一种新型天冬氨酸基金属-有机框架材料的设计、合成及性能

Design,Synthesis and Properties of One Novel Metal Organic-framework Based on Aspartic Acid

手性金属-有机框架材料(CMOFs)因具有可调的多孔结构和独特的手性环境,在拆分手性分子的对映异构体方面受到广泛关注。本文以L-天冬氨酸二甲酯和萘-1,5-二磺酰氯分别作为手性源和桥联体,设计合成了一种含有4个羧酸配位基团的柔性手性桥联配体(H_(4)L),并将H4L与4,4′-联吡啶(bpy)和金属镍离子(Ni^(2+))通过溶剂热反应共同组装了一种新颖的三维手性金属-有机框架材料[Ni_(2)(H_(2)L)_(2)(bpy)_(3)·(H_(2)O)_(2)](CMOF-1)。手性吸附实验显示:CMOF-1能够优先地识别和吸附1-苯基乙醇的S-构型的异构体,获得对映体过剩率(Enantiomeric excess,ee)为51%的手性1-苯基乙醇,CMOF-1为一种具有应用潜力的手性吸附剂。

Chiral metal-organic framework materials(CMOFs)have received widespread attention in the resolution of enantiomers of chiral molecules due to their tunable porous structures and unique chiral environment.In this work,a flexible chiral bridging ligand(H_(4)L)with four carboxylic acid coordination groups has been rational designed and synthesized by using dimethyl L-aspartate as the chiral source and naphthalene-1,5-disulfonyl chloride as the bridging linker,respectively.Subsequently,a novel three-dimensional(3D)chiral metal-organic framework,[Ni_(2)(H_(2)L)_(2)(bpy)_(3)·(H_(2)O)_(2)](CMOF-1)was assembled by the solvothermal reaction of H_(4)L,4,4′-bipyridine(bpy)and nickel ions(Ni^(2+)).In addition,the enantioselective adsorption experiment of CMOF-1 towards 1-phenylethanol showed that CMOF-1 could recognize and absorb preferentially the S-enantiomers of 1-phenylethanol,affording chiral 1-phenylethanol with 51%ee.This result indicated that CMOF-1 is a promising chiral adsorbent.