%0 Journal Article %A Song, Dahae %A Bae, Jinhee %A Ji, Hoon %A Kim, Min-Bum %A Bae, Youn-Sang %A Park, Kyo Sung %A Moon, Dohyun %A Jeong, Nak Cheon %D 2019 %T Coordinative Reduction of Metal Nodes Enhances the Hydrolytic Stability of a Paddlewheel Metal–Organic Framework %U https://acs.figshare.com/articles/journal_contribution/Coordinative_Reduction_of_Metal_Nodes_Enhances_the_Hydrolytic_Stability_of_a_Paddlewheel_Metal_Organic_Framework/7999073 %R 10.1021/jacs.9b02114.s007 %2 https://acs.figshare.com/ndownloader/files/14894000 %K h 2 Q treatment %K coordinative reduction results %K framework %K sphere electron transfer %K Cu %K MOF %K HKUST %K H 2 Q %K Metal Nodes Enhances %K hydrolytic stability %K coordinative reduction %K oxidation state %X 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. %I ACS Publications