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Title: Single-crystal-to-single-crystal metalation of a metal-organic framework: A route toward structurally well-defined catalysts

Abstract

Metal–organic frameworks featuring ligands with open chelating groups are versatile platforms for the preparation of a diverse set of heterogeneous catalysts through postsynthetic metalation. The crystalline nature of these materials allows them to be characterized via X-ray diffraction, which provides valuable insight into the structure of the metal sites that facilitate catalysis. A highly porous and thermally robust zirconium-based metal–organic framework, Zr 6O 4(OH) 4(bpydc) 6 (bpydc 2– = 2,2'-bipyridne-5,5'-dicarboxylate), bears open bipyridine sites that readily react with a variety of solution- and gas-phase metal sources to form the corresponding metalated frameworks. Remarkably, Zr 6O 4(OH) 4(bpydc) 6 undergoes a single-crystal-to-single-crystal transformation upon metalation that involves a change in space group from $$Fm\bar{3}m$$ to $$Pa\bar{3}m$$. This structural transformation leads to an ordering of the metalated linkers within the framework, allowing structural characterization of the resulting metal complexes. Furthermore, Zr 6O 4(OH) 4(bpydc) 6 yields an active heterogeneous catalyst for arene C–H borylation when metalated with [Ir(COD) 2]BF 4 (COD = 1,5-cyclooctadiene). These results highlight the unique potential of metal–organic frameworks as a class of heterogeneous catalysts that allow unparalleled structural characterization and control over their active sites.

Authors:
 [1];  [1];  [1];  [2];  [3]
  1. Univ. of California, Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1176798
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 54; Journal Issue: 6; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gonzalez, Miguel I., Bloch, Eric D., Mason, Jarad A., Teat, Simon J., and Long, Jeffrey R. Single-crystal-to-single-crystal metalation of a metal-organic framework: A route toward structurally well-defined catalysts. United States: N. p., 2015. Web. doi:10.1021/acs.inorgchem.5b00096.
Gonzalez, Miguel I., Bloch, Eric D., Mason, Jarad A., Teat, Simon J., & Long, Jeffrey R. Single-crystal-to-single-crystal metalation of a metal-organic framework: A route toward structurally well-defined catalysts. United States. doi:10.1021/acs.inorgchem.5b00096.
Gonzalez, Miguel I., Bloch, Eric D., Mason, Jarad A., Teat, Simon J., and Long, Jeffrey R. Mon . "Single-crystal-to-single-crystal metalation of a metal-organic framework: A route toward structurally well-defined catalysts". United States. doi:10.1021/acs.inorgchem.5b00096. https://www.osti.gov/servlets/purl/1176798.
@article{osti_1176798,
title = {Single-crystal-to-single-crystal metalation of a metal-organic framework: A route toward structurally well-defined catalysts},
author = {Gonzalez, Miguel I. and Bloch, Eric D. and Mason, Jarad A. and Teat, Simon J. and Long, Jeffrey R.},
abstractNote = {Metal–organic frameworks featuring ligands with open chelating groups are versatile platforms for the preparation of a diverse set of heterogeneous catalysts through postsynthetic metalation. The crystalline nature of these materials allows them to be characterized via X-ray diffraction, which provides valuable insight into the structure of the metal sites that facilitate catalysis. A highly porous and thermally robust zirconium-based metal–organic framework, Zr6O4(OH)4(bpydc)6 (bpydc2– = 2,2'-bipyridne-5,5'-dicarboxylate), bears open bipyridine sites that readily react with a variety of solution- and gas-phase metal sources to form the corresponding metalated frameworks. Remarkably, Zr6O4(OH)4(bpydc)6 undergoes a single-crystal-to-single-crystal transformation upon metalation that involves a change in space group from $Fm\bar{3}m$ to $Pa\bar{3}m$. This structural transformation leads to an ordering of the metalated linkers within the framework, allowing structural characterization of the resulting metal complexes. Furthermore, Zr6O4(OH)4(bpydc)6 yields an active heterogeneous catalyst for arene C–H borylation when metalated with [Ir(COD)2]BF4 (COD = 1,5-cyclooctadiene). These results highlight the unique potential of metal–organic frameworks as a class of heterogeneous catalysts that allow unparalleled structural characterization and control over their active sites.},
doi = {10.1021/acs.inorgchem.5b00096},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 6,
volume = 54,
place = {United States},
year = {2015},
month = {7}
}

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