh(CF 3 ) 2 ) 12 (PPh 3 ) 4 (LS) 2 ] n ( Ag 14 -LS ) 和 [Ag 14 (SPh(CF 3 ) 2 ) ) 12 (PPh 3 ) 4 (LRS) 2 ] n ( Ag 14 -LRS )。正如预期的那样，Ag 14 -LR或Ag 中的构建块14 -LS分别是同手性的R-Ag 14或S-Ag 14。相比之下， Ag 14 -LRS是非手性的，并以包含交替R-Ag 14和S-Ag 14簇的类金刚石结构结晶。在组装过程中，外消旋的Ag 14团簇转化为纯手性结构单元，即， R-银14为银14 -LR和S-银14为银14 -LS. 随后，通过用水水解从Ag 14 -LR和Ag 14 -LS晶体中去除手性连接体，并从分解的固体材料Ag 14 -DR和Ag 14 -DS 中去除光学纯对映异构体R-Ag 14m和S获得-Ag 14m。希望这种简单的组装策略可用于构建基于簇的手性组装材料，随后的拆卸协议可用于从制备的外消旋混合物中获得光学纯的手性簇分子。
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