Spies Within Metal-Organic Frameworks: Investigating Metal Centers Using Solid-State NMR

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	Spies Within Metal-Organic Frameworks: Investigating Metal Centers Using Solid-State NMR
	He, Peng 1; Lucier, Bryan E. G.1; Terskikh, Victor V.2; Shi, Qi 3; Dong, Jinxiang 3; Chu, Yueying 4; Zheng, Anmin 4; Sutrisno, Andre 1; Huang, Yining 1
刊名	JOURNAL OF PHYSICAL CHEMISTRY C
	2014-10-16
卷号	118 期号:41 页码:23728-23744
英文摘要	Structural characterization of metalorganic frameworks (MOFs) is crucial, since an understanding of the relationship between the macroscopic properties of these industrially relevant materials and their molecular-level structures allows for the development of new applications and improvements in current performance. In many MOFs, the incorporated metal centers dictate the short- and long-range structure and porosity of the material. Here we demonstrate that solid-state NMR (SSNMR) spectroscopy targeting NMR-active metal centers at natural abundance, in concert with ab initio density functional theory (DFT) calculations and X-ray diffraction (XRD), is a powerful tool for elucidating the molecular-level structure of MOFs. Zr-91 SSNMR experiments on MIL-140A are paired with DFT calculations and geometry optimizations in order to detect inaccuracies in the reported powder XRD crystal structure. In-115 and La-139 SSNMR experiments on sets of related MOFs at two different magnetic fields illustrate the sensitivity of the In-115/La-139 electric field gradient tensors to subtle differences in coordination, bond length distribution, and ligand geometry about the metal center. Ti-47/49 SSNMR experiments reflect the presence or absence of guest solvent in MIL-125(Ti), and when combined with DFT calculations, these SSNMR experiments permit the study of local hydroxyl group configurations within the MOF channels. Zn-67 SSNMR experiments and DFT calculations are also used to explore the geometry near Zn within a set of four MOFs as well as local disordering caused by distributions of different linkers around the metal. SSNMR spectroscopy of metal centers offers an impressive addition to the arsenal of techniques for MOF characterization and is particularly useful in cases where XRD information may be ambiguous, incomplete, or unavailable.
WOS标题词	Science & Technology ; Physical Sciences ; Technology
类目[WOS]	Chemistry, Physical ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary
研究领域[WOS]	Chemistry ; Science & Technology - Other Topics ; Materials Science
关键词[WOS]	ZEOLITIC IMIDAZOLATE FRAMEWORKS ; NUCLEAR MAGNETIC-RESONANCE ; DENSITY-FUNCTIONAL THEORY ; ELECTRIC-FIELD-GRADIENT ; ZR-91 NMR ; QUADRUPOLAR NUCLEI ; LA-139 NMR ; COORDINATION-COMPLEXES ; ZIRCONIUM-PHOSPHATES ; ADIABATIC PULSES
收录类别	SCI
语种	英语
WOS记录号	WOS:000343333600034
公开日期	2015-07-14
内容类型	期刊论文
源URL	[http://ir.wipm.ac.cn/handle/112942/1349]
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.Taiyuan Univ Technol, Res Inst Special Chem, Taiyuan 030024, Shanxi, Peoples R China 4.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	He, Peng,Lucier, Bryan E. G.,Terskikh, Victor V.,et al. Spies Within Metal-Organic Frameworks: Investigating Metal Centers Using Solid-State NMR[J]. JOURNAL OF PHYSICAL CHEMISTRY C,2014,118(41):23728-23744.
APA	He, Peng.,Lucier, Bryan E. G..,Terskikh, Victor V..,Shi, Qi.,Dong, Jinxiang.,...&Huang, Yining.(2014).Spies Within Metal-Organic Frameworks: Investigating Metal Centers Using Solid-State NMR.JOURNAL OF PHYSICAL CHEMISTRY C,118(41),23728-23744.
MLA	He, Peng,et al."Spies Within Metal-Organic Frameworks: Investigating Metal Centers Using Solid-State NMR".JOURNAL OF PHYSICAL CHEMISTRY C 118.41(2014):23728-23744.