Lattice-Imposed Geometry in Metal-Organic Frameworks: Lacunary Zn4O Clusters in MOF-5 Serve as Tripodal Chelating Ligands for Ni2+
The inorganic clusters in metal–organic frameworks can be used to trap metal ions in coordination geometries that are difficult to achieve in molecular chemistry. We illustrate this concept by using the well-known basic carboxylate clusters in Zn[subscript 4]O(1,4-benzenedicarboxylate)3 (MOF-5) as t...
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| Format: | Article |
| Language: | en_US |
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Royal Society of Chemistry, The
2013
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| Online Access: | http://hdl.handle.net/1721.1/78285 https://orcid.org/0000-0002-1262-1264 |
| _version_ | 1826207779739664384 |
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| author | Brozek, Carl Kavanaugh Dinca, Mircea |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Brozek, Carl Kavanaugh Dinca, Mircea |
| author_sort | Brozek, Carl Kavanaugh |
| collection | MIT |
| description | The inorganic clusters in metal–organic frameworks can be used to trap metal ions in coordination geometries that are difficult to achieve in molecular chemistry. We illustrate this concept by using the well-known basic carboxylate clusters in Zn[subscript 4]O(1,4-benzenedicarboxylate)3 (MOF-5) as tripodal chelating ligands that enforce an unusual pseudo-tetrahedral oxygen ligand field around Ni[superscript 2+]. The new Ni-based MOF-5 analogue is characterized by porosity measurements and a suite of electronic structure spectroscopies. Classical ligand field analysis of the Ni[superscript 2+] ion isolated in MOF-5 classifies the Zn3O(carboxylate)6 “tripodal ligand” as an unusual, stronger field ligand than halides and other oxygen donor ligands. These results may inspire the widespread usage of MOFs as chelating ligands for stabilizing site-isolated metal ions in future reactivity and electronic structure studies. |
| first_indexed | 2024-09-23T13:54:49Z |
| format | Article |
| id | mit-1721.1/78285 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T13:54:49Z |
| publishDate | 2013 |
| publisher | Royal Society of Chemistry, The |
| record_format | dspace |
| spelling | mit-1721.1/782852022-09-28T17:00:10Z Lattice-Imposed Geometry in Metal-Organic Frameworks: Lacunary Zn4O Clusters in MOF-5 Serve as Tripodal Chelating Ligands for Ni2+ Brozek, Carl Kavanaugh Dinca, Mircea Massachusetts Institute of Technology. Department of Chemistry Dinca, Mircea Brozek, Carl Kavanaugh Dinca, Mircea The inorganic clusters in metal–organic frameworks can be used to trap metal ions in coordination geometries that are difficult to achieve in molecular chemistry. We illustrate this concept by using the well-known basic carboxylate clusters in Zn[subscript 4]O(1,4-benzenedicarboxylate)3 (MOF-5) as tripodal chelating ligands that enforce an unusual pseudo-tetrahedral oxygen ligand field around Ni[superscript 2+]. The new Ni-based MOF-5 analogue is characterized by porosity measurements and a suite of electronic structure spectroscopies. Classical ligand field analysis of the Ni[superscript 2+] ion isolated in MOF-5 classifies the Zn3O(carboxylate)6 “tripodal ligand” as an unusual, stronger field ligand than halides and other oxygen donor ligands. These results may inspire the widespread usage of MOFs as chelating ligands for stabilizing site-isolated metal ions in future reactivity and electronic structure studies. United States. Dept. of Energy. Office of Science (Award DE-SC0006937) 2013-04-04T16:57:22Z 2013-04-04T16:57:22Z 2012-04 2012-03 Article http://purl.org/eprint/type/JournalArticle 2041-6520 http://hdl.handle.net/1721.1/78285 Brozek, Carl K., and Mircea Dincă. “Lattice-imposed Geometry in Metal–organic Frameworks: Lacunary Zn4O Clusters in MOF-5 Serve as Tripodal Chelating Ligands for Ni2+.” Chemical Science 3.6 (2012): 2110. https://orcid.org/0000-0002-1262-1264 en_US http://dx.doi.org/ 10.1039/C2SC20306E Chemical Science Creative Commons Attribution-Noncommercial-Share Alike 3.0 http://creativecommons.org/licenses/by-nc-sa/3.0/ application/pdf Royal Society of Chemistry, The Prof. Dinca via Erja Kajosalo |
| spellingShingle | Brozek, Carl Kavanaugh Dinca, Mircea Lattice-Imposed Geometry in Metal-Organic Frameworks: Lacunary Zn4O Clusters in MOF-5 Serve as Tripodal Chelating Ligands for Ni2+ |
| title | Lattice-Imposed Geometry in Metal-Organic Frameworks: Lacunary Zn4O Clusters in MOF-5 Serve as Tripodal Chelating Ligands for Ni2+ |
| title_full | Lattice-Imposed Geometry in Metal-Organic Frameworks: Lacunary Zn4O Clusters in MOF-5 Serve as Tripodal Chelating Ligands for Ni2+ |
| title_fullStr | Lattice-Imposed Geometry in Metal-Organic Frameworks: Lacunary Zn4O Clusters in MOF-5 Serve as Tripodal Chelating Ligands for Ni2+ |
| title_full_unstemmed | Lattice-Imposed Geometry in Metal-Organic Frameworks: Lacunary Zn4O Clusters in MOF-5 Serve as Tripodal Chelating Ligands for Ni2+ |
| title_short | Lattice-Imposed Geometry in Metal-Organic Frameworks: Lacunary Zn4O Clusters in MOF-5 Serve as Tripodal Chelating Ligands for Ni2+ |
| title_sort | lattice imposed geometry in metal organic frameworks lacunary zn4o clusters in mof 5 serve as tripodal chelating ligands for ni2 |
| url | http://hdl.handle.net/1721.1/78285 https://orcid.org/0000-0002-1262-1264 |
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