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

Dahae Song, Jinhee Bae, Hoon Ji, Min Bum Kim, Youn Sang Bae, Kyo Sung Park, Dohyun Moon, Nak Cheon Jeong

Research output: Contribution to journalArticle

12 Citations (Scopus)

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 Cu2+ ion, which is realized in a paddlewheel MOF, HKUST-1, with a postsynthetic manner via inner sphere "single" electron transfer from hydroquinone (H2Q) to Cu2+ through its coordination bond. H2Q treatment of HKUST-1 under anhydrous conditions leads to the single charge (1+) reduction of approximately 30% of Cu2+ ions. Thus, this coordinative reduction is an excellent reduction process to be self-controlled in both oxidation state and quantity. As described below, once Cu2+ 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.

Original languageEnglish
Pages (from-to)7853-7864
Number of pages12
JournalJournal of the American Chemical Society
Volume141
Issue number19
DOIs
Publication statusPublished - 2019 May 15

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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