Harnessing Structural Dynamics in a 2D Manganese-Benzoquinoid Framework To Dramatically Accelerate Metal Transport in Diffusion-Limited Metal Exchange Reactions

doi:10.1021/jacs.8b06774

CORC > 化学研究所 > 中国科学院化学研究所

	Harnessing Structural Dynamics in a 2D Manganese-Benzoquinoid Framework To Dramatically Accelerate Metal Transport in Diffusion-Limited Metal Exchange Reactions
	Liu, Lujia 1; Li, Liang 1,2,4; DeGayner, Jordan A.1; Winegar, Peter H.1; Fang, Yu 3; Harris, T. David 1
刊名	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
	2018-09-12
卷号	140 期号:36 页码:11444-11453
ISSN号	0002-7863
DOI	10.1021/jacs.8b06774
英文摘要	Postsynthetic metal exchange represents a powerful synthetic method to generate metal organic frameworks (MOFs) that are not accessible through direct synthesis, yet it is often hampered by slow reaction kinetics and incomplete exchange. While studies of metal exchange reactions have primarily focused on the transmetalation process, transport of exogenous metal ions into the framework structure represents a critical yet underexplored process. Here, we employ X-ray crystallography, electron microscopy, and energy dispersive X-ray spectroscopy to comprehensively examine the transport of Co2+ and Zn2+ ions during postsynthetic metal exchange reactions within the 2D manganese-benzoquinoid framework (Et4N)(2)[Mn2L3] (H2L = 3,6-dichloro-2,5-dihydroxy-1,4-benzoquinone). These studies reveal that exogenous metal ions diffuse primarily through the 1D channel along the crystallographic c axis, and this transport represents the rate determining step. In addition, the Mn framework exhibits reversible dynamic structure behavior, contracting upon desolvation and then rapidly restoring its original structure and full volume upon resolvation. When conducting metal exchange reactions using a partially desolvated sample, these structural dynamics lead to acceleration of metal transport by up to 2000-fold, improve product purity, and give exchange of a larger fraction of metal sites. Finally, upon performing metal exchange using full-solvated crystals, an intermediate product can be isolated that constitutes a unique example of a 2D material with a gradient vertical heterostructure.
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000444793400044
内容类型	期刊论文
源URL	[http://ir.iccas.ac.cn/handle/121111/43039]
专题	中国科学院化学研究所
通讯作者	Harris, T. David
作者单位	1.Northwestern Univ, Dept Chem, 2145 Sheridan Rd, Evanston, IL 60208 USA 2.Nankai Univ, Dept Chem, Tianjin 300071, Peoples R China 3.Texas A&M Univ, Dept Chem, College Stn, TX 77843 USA 4.Peking Univ, Coll Chem & Mol Engn, Beijing Natl Lab Mol Sci, State Key Lab Rare Earth Mat Chem & Applicat, Beijing 100871, Peoples R China
推荐引用方式 GB/T 7714	Liu, Lujia,Li, Liang,DeGayner, Jordan A.,et al. Harnessing Structural Dynamics in a 2D Manganese-Benzoquinoid Framework To Dramatically Accelerate Metal Transport in Diffusion-Limited Metal Exchange Reactions[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2018,140(36):11444-11453.
APA	Liu, Lujia,Li, Liang,DeGayner, Jordan A.,Winegar, Peter H.,Fang, Yu,&Harris, T. David.(2018).Harnessing Structural Dynamics in a 2D Manganese-Benzoquinoid Framework To Dramatically Accelerate Metal Transport in Diffusion-Limited Metal Exchange Reactions.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,140(36),11444-11453.
MLA	Liu, Lujia,et al."Harnessing Structural Dynamics in a 2D Manganese-Benzoquinoid Framework To Dramatically Accelerate Metal Transport in Diffusion-Limited Metal Exchange Reactions".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 140.36(2018):11444-11453.