Abstract
Catalytic activity for acyl transfer from N-acetylimidazole (NAI) to different pyridylcarbinol (PC) regioisomers (2-PC, 3-PC, and 4-PC) is demonstrated for a set of topologically diverse, zirconium-based (porphinato)zinc metal-organic frameworks (MOFs). The MOFs studied are PCN-222, MOF-525, and NU-902, which are based on the csq, ftw, and scu topologies, respectively. The experimentally obtained reaction kinetics are discussed in light of molecular modeling results. The catalytic activity is shown to vary across the series of MOFs due to the different extent to which each topology facilitates reactant preconcentration and alignment of PC and NAI via coordination to framework porphyrin sites (orientation effects). Trends of experimental initial reaction rates with MOF topology and PC regioisomer are consistent with preconcentration effects, which depend on the number of porphyrin sites per volume of MOF, as well as with orientation effects, which depend on the number of porphyrin pairs per volume of MOF that bind PC and NAI in such a way that they are primed to form the required transition state. The present work shows how the proper alignment of catalytic linkers can enhance reaction rates in MOFs.
Original language | English (US) |
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Pages (from-to) | 14449-14457 |
Number of pages | 9 |
Journal | Journal of the American Chemical Society |
Volume | 138 |
Issue number | 43 |
DOIs | |
State | Published - Nov 2 2016 |
Funding
We gratefully acknowledge funding from the National Science Foundation (grant DMR-1334928). DFT calculations were made possible thanks to NERSC computational resources. PXRD data were collected at the J.B. Cohen X-ray Diffraction Facility (supported by the NSF MRSEC program DMR-1121262) of the Materials Research Center of Northwestern University. FT-IR data were collected in the NUANCE Center (supported by the NSF-NSEC and -MRSEC programs, the Keck Foundation, the State of Illinois, and Northwestern University) at Northwestern University.
ASJC Scopus subject areas
- General Chemistry
- Biochemistry
- Catalysis
- Colloid and Surface Chemistry
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CCDC 1988217: Experimental Crystal Structure Determination
Deria, P. (Contributor), Gómez-Gualdrón, D. A. (Contributor), Hod, I. (Contributor), Snurr, R. Q. (Contributor), Hupp, J. T. (Contributor) & Farha, O. K. (Contributor), Cambridge Crystallographic Data Centre, 2020
DOI: 10.5517/ccdc.csd.cc24qx1v, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc24qx1v&sid=DataCite
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