DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

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.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [3];  [4];  [1]; ORCiD logo [1];  [1];  [1];  [1];  [5];  [5]; ORCiD logo [2]; ORCiD logo [1]
  1. Texas A & M Univ., College Station, TX (United States)
  2. China Univ. of Petroleum (East China), Shandong (China)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Texas A&M Univ. at Qatar, Doha (Qatar)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Fossil Energy (FE)
OSTI Identifier:
1475583
Grant/Contract Number:  
A-0030; IIP-1632486; SC0001015; DGE-1252521; NPRP9-377-1-080; FE0026472
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 34; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

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, and Zhou, Hong -Cai. Exposed Equatorial Positions of Metal Centers via Sequential Ligand Elimination and Installation in MOFs. United States: N. p., 2018. Web. doi:10.1021/jacs.8b04886.
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. Exposed Equatorial Positions of Metal Centers via Sequential Ligand Elimination and Installation in MOFs. United States. https://doi.org/10.1021/jacs.8b04886
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, and Zhou, Hong -Cai. Wed . "Exposed Equatorial Positions of Metal Centers via Sequential Ligand Elimination and Installation in MOFs". United States. https://doi.org/10.1021/jacs.8b04886. https://www.osti.gov/servlets/purl/1475583.
@article{osti_1475583,
title = {Exposed Equatorial Positions of Metal Centers via Sequential Ligand Elimination and Installation in MOFs},
author = {Yuan, Shuai and Zhang, Peng and Zhang, Liangliang and Garcia-Esparza, Angel T. and Sokaras, Dimosthenis and Qin, Jun -Sheng and Feng, Liang and Day, Gregory S. and Chen, Wenmiao and Drake, Hannah F. and Elumalai, Palani and Madrahimov, Sherzod T. and Sun, Daofeng and Zhou, Hong -Cai},
abstractNote = {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.},
doi = {10.1021/jacs.8b04886},
journal = {Journal of the American Chemical Society},
number = 34,
volume = 140,
place = {United States},
year = {2018},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 14 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Design and synthesis of an exceptionally stable and highly porous metal-organic framework
journal, November 1999

  • Li, Hailian; Eddaoudi, Mohamed; M., O'Keeffe
  • Nature, Vol. 402, Issue 6759, p. 276-279
  • DOI: 10.1038/46248

Introduction to Metal–Organic Frameworks
journal, September 2011

  • Zhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M.
  • Chemical Reviews, Vol. 112, Issue 2, p. 673-674
  • DOI: 10.1021/cr300014x

The Chemistry and Applications of Metal-Organic Frameworks
journal, August 2013

  • Furukawa, H.; Cordova, K. E.; O'Keeffe, M.
  • Science, Vol. 341, Issue 6149, p. 1230444-1230444
  • DOI: 10.1126/science.1230444

Exceptional chemical and thermal stability of zeolitic imidazolate frameworks
journal, June 2006

  • Park, K. S.; Ni, Z.; Cote, A. P.
  • Proceedings of the National Academy of Sciences, Vol. 103, Issue 27, p. 10186-10191
  • DOI: 10.1073/pnas.0602439103

Secondary building units, nets and bonding in the chemistry of metal–organic frameworks
journal, January 2009

  • Tranchemontagne, David J.; Mendoza-Cortés, José L.; O’Keeffe, Michael
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1257-1283
  • DOI: 10.1039/b817735j

Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage
journal, January 2002

  • Eddaoudi, Mohamed; Kim, Jaheon; Rosi, Nathaniel
  • Science, Vol. 295, Issue 5554, p. 469-472
  • DOI: 10.1126/science.1067208

Hydrogen Storage in Microporous Metal-Organic Frameworks
journal, May 2003

  • Rosi, Nathaniel L.; Eckert, Juergen; Eddaoudi, Mohamed
  • Science, Vol. 300, Issue 5622, p. 1127-1129
  • DOI: 10.1126/science.1083440

Carbon Dioxide Capture in Metal–Organic Frameworks
journal, September 2011

  • Sumida, Kenji; Rogow, David L.; Mason, Jarad A.
  • Chemical Reviews, Vol. 112, Issue 2, p. 724-781
  • DOI: 10.1021/cr2003272

Destruction of chemical warfare agents using metal–organic frameworks
journal, March 2015

  • Mondloch, Joseph E.; Katz, Michael J.; Isley III, William C.
  • Nature Materials, Vol. 14, Issue 5
  • DOI: 10.1038/nmat4238

Very Large Breathing Effect in the First Nanoporous Chromium(III)-Based Solids MIL-53 or CrIII(OH)·{O2C−C6H4−CO2}·{HO2C−C6H4−CO2H}x·H2Oy
journal, November 2002

  • Serre, Christian; Millange, Franck; Thouvenot, Christelle
  • Journal of the American Chemical Society, Vol. 124, Issue 45, p. 13519-13526
  • DOI: 10.1021/ja0276974

Broadly Hysteretic H 2 Adsorption in the Microporous Metal−Organic Framework Co(1,4-benzenedipyrazolate)
journal, June 2008

  • Choi, Hye Jin; Dincă, Mircea; Long, Jeffrey R.
  • Journal of the American Chemical Society, Vol. 130, Issue 25
  • DOI: 10.1021/ja8024092

Cooperative insertion of CO2 in diamine-appended metal-organic frameworks
journal, March 2015

  • McDonald, Thomas M.; Mason, Jarad A.; Kong, Xueqian
  • Nature, Vol. 519, Issue 7543
  • DOI: 10.1038/nature14327

Methane storage in flexible metal–organic frameworks with intrinsic thermal management
journal, October 2015

  • Mason, Jarad A.; Oktawiec, Julia; Taylor, Mercedes K.
  • Nature, Vol. 527, Issue 7578
  • DOI: 10.1038/nature15732

A spin transition mechanism for cooperative adsorption in metal–organic frameworks
journal, September 2017

  • Reed, Douglas A.; Keitz, Benjamin K.; Oktawiec, Julia
  • Nature, Vol. 550, Issue 7674
  • DOI: 10.1038/nature23674

Postsynthetic Methods for the Functionalization of Metal–Organic Frameworks
journal, September 2011

  • Cohen, Seth M.
  • Chemical Reviews, Vol. 112, Issue 2, p. 970-1000
  • DOI: 10.1021/cr200179u

Cooperative Cluster Metalation and Ligand Migration in Zirconium Metal-Organic Frameworks
journal, October 2015

  • Yuan, Shuai; Chen, Ying-Pin; Qin, Junsheng
  • Angewandte Chemie International Edition, Vol. 54, Issue 49
  • DOI: 10.1002/anie.201505625

Stereochemistry of complex inorganic compounds. XXXV. Complex containing a ligand that spans trans positions
journal, May 1975

  • Mochida, Isao; Mattern, J. Arthur; Bailar, John C.
  • Journal of the American Chemical Society, Vol. 97, Issue 11
  • DOI: 10.1021/ja00844a017

Unique 2:1 Complex with a trans -Chelating Bis-Pyridine Ligand
journal, March 2002

  • Hu, Yi-Zhen; Chamchoumis, Charles; Grebowicz, Janusz S.
  • Inorganic Chemistry, Vol. 41, Issue 8
  • DOI: 10.1021/ic010965z

Synthesis and Properties of TRANSDIP, a Rigid Chelator Built upon a Cyclodextrin Cavity: Is TRANSDIP an Authentictrans-Spanning Ligand?
journal, November 2007

  • Poorters, Laurent; Armspach, Dominique; Matt, Dominique
  • Chemistry - A European Journal, Vol. 13, Issue 34
  • DOI: 10.1002/chem.200700831

Works referencing / citing this record:

The chemistry of multi-component and hierarchical framework compounds
journal, January 2019

  • Feng, Liang; Wang, Kun-Yu; Day, Gregory S.
  • Chemical Society Reviews, Vol. 48, Issue 18
  • DOI: 10.1039/c9cs00250b

New linker installation in metal–organic frameworks
journal, January 2019

  • Pang, Qingqing; Tu, Binbin; Li, Qiaowei
  • Dalton Transactions, Vol. 48, Issue 32
  • DOI: 10.1039/c9dt02335f

A fivefold linker length reduction in an interpenetrated metal–organic framework via sequential solvent-assisted linker exchange
journal, January 2019

  • Cao, Li-Hui; Liu, Xin; Tang, Xiao-Han
  • Chemical Communications, Vol. 55, Issue 84
  • DOI: 10.1039/c9cc06739f

Metal‐Organic Frameworks as Platform for Lewis‐Acid‐Catalyzed Organic Transformations
journal, July 2019