Fabrication of Porous Covalent Organic Cages Using Cyclodextrin Metal-Organic Frameworks as Template

	Fabrication of Porous Covalent Organic Cages Using Cyclodextrin Metal-Organic Frameworks as Template
	Li Yangxue 1; Zhang Wei 1; Liu Zhi 2; Xie Zhigang 1
刊名	ACTA CHIMICA SINICA
	2015-06-15
卷号	73 期号:6 页码:641-645
关键词	gamma-CD metal-organic frameworks organic cage cross-linked polymers templated synthesis
英文摘要	Up to now, transformation from metal-organic frameworks (MOFs) to covalent-organic-framework cages (COF-Cages) has never been reported. In this report, we demonstrated an organic cage crystal by transformation from a cyclodextrin MOF, via boronate ester formation reaction of the hydroxy groups of gamma-CD inside the MOF, followed by removing of the potassium ions. First, CD-MOF was prepared by reacting gamma-CD with potassium hydroxide in aqueous solution, followed by vapor diffusion of methanol into the solution according to a previously reported method. The freshly prepared CD-MOF was first washed with ethanol three times to remove the unreacted reactants, and then added to an ethanol saturated solution of benzene-1,4-diboronic acid (BDBA) in a screw top vial, and kept it at 65 degrees C for three days. Finally, the covalent cross-linked CD-MOF (CL-CD-MOF) was obtained by forming boronic esters between the uncoordinated C(2) and C(3) hydroxy groups of contiguous gamma-CD sides in the CD-MOF pores and two boronic acid groups of BDBA. Structure and physical properties of Z-Cages were fully characterized by thermogravimetric analysis (TGA), infrared spectroscopy (IR), powder X-ray diffraction (PXRD), solid-state C-13 and B-11 cross polarization/magic angle spining nuclear magnetic resonance (CP/MAS/NMR) spectroscopy and nitrogen adsorption. The obtained zeolite-type organic cage (Z-cage) displayed a targeted sodalite-type crystalline structure and permanent porosity with the surface area of 862 m(2).g(-1). A control experiment, the cross-linked polymers (CL-polymer) formed by coupling of gamma-CD and BDBA was done by solvothermal method. The CL-polymer was synthesized by the heating of a 4 : 1 stoichiometric mixture of BDBA and gamma-CD at 90 degrees C for three days in dimethylformamide (DMF). PXRD pattern shows the CL-polymer are crystalline, but totally different with Z-cage. This transformation from crystalline inorganic-organic hybrid framework of MOF to crystalline organic framework provides an opportunity for crystal-to-crystal in porous crystalline materials.
收录类别	SCI
语种	英语
公开日期	2015-10-27
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/27717]
专题	化学研究所_高分子物理与化学实验室
作者单位	1.Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China 2.Food Inspect Jilin, Changchun 130103, Peoples R China
推荐引用方式 GB/T 7714	Li Yangxue,Zhang Wei,Liu Zhi,et al. Fabrication of Porous Covalent Organic Cages Using Cyclodextrin Metal-Organic Frameworks as Template[J]. ACTA CHIMICA SINICA,2015,73(6):641-645.
APA	Li Yangxue,Zhang Wei,Liu Zhi,&Xie Zhigang.(2015).Fabrication of Porous Covalent Organic Cages Using Cyclodextrin Metal-Organic Frameworks as Template.ACTA CHIMICA SINICA,73(6),641-645.
MLA	Li Yangxue,et al."Fabrication of Porous Covalent Organic Cages Using Cyclodextrin Metal-Organic Frameworks as Template".ACTA CHIMICA SINICA 73.6(2015):641-645.