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Coordinative Reduction of Metal Nodes Enhances the Hydrolytic Stability of a Paddlewheel Metal-Organic Framework

Title
Coordinative Reduction of Metal Nodes Enhances the Hydrolytic Stability of a Paddlewheel Metal-Organic Framework
Authors
Song, DahaeBae, JinheeJi, HoonKim, Min-BumBae, Youn-SangPark, Kyo SungMoon, DohyunJeong, Nak Cheon
DGIST Authors
Jeong, Nak Cheon
Issue Date
2019-05
Citation
Journal of the American Chemical Society, 141(19), 7853-7864
Type
Article
Article Type
Article
Keyword
HIGH H-2 ADSORPTION; X-RAY-STRUCTURE; WATER STABILITY; LIGAND-EXCHANGE; POSTSYNTHETIC LIGAND; STEPWISE SYNTHESIS; COPPER; ZIRCONIUM; FUNCTIONALIZATION; ACTIVATION
ISSN
0002-7863
Abstract
Enhancement of hydrolytic stability of metal-organic frameworks (MOFs) is a challenging issue in MOF chemistry because most MOFs have shown limitations in their applications under a humid environment. Meanwhile, inner sphere electron transfer has constituted one of the most intensively studied subjects in contemporary chemistry. In this report, we show, for the first time, a new conceptual coordinative reduction of Cu 2+ ion, which is realized in a paddlewheel MOF, HKUST-1, with a postsynthetic manner via inner sphere single electron transfer from hydroquinone (H 2 Q) to Cu 2+ through its coordination bond. H 2 Q treatment of HKUST-1 under anhydrous conditions leads to the single charge (1+) reduction of approximately 30% of Cu 2+ ions. Thus, this coordinative reduction is an excellent reduction process to be self-controlled in both oxidation state and quantity. As described below, once Cu 2+ ions are reduced to Cu + , the reduction reaction does not proceed further, in terms of their oxidation state as well as their amount. Also, we demonstrate that a half of the Cu + ions (about 15%) remains in paddlewheel framework with pseudo square planar geometry and the other half of the Cu + ions (about 15%) forms [Cu(MeCN) 4 ] + complex in a small cage in the fashion of a ship-in-a-bottle after dissociation from the framework. Furthermore, we show that the coordinative reduction results in substantial enhancement of the hydrolytic stability of HKUST-1 to the extent that its structure remains intact even after exposure to humid air for two years. © 2019 American Chemical Society.
URI
http://hdl.handle.net/20.500.11750/9899
DOI
10.1021/jacs.9b02114
Publisher
American Chemical Society
Related Researcher
  • Author Jeong, Nak Cheon Nanoporous Chemistry Laboratory
  • Research Interests Inorganic Chemistry; Metal-Organic Framework; Nanoporous Materials; Electron Transport;Ion Transport
Files:
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Collection:
Department of Emerging Materials ScienceNanoporous Chemistry Laboratory1. Journal Articles


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