Bao Xiaoying, Snurr Randall Q, Broadbelt Linda J
Department of Chemical and Biological Engineering, Northwestern University, Evanston, Illinois 60208, USA.
Langmuir. 2009 Sep 15;25(18):10730-6. doi: 10.1021/la901240n.
Molecular simulations were performed to predict the adsorption of racemic mixtures of (R,S)-1,3-dimethylallene (DMA) in three homochiral metal-organic frameworks (HMOFs). All three HMOFs include the same chiral linker, (R)-6,6'-dichloro-2,2'-dihydroxy-1,1'-binaphthyl-4,4'-bipyridine (L), but have different topologies. While a single linker L shows very little enantioselectivity between the DMA enantiomers, the three HMOFs with closely packed linkers L have enantiomeric excesses of 6%, 28%, and 45%, showing that closely situated chiral selectors function synergistically to enhance the enantioselectivity. Both the confinement created by the linkers and the number of chiral linkers that form the confinement are important in enhancing the enantioselectivity. In addition, the simulations show that the enantioselectivity of the three HMOFs may be further enhanced by modifying the composition of the linker L.
进行了分子模拟，以预测外消旋混合物（R,S）-1,3-二甲基丙二烯（DMA）在三种手性金属有机骨架（HMOF）中的吸附情况。所有这三种HMOF都包含相同的手性连接体，即（R）-6,6'-二氯-2,2'-二羟基-1,1'-联萘-4,4'-联吡啶（L），但具有不同的拓扑结构。虽然单个连接体L对外消旋体DMA的对映选择性非常低，但具有紧密堆积连接体L的三种HMOF的对映体过量分别为6%、28%和45%，这表明紧密排列的手性选择剂协同作用可提高对映选择性。连接体产生的限制作用以及形成限制作用的手性连接体数量对于提高对映选择性都很重要。此外，模拟结果表明，通过改变连接体L的组成，这三种HMOF的对映选择性可能会进一步提高。
