Quest for Highly-connected MOF Platforms: Rare-Earth Polynuclear Clusters Versatility Meets Net Topology Needs.

Handle URI:
http://hdl.handle.net/10754/528236
Title:
Quest for Highly-connected MOF Platforms: Rare-Earth Polynuclear Clusters Versatility Meets Net Topology Needs.
Authors:
Alezi, Dalal ( 0000-0002-3462-1193 ) ; Peedikakkal, Abdul Malik P.; Weselinski, Lukasz J.; Guillerm, Vincent ( 0000-0003-3460-223X ) ; Belmabkhout, Youssef ( 0000-0001-9952-5007 ) ; Cairns, Amy J; Chen, Zhijie; Wojtas, Lukasz; Eddaoudi, Mohamed ( 0000-0003-1916-9837 )
Abstract:
Gaining control over the assembly of highly porous rare-earth (RE) based metal-organic frameworks (MOFs) remains challenging. Here we report the latest discoveries on our continuous quest for highly-connected nets. The topological exploration based on the non-compatibility of 12-connected RE polynuclear carboxylate-based cluster, points of extension matching the 12 vertices of the cuboctahedron (cuo), with 3-connected organic ligands led to the discovery of two fascinating and highly-connected minimal edge-transitive nets, pek and aea. The reduced symmetry of the employed triangular tricarboxylate ligand, as compared to the prototype highly symmetrical 1,3,5-benzene(tris)benzoic acid guided the concurrent occurrence of nonanuclear [RE9(μ3-OH)12(μ3-O)2(O2C–)12] and hexanuclear [RE6(OH)8(O2C–)8] carboxylate-based clusters as 12-connected and 8-connected molecular building blocks in the structure of a 3-periodic pek-MOF based on a novel (3,8,12)-c trinodal net. The use of a tricarboxylate ligand with modified angles between carboxylate moieties led to the formation of a second MOF containing solely nonanuclear clusters and exhibiting once more a novel and a highly-connected (3,12,12)-c trinodal net with aea topology. Notably, it is the first time that RE-MOFs with double six-membered ring (d6R) secondary building units are isolated, representing therefore a critical step forward toward the design of novel and highly coordinated materials using the supermolecular building layer approach while considering the d6Rs as building pillars. Lastly, the potential of these new MOFs for gas separation/storage was investigated by performing gas adsorption studies of various probe gas molecules over a wide range of pressures. Noticeably, pek-MOF-1 showed excellent volumetric CO2 and CH4 uptakes at high pressures.
KAUST Department:
Functional Materials Design, Discovery and Development (FMD3); Advanced Membranes and Porous Materials Research Center; Physical Sciences and Engineering (PSE) Division
Citation:
Quest for Highly-connected MOF Platforms: Rare-Earth Polynuclear Clusters Versatility Meets Net Topology Needs. 2015:150407200837004 Journal of the American Chemical Society
Publisher:
American Chemical Society (ACS)
Journal:
Journal of the American Chemical Society
Issue Date:
7-Apr-2015
DOI:
10.1021/jacs.5b00450
Type:
Article
ISSN:
0002-7863; 1520-5126
Is Supplemented By:
Alezi, D., Peedikakkal, A. M. P., Weseliński, Ł. J., Guillerm, V., Belmabkhout, Y., Cairns, A. J., … Eddaoudi, M. (2015). CCDC 1410819: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jc298; DOI:10.5517/cc1jc298; HANDLE:http://hdl.handle.net/10754/624447; Alezi, D., Peedikakkal, A. M. P., Weseliński, Ł. J., Guillerm, V., Belmabkhout, Y., Cairns, A. J., … Eddaoudi, M. (2015). CCDC 1410820: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jc2b9; DOI:10.5517/cc1jc2b9; HANDLE:http://hdl.handle.net/10754/624448; Alezi, D., Peedikakkal, A. M. P., Weseliński, Ł. J., Guillerm, V., Belmabkhout, Y., Cairns, A. J., … Eddaoudi, M. (2015). CCDC 1410821: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jc2cb; DOI:10.5517/cc1jc2cb; HANDLE:http://hdl.handle.net/10754/624449; Alezi, D., Peedikakkal, A. M. P., Weseliński, Ł. J., Guillerm, V., Belmabkhout, Y., Cairns, A. J., … Eddaoudi, M. (2015). CCDC 1410822: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jc2dc; DOI:10.5517/cc1jc2dc; HANDLE:http://hdl.handle.net/10754/624450; Alezi, D., Peedikakkal, A. M. P., Weseliński, Ł. J., Guillerm, V., Belmabkhout, Y., Cairns, A. J., … Eddaoudi, M. (2015). CCDC 1410823: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jc2fd; DOI:10.5517/cc1jc2fd; HANDLE:http://hdl.handle.net/10754/624451
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/jacs.5b00450
Appears in Collections:
Articles; Advanced Membranes and Porous Materials Research Center; Physical Sciences and Engineering (PSE) Division; Functional Materials Design, Discovery and Development (FMD3)

Full metadata record

DC FieldValue Language
dc.contributor.authorAlezi, Dalalen
dc.contributor.authorPeedikakkal, Abdul Malik P.en
dc.contributor.authorWeselinski, Lukasz J.en
dc.contributor.authorGuillerm, Vincenten
dc.contributor.authorBelmabkhout, Youssefen
dc.contributor.authorCairns, Amy Jen
dc.contributor.authorChen, Zhijieen
dc.contributor.authorWojtas, Lukaszen
dc.contributor.authorEddaoudi, Mohameden
dc.date.accessioned2015-04-12T06:32:35Zen
dc.date.available2015-04-12T06:32:35Zen
dc.date.issued2015-04-07en
dc.identifier.citationQuest for Highly-connected MOF Platforms: Rare-Earth Polynuclear Clusters Versatility Meets Net Topology Needs. 2015:150407200837004 Journal of the American Chemical Societyen
dc.identifier.issn0002-7863en
dc.identifier.issn1520-5126en
dc.identifier.doi10.1021/jacs.5b00450en
dc.identifier.urihttp://hdl.handle.net/10754/528236en
dc.description.abstractGaining control over the assembly of highly porous rare-earth (RE) based metal-organic frameworks (MOFs) remains challenging. Here we report the latest discoveries on our continuous quest for highly-connected nets. The topological exploration based on the non-compatibility of 12-connected RE polynuclear carboxylate-based cluster, points of extension matching the 12 vertices of the cuboctahedron (cuo), with 3-connected organic ligands led to the discovery of two fascinating and highly-connected minimal edge-transitive nets, pek and aea. The reduced symmetry of the employed triangular tricarboxylate ligand, as compared to the prototype highly symmetrical 1,3,5-benzene(tris)benzoic acid guided the concurrent occurrence of nonanuclear [RE9(μ3-OH)12(μ3-O)2(O2C–)12] and hexanuclear [RE6(OH)8(O2C–)8] carboxylate-based clusters as 12-connected and 8-connected molecular building blocks in the structure of a 3-periodic pek-MOF based on a novel (3,8,12)-c trinodal net. The use of a tricarboxylate ligand with modified angles between carboxylate moieties led to the formation of a second MOF containing solely nonanuclear clusters and exhibiting once more a novel and a highly-connected (3,12,12)-c trinodal net with aea topology. Notably, it is the first time that RE-MOFs with double six-membered ring (d6R) secondary building units are isolated, representing therefore a critical step forward toward the design of novel and highly coordinated materials using the supermolecular building layer approach while considering the d6Rs as building pillars. Lastly, the potential of these new MOFs for gas separation/storage was investigated by performing gas adsorption studies of various probe gas molecules over a wide range of pressures. Noticeably, pek-MOF-1 showed excellent volumetric CO2 and CH4 uptakes at high pressures.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/jacs.5b00450en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jacs.5b00450.en
dc.titleQuest for Highly-connected MOF Platforms: Rare-Earth Polynuclear Clusters Versatility Meets Net Topology Needs.en
dc.typeArticleen
dc.contributor.departmentFunctional Materials Design, Discovery and Development (FMD3)en
dc.contributor.departmentAdvanced Membranes and Porous Materials Research Centeren
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalJournal of the American Chemical Societyen
dc.eprint.versionPost-printen
dc.contributor.institutionDepartment of Chemistry, University of South Florida, 4202 East Fowler Avenue, Tampa, Florida 33620, United Statesen
kaust.authorWeselinski, Lukasz Janen
kaust.authorGuillerm, Vincenten
kaust.authorBelmabkhout, Youssefen
kaust.authorCairns, Amyen
kaust.authorEddaoudi, Mohameden
kaust.authorAlezi, Dalalen
kaust.authorPuthan Peedikakkal, Abdul Maliken
kaust.authorChen, Zhijieen
dc.relation.isSupplementedByAlezi, D., Peedikakkal, A. M. P., Weseliński, Ł. J., Guillerm, V., Belmabkhout, Y., Cairns, A. J., … Eddaoudi, M. (2015). CCDC 1410819: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jc298en
dc.relation.isSupplementedByDOI:10.5517/cc1jc298en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624447en
dc.relation.isSupplementedByAlezi, D., Peedikakkal, A. M. P., Weseliński, Ł. J., Guillerm, V., Belmabkhout, Y., Cairns, A. J., … Eddaoudi, M. (2015). CCDC 1410820: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jc2b9en
dc.relation.isSupplementedByDOI:10.5517/cc1jc2b9en
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624448en
dc.relation.isSupplementedByAlezi, D., Peedikakkal, A. M. P., Weseliński, Ł. J., Guillerm, V., Belmabkhout, Y., Cairns, A. J., … Eddaoudi, M. (2015). CCDC 1410821: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jc2cben
dc.relation.isSupplementedByDOI:10.5517/cc1jc2cben
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624449en
dc.relation.isSupplementedByAlezi, D., Peedikakkal, A. M. P., Weseliński, Ł. J., Guillerm, V., Belmabkhout, Y., Cairns, A. J., … Eddaoudi, M. (2015). CCDC 1410822: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jc2dcen
dc.relation.isSupplementedByDOI:10.5517/cc1jc2dcen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624450en
dc.relation.isSupplementedByAlezi, D., Peedikakkal, A. M. P., Weseliński, Ł. J., Guillerm, V., Belmabkhout, Y., Cairns, A. J., … Eddaoudi, M. (2015). CCDC 1410823: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/cc1jc2fden
dc.relation.isSupplementedByDOI:10.5517/cc1jc2fden
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624451en
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