Kim Hyehyun, Kim Dongwook, Moon Dohyun, Choi Yong Nam, Baek Seung Bin, Lah Myoung Soo
Department of Chemistry , Ulsan National Institute of Science and Technology , Ulsan 44919 , Korea . Email:
Pohang Acceleratory Laboratory , Pohang 37673 , Korea.
Chem Sci. 2019 May 7;10(22):5801-5806. doi: 10.1039/c9sc01301f. eCollection 2019 Jun 14.
While the one-pot reaction of zirconium metal ions with a mixture of two dicarboxylate heterolinkers yielded a 12-c Zr MOF with randomly distributed linkers, the symmetry-guided stepwise reaction produced the same MOF with both linkers precisely located in the framework. In the latter method, linear terephthalic acid (HBDC) derivatives with symmetry were inserted into the -symmetry sites of the flexible Zr MOF with 8-c topology (), which is composed of zigzag 2,6-naphthalenedicarboxylic acid with 2/ symmetry. Although the length of the symmetry-matching BDC derivatives was much shorter than the distance between the unlinked nearest-neighbor Zr clusters in , induced fitting of the derivatives into the framework was possible, resulting in well-defined locations for the two different dicarboxylate linkers. Thus, controlled synthesis of MOFs with the desired topology and functionality can be achieved using a symmetry-guided approach.
虽然锆金属离子与两种二羧酸杂连接体的混合物进行一锅反应生成了具有随机分布连接体的12-c锆金属有机框架（MOF），但对称引导的逐步反应生成了相同的MOF，且两种连接体都精确地位于框架中。在后一种方法中，具有对称性的线性对苯二甲酸（HBDC）衍生物被插入到具有8-c拓扑结构（）的柔性锆MOF的-对称位点中，该MOF由具有2/对称性的之字形2,6-萘二甲酸组成。尽管对称匹配的BDC衍生物的长度比中未连接的最近邻锆簇之间的距离短得多，但衍生物仍有可能通过诱导拟合进入框架，从而使两种不同的二羧酸连接体具有明确的位置。因此，使用对称引导方法可以实现具有所需拓扑结构和功能的MOF的可控合成。
