Li Ya, Wang Hongwei, Wang Chang, Xu Junwen, Ma Shujuan, Ou Junjie, Zhang Jiangwei, Li Gao, Wei Yinmao, Ye Mingliang
CAS Key Laboratory of Separation Science for Analytical Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Key Laboratory of Synthetic and Natural Function Molecule Chemistry of Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi'an 710069, China.
ACS Appl Mater Interfaces. 2020 Apr 15;12(15):17815-17823. doi: 10.1021/acsami.0c00648. Epub 2020 Apr 3.
A novel porous organic cage (POC) was prepared via condensation reaction between 1,3,5-triformylbenzene (TFB) and (1,2)-4-cyclohexene-1,2-diamine (CHEDA). This POC could pack in either an amorphous structure or a crystalline one. Atomically precise structure determination of POC was achieved through ab initio powder X-ray diffraction (PXRD) structure analysis in the chiral trigonal space group 3. The same atomically precise structure determination of POC from single-crystal X-ray diffraction (SXRD) structure analysis could be obtained independently with a slight difference in cell parameter, indicating that the refinement method through ab initio PXRD structure analysis is reliable and may serve as an essential method for atomically precise structure determination. The cage could adsorb up to 8 mmol/g CO at 298 K and 1 bar. Furthermore, 1-thioglycerol and 1-octadecanethiol were chosen to prove that postmodification of this POC was flexible. After post-synthetic modification (PSM) via highly efficient photoinitiated thiol-ene click reaction, the products still kept porous with relatively higher special surface area (337 m/g of and 156 m/g of ) than mostly reported cages via the reduced-amine approach.
通过1,3,5-三甲醛苯（TFB）与（1,2）-4-环己烯-1,2-二胺（CHEDA）之间的缩合反应制备了一种新型多孔有机笼（POC）。这种POC可以以无定形结构或晶体结构堆积。通过在手性三角空间群3中的从头算粉末X射线衍射（PXRD）结构分析实现了POC的原子精确结构测定。通过单晶X射线衍射（SXRD）结构分析对POC进行相同的原子精确结构测定，独立获得的晶胞参数略有差异，这表明通过从头算PXRD结构分析的精修方法是可靠的，并且可以作为原子精确结构测定的重要方法。该笼在298 K和1 bar下可吸附高达8 mmol/g的CO。此外，选择1-硫代甘油和1-十八烷硫醇来证明这种POC的后修饰是灵活的。通过高效光引发硫醇-烯点击反应进行后合成修饰（PSM）后，产物仍然保持多孔结构，比大多数通过还原胺法报道的笼具有相对更高的比表面积（分别为337 m²/g和156 m²/g）。
