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.
Bibliographical noteFunding Information:
This work was supported by the Ministry of Science and ICT (MSIT) of Korea under the auspices of the Basic Science Research Program sponsored by the National Research Foundation (NRF) (grant no. NRF-2016R1A2B2014918) and by the DGIST R&D Program (grant no. 19-BD-0403). MSIT and POSTECH supported X-ray crystallography analysis and XANES experiments performed at 2D-SMC and 7D beamline in PLS-II.
© 2019 American Chemical Society.
All Science Journal Classification (ASJC) codes
- Colloid and Surface Chemistry