Exposed Equatorial Positions of Metal Centers via Sequential Ligand Elimination and Installation in MOFs

Yuan, Shuai; Zhang, Peng; Zhang, Liangliang; Garcia-Esparza, Angel T.; Sokaras, Dimosthenis; Qin, Jun -Sheng; Feng, Liang; Day, Gregory S.; Chen, Wenmiao; Drake, Hannah F.; Elumalai, Palani; Madrahimov, Sherzod T.; Sun, Daofeng; Zhou, Hong -Cai

doi:10.1021/jacs.8b04886

Title: Exposed Equatorial Positions of Metal Centers via Sequential Ligand Elimination and Installation in MOFs

Journal Article · Wed Aug 08 00:00:00 EDT 2018 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.8b04886· OSTI ID:1475583

^[1]; Zhang, Peng ^[1]; Zhang, Liangliang ^[2];

^[3]; Sokaras, Dimosthenis ^[4]; Qin, Jun -Sheng ^[1];

^[1]; Day, Gregory S. ^[1]; Chen, Wenmiao ^[1]; Drake, Hannah F. ^[1]; Elumalai, Palani ^[5]; Madrahimov, Sherzod T. ^[5];

^[2];

^[1]

Texas A & M Univ., College Station, TX (United States)
China Univ. of Petroleum (East China), Shandong (China)
SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Texas A&M Univ. at Qatar, Doha (Qatar)

Here, metal–organic frameworks (MOFs) provide highly designable platforms to construct complex coordination architectures for targeted applications. Herein, we demonstrate that trans-coordinated metal centers with exposed equatorial positions can be placed in a MOF matrix. A Zr-based MOF, namely, PCN-160, was initially synthesized as a scaffold structure. Postsynthetic linker labilization was subsequently implemented to partially remove the original dicarboxylate linkers and incorporate pyridinecarboxylates. A pair of neighboring pyridyl groups was arranged at proper proximity within the framework to form trans-binding sites that accommodate different metal cations including Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Pd²⁺. Furthermore, the trans-coordinated Ni²⁺ sites in porous frameworks can be readily accessed by substrates along the equatorial plane, facilitating the catalysis as manifested by the superior activity in ethylene dimerization over that observed for a cis-chelated catalyst.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Fossil Energy (FE)

Grant/Contract Number:: A-0030; IIP-1632486; SC0001015; DGE-1252521; NPRP9-377-1-080; FE0026472

OSTI ID:: 1475583

Journal Information:: Journal of the American Chemical Society, Vol. 140, Issue 34; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 63 works

Citation information provided by
Web of Science

References (52)

Design and synthesis of an exceptionally stable and highly porous metal-organic framework Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe Nature, Vol. 402, Issue 6759, p. 276-279 https://doi.org/10.1038/46248	journal	November 1999
Introduction to Metal–Organic Frameworks Zhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M. Chemical Reviews, Vol. 112, Issue 2, p. 673-674 https://doi.org/10.1021/cr300014x	journal	September 2011
The Chemistry and Applications of Metal-Organic Frameworks Furukawa, H.; Cordova, K. E.; O'Keeffe, M. Science, Vol. 341, Issue 6149, p. 1230444-1230444 https://doi.org/10.1126/science.1230444	journal	August 2013
A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area Ferey, G.; Mellot-Draznieks, C.; Serre, C. Science, Vol. 309, Issue 5743, p. 2040-2042 https://doi.org/10.1126/science.1116275	journal	September 2005
Exceptional chemical and thermal stability of zeolitic imidazolate frameworks Park, K. S.; Ni, Z.; Cote, A. P. Proceedings of the National Academy of Sciences, Vol. 103, Issue 27, p. 10186-10191 https://doi.org/10.1073/pnas.0602439103	journal	June 2006
Secondary building units, nets and bonding in the chemistry of metal–organic frameworks Tranchemontagne, David J.; Mendoza-Cortés, José L.; O’Keeffe, Michael Chemical Society Reviews, Vol. 38, Issue 5, p. 1257-1283 https://doi.org/10.1039/b817735j	journal	January 2009
Topological Analysis of Metal–Organic Frameworks with Polytopic Linkers and/or Multiple Building Units and the Minimal Transitivity Principle Li, Mian; Li, Dan; O’Keeffe, Michael Chemical Reviews, Vol. 114, Issue 2 https://doi.org/10.1021/cr400392k	journal	November 2013
Tuning the structure and function of metal–organic frameworks via linker design Lu, Weigang; Wei, Zhangwen; Gu, Zhi-Yuan Chem. Soc. Rev., Vol. 43, Issue 16 https://doi.org/10.1039/C4CS00003J	journal	January 2014
Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage Eddaoudi, Mohamed; Kim, Jaheon; Rosi, Nathaniel Science, Vol. 295, Issue 5554, p. 469-472 https://doi.org/10.1126/science.1067208	journal	January 2002
Hydrogen Storage in Microporous Metal-Organic Frameworks Rosi, Nathaniel L.; Eckert, Juergen; Eddaoudi, Mohamed Science, Vol. 300, Issue 5622, p. 1127-1129 https://doi.org/10.1126/science.1083440	journal	May 2003
Carbon Dioxide Capture in Metal–Organic Frameworks Sumida, Kenji; Rogow, David L.; Mason, Jarad A. Chemical Reviews, Vol. 112, Issue 2, p. 724-781 https://doi.org/10.1021/cr2003272	journal	September 2011
Luminescent Functional Metal–Organic Frameworks Cui, Yuanjing; Yue, Yanfeng; Qian, Guodong Chemical Reviews, Vol. 112, Issue 2 https://doi.org/10.1021/cr200101d	journal	June 2011
Metal–organic frameworks for artificial photosynthesis and photocatalysis Zhang, Teng; Lin, Wenbin Chem. Soc. Rev., Vol. 43, Issue 16 https://doi.org/10.1039/C4CS00103F	journal	January 2014
Destruction of chemical warfare agents using metal–organic frameworks Mondloch, Joseph E.; Katz, Michael J.; Isley III, William C. Nature Materials, Vol. 14, Issue 5 https://doi.org/10.1038/nmat4238	journal	March 2015
Very Large Breathing Effect in the First Nanoporous Chromium(III)-Based Solids MIL-53 or Cr^III(OH)·{O₂C−C₆H₄−CO₂}·{HO₂C−C₆H₄−CO₂H}_x·H₂O_y Serre, Christian; Millange, Franck; Thouvenot, Christelle Journal of the American Chemical Society, Vol. 124, Issue 45, p. 13519-13526 https://doi.org/10.1021/ja0276974	journal	November 2002
Broadly Hysteretic H ₂ Adsorption in the Microporous Metal−Organic Framework Co(1,4-benzenedipyrazolate) Choi, Hye Jin; Dincă, Mircea; Long, Jeffrey R. Journal of the American Chemical Society, Vol. 130, Issue 25 https://doi.org/10.1021/ja8024092	journal	June 2008
Hydrocarbon Separations in a Metal-Organic Framework with Open Iron(II) Coordination Sites Bloch, E. D.; Queen, W. L.; Krishna, R. Science, Vol. 335, Issue 6076, p. 1606-1610 https://doi.org/10.1126/science.1217544	journal	March 2012
Cooperative insertion of CO2 in diamine-appended metal-organic frameworks McDonald, Thomas M.; Mason, Jarad A.; Kong, Xueqian Nature, Vol. 519, Issue 7543 https://doi.org/10.1038/nature14327	journal	March 2015
Retrosynthesis of multi-component metal−organic frameworks Yuan, Shuai; Qin, Jun-Sheng; Li, Jialuo Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-03102-5	journal	February 2018
Self-Accelerating CO Sorption in a Soft Nanoporous Crystal Sato, H.; Kosaka, W.; Matsuda, R. Science, Vol. 343, Issue 6167 https://doi.org/10.1126/science.1246423	journal	December 2013
Methane storage in flexible metal–organic frameworks with intrinsic thermal management Mason, Jarad A.; Oktawiec, Julia; Taylor, Mercedes K. Nature, Vol. 527, Issue 7578 https://doi.org/10.1038/nature15732	journal	October 2015
A spin transition mechanism for cooperative adsorption in metal–organic frameworks Reed, Douglas A.; Keitz, Benjamin K.; Oktawiec, Julia Nature, Vol. 550, Issue 7674 https://doi.org/10.1038/nature23674	journal	September 2017
Postsynthetic Methods for the Functionalization of Metal–Organic Frameworks Cohen, Seth M. Chemical Reviews, Vol. 112, Issue 2, p. 970-1000 https://doi.org/10.1021/cr200179u	journal	September 2011
A homochiral metal–organic porous material for enantioselective separation and catalysis Seo, Jung Soo; Whang, Dongmok; Lee, Hyoyoung Nature, Vol. 404, Issue 6781, p. 982-986 https://doi.org/10.1038/35010088	journal	April 2000
Postsynthetic Covalent Modification of a Neutral Metal−Organic Framework Wang, Zhenqiang; Cohen, Seth M. Journal of the American Chemical Society, Vol. 129, Issue 41, p. 12368-12369 https://doi.org/10.1021/ja074366o	journal	October 2007
Framework functionalisation triggers metal complex binding Ingleson, Michael J.; Perez Barrio, Jorge; Guilbaud, Jean-Baptiste Chemical Communications, Vol. 0, Issue 23, p. 2680-2682 https://doi.org/10.1039/b718367d	journal	January 2008
Postsynthetic Ligand and Cation Exchange in Robust Metal–Organic Frameworks Kim, Min; Cahill, John F.; Fei, Honghan Journal of the American Chemical Society, Vol. 134, Issue 43 https://doi.org/10.1021/ja3079219	journal	October 2012
Solvent-Assisted Linker Exchange: An Alternative to the De Novo Synthesis of Unattainable Metal-Organic Frameworks Karagiaridi, Olga; Bury, Wojciech; Mondloch, Joseph E. Angewandte Chemie International Edition, Vol. 53, Issue 18 https://doi.org/10.1002/anie.201306923	journal	March 2014
Ti ³⁺ -, V ^2+/3+ -, Cr ^2+/3+ -, Mn ²⁺ -, and Fe ²⁺ -Substituted MOF-5 and Redox Reactivity in Cr- and Fe-MOF-5 Brozek, Carl K.; Dincă, Mircea Journal of the American Chemical Society, Vol. 135, Issue 34 https://doi.org/10.1021/ja4064475	journal	August 2013
Cation exchange at the secondary building units of metal–organic frameworks Brozek, C. K.; Dincă, M. Chem. Soc. Rev., Vol. 43, Issue 16 https://doi.org/10.1039/C4CS00002A	journal	January 2014
Beyond post-synthesis modification: evolution of metal–organic frameworks via building block replacement Deria, Pravas; Mondloch, Joseph E.; Karagiaridi, Olga Chem. Soc. Rev., Vol. 43, Issue 16 https://doi.org/10.1039/C4CS00067F	journal	January 2014
Stepwise Synthesis of Metal–Organic Frameworks Bosch, Mathieu; Yuan, Shuai; Rutledge, William Accounts of Chemical Research, Vol. 50, Issue 4 https://doi.org/10.1021/acs.accounts.6b00457	journal	February 2017
Perfluoroalkane Functionalization of NU-1000 via Solvent-Assisted Ligand Incorporation: Synthesis and CO₂ Adsorption Studies Deria, Pravas; Mondloch, Joseph E.; Tylianakis, Emmanuel Journal of the American Chemical Society, Vol. 135, Issue 45, p. 16801-16804 https://doi.org/10.1021/ja408959g	journal	October 2013
Versatile functionalization of the NU-1000 platform by solvent-assisted ligand incorporation Deria, Pravas; Bury, Wojciech; Hupp, Joseph T. Chemical Communications, Vol. 50, Issue 16, p. 1965-1968 https://doi.org/10.1039/c3cc48562e	journal	January 2014
Sequential Linker Installation: Precise Placement of Functional Groups in Multivariate Metal–Organic Frameworks Yuan, Shuai; Lu, Weigang; Chen, Ying-Pin Journal of the American Chemical Society, Vol. 137, Issue 9 https://doi.org/10.1021/ja512762r	journal	March 2015
Linker Installation: Engineering Pore Environment with Precisely Placed Functionalities in Zirconium MOFs Yuan, Shuai; Chen, Ying-Pin; Qin, Jun-Sheng Journal of the American Chemical Society, Vol. 138, Issue 28 https://doi.org/10.1021/jacs.6b04501	journal	July 2016
Metal–Organic Framework Nodes Support Single-Site Magnesium–Alkyl Catalysts for Hydroboration and Hydroamination Reactions Manna, Kuntal; Ji, Pengfei; Greene, Francis X. Journal of the American Chemical Society, Vol. 138, Issue 24 https://doi.org/10.1021/jacs.6b03689	journal	June 2016
Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks Yuan, Shuai; Chen, Ying-Pin; Qin, Junsheng Angewandte Chemie International Edition, Vol. 54, Issue 49 https://doi.org/10.1002/anie.201505625	journal	October 2015
Stereochemistry of complex inorganic compounds. XXXV. Complex containing a ligand that spans trans positions Mochida, Isao; Mattern, J. Arthur; Bailar, John C. Journal of the American Chemical Society, Vol. 97, Issue 11 https://doi.org/10.1021/ja00844a017	journal	May 1975
Unique 2:1 Complex with a trans -Chelating Bis-Pyridine Ligand Hu, Yi-Zhen; Chamchoumis, Charles; Grebowicz, Janusz S. Inorganic Chemistry, Vol. 41, Issue 8 https://doi.org/10.1021/ic010965z	journal	March 2002
Synthesis and Properties of TRANSDIP, a Rigid Chelator Built upon a Cyclodextrin Cavity: Is TRANSDIP an Authentictrans-Spanning Ligand? Poorters, Laurent; Armspach, Dominique; Matt, Dominique Chemistry - A European Journal, Vol. 13, Issue 34 https://doi.org/10.1002/chem.200700831	journal	November 2007
A trans -bidentate bis-pyridinyl ligand with a transition metal hinge Vieira, Noah C.; Pienkos, Jared A.; McMillen, Colin D. Dalton Transactions, Vol. 46, Issue 44 https://doi.org/10.1039/C7DT03252H	journal	January 2017
CH₄ storage and CO₂ capture in highly porous zirconium oxide based metal–organic frameworks Yang, Qingyuan; Guillerm, Vincent; Ragon, Florence Chemical Communications, Vol. 48, Issue 79, p. 9831-9833 https://doi.org/10.1039/c2cc34714h	journal	January 2012
An azobenzene-containing metal–organic framework as an efficient heterogeneous catalyst for direct amidation of benzoic acids: synthesis of bioactive compounds Hoang, Linh T. M.; Ngo, Long H.; Nguyen, Ha L. Chemical Communications, Vol. 51, Issue 96 https://doi.org/10.1039/C5CC05985B	journal	January 2015
Amino acids as highly efficient modulators for single crystals of zirconium and hafnium metal–organic frameworks Marshall, Ross J.; Hobday, Claire L.; Murphie, Colin F. Journal of Materials Chemistry A, Vol. 4, Issue 18 https://doi.org/10.1039/C5TA10401G	journal	January 2016
Two highly porous single-crystalline zirconium-based metal-organic frameworks Gao, Wen-Yang; Thiounn, Timmy; Wojtas, Lukasz Science China Chemistry, Vol. 59, Issue 8 https://doi.org/10.1007/s11426-016-0071-8	journal	July 2016
Characterizing Defects in a UiO-AZB Metal–Organic Framework Epley, Charity C.; Love, Madeline D.; Morris, Amanda J. Inorganic Chemistry, Vol. 56, Issue 22 https://doi.org/10.1021/acs.inorgchem.7b01801	journal	November 2017
Construction of hierarchically porous metal–organic frameworks through linker labilization Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15356	journal	May 2017
Heterometallic In(III)–Pd(II) Porous Metal–Organic Framework with Square-Octahedron Topology Displaying High CO ₂ Uptake and Selectivity toward CH ₄ and N ₂ Bratsos, Ioannis; Tampaxis, Christos; Spanopoulos, Ioannis Inorganic Chemistry, Vol. 57, Issue 12 https://doi.org/10.1021/acs.inorgchem.8b00910	journal	June 2018
Programmable Topology in New Families of Heterobimetallic Metal–Organic Frameworks Muldoon, Patrick F.; Liu, Chong; Miller, Carson C. Journal of the American Chemical Society, Vol. 140, Issue 20 https://doi.org/10.1021/jacs.8b02192	journal	May 2018
MOF-Supported Selective Ethylene Dimerization Single-Site Catalysts through One-Pot Postsynthetic Modification Canivet, Jerome; Aguado, Sonia; Schuurman, Yves Journal of the American Chemical Society, Vol. 135, Issue 11 https://doi.org/10.1021/ja312120x	journal	March 2013
Gas-Phase Dimerization of Ethylene under Mild Conditions Catalyzed by MOF Materials Containing (bpy)Ni ^II Complexes Madrahimov, Sherzod T.; Gallagher, James R.; Zhang, Guanghui ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b01604	journal	October 2015

Cited By (4)

New linker installation in metal–organic frameworks Pang, Qingqing; Tu, Binbin; Li, Qiaowei Dalton Transactions, Vol. 48, Issue 32 https://doi.org/10.1039/c9dt02335f	journal	January 2019
A fivefold linker length reduction in an interpenetrated metal–organic framework via sequential solvent-assisted linker exchange Cao, Li-Hui; Liu, Xin; Tang, Xiao-Han Chemical Communications, Vol. 55, Issue 84 https://doi.org/10.1039/c9cc06739f	journal	January 2019
Metal‐Organic Frameworks as Platform for Lewis‐Acid‐Catalyzed Organic Transformations Yadav, Anand; Kanoo, Prakash Chemistry – An Asian Journal, Vol. 14, Issue 20 https://doi.org/10.1002/asia.201900876	journal	July 2019
Quest for 9-connected robust metal–organic framework platforms based on [M ₃ (O/OH)(COO) ₆ (pyridine) ₃ ] clusters as excellent gas separation and asymmetric supercapacitor materials Xue, Ying-Ying; Li, Shu-Ni; Jiang, Yu-Cheng Journal of Materials Chemistry A, Vol. 7, Issue 9 https://doi.org/10.1039/c8ta09080g	journal	January 2019

Linked Research (7)

Similar Records

Influence of Metal Identity on Light-Induced Switchable Adsorption in Azobenzene-Based Metal–Organic Frameworks

Journal Article · Tue Feb 22 00:00:00 EST 2022 · ACS Applied Materials and Interfaces · OSTI ID:1475583

Drake, Hannah F.; Xiao, Zhifeng; Day, Gregory S.; +8 more

The thermally induced decarboxylation mechanism of a mixed-oxidation state carboxylate-based iron metal–organic framework

Journal Article · Tue Sep 24 00:00:00 EDT 2019 · ChemComm · OSTI ID:1475583

Drake, Hannah F.; Day, Gregory S.; Vali, Shaik Waseem; +10 more

Photosensitizer‐Anchored 2D MOF Nanosheets as Highly Stable and Accessible Catalysts toward Artemisinin Production

Journal Article · Tue Apr 09 00:00:00 EDT 2019 · Advanced Science · OSTI ID:1475583

Wang, Ying; Feng, Liang; Pang, Jiandong; +12 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

CCDC 1841688: Experimental Crystal Structure Determination Yuan, Shuai; Zhang, Peng; Zhang, Liangliang https://doi.org/10.5517/ccdc.csd.cc1ztf9j The current record is supplemented by this dataset	dataset	June 2018
CCDC 1841692: Experimental Crystal Structure Determination: FIPHEU : dichloro-bis(dimethyl sulfoxide)-bis(pyridine-4-carboxylic acid)-nickel dimethyl sulfoxide solvate Yuan, Shuai; Zhang, Peng; Zhang, Liangliang https://doi.org/10.5517/ccdc.csd.cc1ztffn The current record is supplemented by this dataset	dataset	May 2018
CCDC 1841689: Experimental Crystal Structure Determination Yuan, Shuai; Zhang, Peng; Zhang, Liangliang https://doi.org/10.5517/ccdc.csd.cc1ztfbk The current record is supplemented by this dataset	dataset	June 2018
CCDC 1841690: Experimental Crystal Structure Determination: HAHFON01 : dichloro-bis[dimethyl sulfoxide]-bis(pyridine-4-carboxylic acid)-copper(ii) dimethyl sulfoxide solvate Yuan, Shuai; Zhang, Peng; Zhang, Liangliang https://doi.org/10.5517/ccdc.csd.cc1ztfcl The current record is supplemented by this dataset	dataset	May 2018
CCDC 1841691: Experimental Crystal Structure Determination: FINXUY : diaqua-dihydroxy-bis(pyridine-4-carboxylic acid)-copper Yuan, Shuai; Zhang, Peng; Zhang, Liangliang https://doi.org/10.5517/ccdc.csd.cc1ztfdm The current record is supplemented by this dataset	dataset	May 2018
CCDC 1841693: Experimental Crystal Structure Determination: FIPHIY : diaqua-bis(hydroxy)-bis(pyridine-4-carboxylic acid)-nickel Yuan, Shuai; Zhang, Peng; Zhang, Liangliang https://doi.org/10.5517/ccdc.csd.cc1ztfgp The current record is supplemented by this dataset	dataset	May 2018
CCDC 1841694: Experimental Crystal Structure Determination: FIPHOE : dichloro-bis(pyridine-4-carboxylic acid)-palladium dimethyl sulfoxide solvate Yuan, Shuai; Zhang, Peng; Zhang, Liangliang https://doi.org/10.5517/ccdc.csd.cc1ztfhq The current record is supplemented by this dataset	dataset	May 2018