Mapping Out Chemically Similar, Crystallographically Nonequivalent Hydrogen Sites in Metal-Organic Frameworks by H-1 Solid-State NMR Spectroscopy

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	Mapping Out Chemically Similar, Crystallographically Nonequivalent Hydrogen Sites in Metal-Organic Frameworks by H-1 Solid-State NMR Spectroscopy
	Xu, Jun 1; Terskikh, Victor V.2; Chu, Yueying 3; Zheng, Anmin 3; Huang, Yining 1
刊名	CHEMISTRY OF MATERIALS
	2015-05-12
卷号	27 期号:9 页码:3306-3316
英文摘要	Metal-organic frameworks (MOEs) are important materials with many actual and potential applications. Crystal structure of many MOFs is determined by single-crystal X-ray diffraction. However, due to the inability of XRD to accurately locate hydrogen atoms, the local structures around framework hydrogen are Usually poorly characterized even if the overall framework has been accurately determined. H-1 solid-state NMR (SSNMR) spectroscopy should, in principle, be used as a complementary method to XRD for characterizing hydrogen local environments. However, the spectral resolution of H-1 SSNMR is severely limited by the strong H-1-H-1 homonuclear dipolar coupling. In this work, we demonstrate that high-resolution H-1 MAS spectra of MOP-based material can be obtained by ultrafast sample spinning at high magnetic field in combination with isotopic dilution. In particular, we examined an important MOF, microporous alpha-Mg3(HCOO)(6) and alpha-Mg-3(HCOO)(6) in the presence of several guest species. All six chemically very similar, but crystallographically, nonequivalent H sites of these MOFs were resolved in a chemical shift range as small as 0.8 ppm. Although the assignment of H-1 peaks due to crystallographically nonequivalent hydrogens is difficult due to that they all have almost identical chemical environments, we are able to show that they can be assigned from H-1-H-1 proximity maps obtained from 2D H-1-H-1 double quantum (DQ) experiments in conjunction with theoretical calculations. H-1 MAS spectra of framework hydrogen are very sensitive to the guest molecules present inside the pores and they provide insight into host-guest interaction and dynamics of guest molecule. The ability of achieving very high tesolution for H-1 MAS NMR in MOP-based materials and subsequent spectral assignment demonstrated in this work allows one to obtain new structural information complementary to that obtained from single-crystal XRD.
WOS标题词	Science & Technology ; Physical Sciences ; Technology
类目[WOS]	Chemistry, Physical ; Materials Science, Multidisciplinary
研究领域[WOS]	Chemistry ; Materials Science
关键词[WOS]	RESOLUTION H-1-NMR SPECTROSCOPY ; MAGNETIC-RESONANCE ; PERDEUTERATED PROTEINS ; HIGH-FIELD ; MAS NMR ; X-RAY ; DYNAMICS ; SPECTRA ; BENZENE ; SYSTEMS
收录类别	SCI
语种	英语
WOS记录号	WOS:000354578600019
公开日期	2015-07-28
内容类型	期刊论文
源URL	[http://ir.wipm.ac.cn/handle/112942/4737]
专题	武汉物理与数学研究所_磁共振应用研究部
作者单位	1.Univ Western Ontario, Dept Chem, London, ON N6A 5B7, Canada 2.Univ Ottawa, Dept Chem, Ottawa, ON K1N 6N5, Canada 3.Chinese Acad Sci, State Key Lab Magnet Resonance & Atom & Mol Phys, Wuhan Ctr Magnet Resonance, Wuhan Inst Phys & Math, Wuhan 430071, Peoples R China
推荐引用方式 GB/T 7714	Xu, Jun,Terskikh, Victor V.,Chu, Yueying,et al. Mapping Out Chemically Similar, Crystallographically Nonequivalent Hydrogen Sites in Metal-Organic Frameworks by H-1 Solid-State NMR Spectroscopy[J]. CHEMISTRY OF MATERIALS,2015,27(9):3306-3316.
APA	Xu, Jun,Terskikh, Victor V.,Chu, Yueying,Zheng, Anmin,&Huang, Yining.(2015).Mapping Out Chemically Similar, Crystallographically Nonequivalent Hydrogen Sites in Metal-Organic Frameworks by H-1 Solid-State NMR Spectroscopy.CHEMISTRY OF MATERIALS,27(9),3306-3316.
MLA	Xu, Jun,et al."Mapping Out Chemically Similar, Crystallographically Nonequivalent Hydrogen Sites in Metal-Organic Frameworks by H-1 Solid-State NMR Spectroscopy".CHEMISTRY OF MATERIALS 27.9(2015):3306-3316.