A tale of three carboxylates: cooperative asymmetric crystallization of a three-dimensional microporous framework from achiral precursors.

A tale of three carboxylates: cooperative asymmetric crystallization of a three-dimensional microporous framework from achiral precursors.
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DOI:
10.1002/anie.200906248
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发表时间:
2010-02-08
影响因子:
16.6
通讯作者:
Bu, Xianhui
Bu, Xianhui
中科院分区:
化学1区
文献类型:
--
作者:
Zhang, Jian;Chen, Shumei;Nieto, Ruben A.;Wu, Tao;Feng, Pingyun;Bu, Xianhui

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多孔MOF中的手性诱导手性诱导试剂(例如,D-,L-草酸)表现出两种不同的作用:(1)使能和催化手性晶体的生长,和(2)控制Mn 3(HCOO)4(Mn)晶体的体手性(H2 Mn =金刚烷-1,3-二羧酸)。时间依赖性实验显示了非手性相Mn(HCOO)的初始结晶,其在不存在手性诱导剂的情况下持续存在,但在手性诱导剂如D-酒石酸的存在下缓慢转化为对映体富集的Mn 3(HCOO)4(HCOO)4(HCOO),与原位产生的甲酸盐协同作用。
Chirality Induction in Porous MOF The chiral induction reagent (e.g., D-, L-camphoric acid) exhibits two distinct roles: (1) enable and catalyze growth of chiral crystals, and (2) control bulk chirality of Mn3(HCOO)4(adc) crystals (H2adc = adamantane-1,3-dicarboxylic acid. Time-dependent experiments show the initial crystallization of an achiral phase Mn(adc), which persists in the absence of chiral induction agent, but is slowly converted into enantioenriched Mn3(HCOO)4(adc) in the presence of chiral induction agent such as D-camphoric acid, operating in synergy with in situ generated formate.
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