Remote stabilization of copper paddlewheel based molecular building blocks in metal-organic frameworks
Pham, Tony T.
Forrest, Katherine A.
Nugent, Patrick S.
Williams, Kia R.
Weselinski, Lukasz Jan
Zaworotko, Michael J.
KAUST DepartmentFunctional Materials Design, Discovery and Development (FMD3)
Physical Sciences and Engineering (PSE) Division
Chemical Science Program
Advanced Membranes and Porous Materials Research Center
Permanent link to this recordhttp://hdl.handle.net/10754/564111
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AbstractCopper paddlewheel based molecular building blocks (MBBs) are ubiquitous and have been widely employed for the construction of highly porous metal-organic frameworks (MOFs). However, most copper paddlewheel based MOFs fail to retain their structural integrity in the presence of water. This instability is directly correlated to the plausible displacement of coordinating carboxylates in the copper paddlewheel MBB, [Cu2(O2C-)4], by the strongly coordinating water molecules. In this comprehensive study, we illustrate the chemical stability control in the rht-MOF platform via strengthening the coordinating bonds within the triangular inorganic MBB, [Cu3O(N4-x(CH)xC-)3] (x = 0, 1, or 2). Remotely, the chemical stabilization propagated into the paddlewheel MBB to afford isoreticular rht-MOFs with remarkably enhanced water/chemical stabilities compared to the prototypal rht-MOF-1. © 2015 American Chemical Society.
SponsorsThe authors acknowledge NSF (DMR-1352065) and USF for financial support of this work. B.S. acknowledges the National Science Foundation (Award No. CHE-1152362), the computational resources that were made available by an XSEDE Grant (No. TG-DMR090028), and the use of the services provided by Research Computing at the University of South Florida. X.S. thanks NSF for the financial support (CHE-0844602). The single-crystal X-ray diffraction of rht-MOF-tri and rht-MOF-pyr was carried out at the Advanced Photon Source on beamline 15-ID-B of ChemMatCARS Sector 15, supported by the National Science Foundation under grant number NSF/CHE-1346572. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. M.E. acknowledges the financial support from King Abdullah University of Science and Technology.
PublisherAmerican Chemical Society (ACS)
JournalChemistry of Materials