skip to main content

DOE PAGESDOE PAGES

Title: Retrosynthesis of multi–component metal-organic frameworks

Crystal engineering of metal–organic frameworks (MOFs) has allowed the construction of complex structures at atomic precision, but has yet to reach the same level of sophistication as organic synthesis. The synthesis of complex MOFs with multiple organic and/or inorganic components is ultimately limited by the lack of control over framework assembly in one-pot reactions. Herein, we demonstrate that multi-component MOFs with unprecedented complexity can be constructed in a predictable and stepwise manner under simple kinetic guidance, which conceptually mimics the retrosynthetic approach utilized to construct complicated organic molecules. Four multi-component MOFs were synthesized by the subsequent incorporation of organic linkers and inorganic clusters into the cavity of a mesoporous MOF, each composed of up to three different metals and two different linkers. Furthermore, we demonstrated the utility of such a retrosynthetic design through the construction of a cooperative bimetallic catalytic system with two collaborative metal sites for three-component Strecker reactions.
Authors:
 [1] ;  [1] ;  [1] ; ORCiD logo [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1] ; ORCiD logo [2] ; ORCiD logo [3] ;  [1] ; ORCiD logo [4]
  1. Texas A & M Univ., College Station, TX (United States)
  2. Shandong Univ., Jinan (China)
  3. King Saud Univ., Riyadh (Saudi Arabia)
  4. Texas A & M Univ., College Station, TX (United States); King Saud Univ., Riyadh (Saudi Arabia)
Publication Date:
Grant/Contract Number:
SC0001015
Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Research Org:
Energy Frontier Research Centers (EFRC), Washington, D.C. (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)
OSTI Identifier:
1470209

Yuan, Shuai, Qin, Jun-Sheng, Li, Jialuo, Huang, Lan, Feng, Liang, Fang, Yu, Lollar, Christina, Pang, Jiandong, Zhang, Liangliang, Sun, Di, Alsalme, Ali, Cagin, Tahir, and Zhou, Hong-Cai. Retrosynthesis of multi–component metal-organic frameworks. United States: N. p., Web. doi:10.1038/s41467-018-03102-5.
Yuan, Shuai, Qin, Jun-Sheng, Li, Jialuo, Huang, Lan, Feng, Liang, Fang, Yu, Lollar, Christina, Pang, Jiandong, Zhang, Liangliang, Sun, Di, Alsalme, Ali, Cagin, Tahir, & Zhou, Hong-Cai. Retrosynthesis of multi–component metal-organic frameworks. United States. doi:10.1038/s41467-018-03102-5.
Yuan, Shuai, Qin, Jun-Sheng, Li, Jialuo, Huang, Lan, Feng, Liang, Fang, Yu, Lollar, Christina, Pang, Jiandong, Zhang, Liangliang, Sun, Di, Alsalme, Ali, Cagin, Tahir, and Zhou, Hong-Cai. 2018. "Retrosynthesis of multi–component metal-organic frameworks". United States. doi:10.1038/s41467-018-03102-5. https://www.osti.gov/servlets/purl/1470209.
@article{osti_1470209,
title = {Retrosynthesis of multi–component metal-organic frameworks},
author = {Yuan, Shuai and Qin, Jun-Sheng and Li, Jialuo and Huang, Lan and Feng, Liang and Fang, Yu and Lollar, Christina and Pang, Jiandong and Zhang, Liangliang and Sun, Di and Alsalme, Ali and Cagin, Tahir and Zhou, Hong-Cai},
abstractNote = {Crystal engineering of metal–organic frameworks (MOFs) has allowed the construction of complex structures at atomic precision, but has yet to reach the same level of sophistication as organic synthesis. The synthesis of complex MOFs with multiple organic and/or inorganic components is ultimately limited by the lack of control over framework assembly in one-pot reactions. Herein, we demonstrate that multi-component MOFs with unprecedented complexity can be constructed in a predictable and stepwise manner under simple kinetic guidance, which conceptually mimics the retrosynthetic approach utilized to construct complicated organic molecules. Four multi-component MOFs were synthesized by the subsequent incorporation of organic linkers and inorganic clusters into the cavity of a mesoporous MOF, each composed of up to three different metals and two different linkers. Furthermore, we demonstrated the utility of such a retrosynthetic design through the construction of a cooperative bimetallic catalytic system with two collaborative metal sites for three-component Strecker reactions.},
doi = {10.1038/s41467-018-03102-5},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {2}
}

Works referenced in this record:

The Reticular Chemistry Structure Resource (RCSR) Database of, and Symbols for, Crystal Nets
journal, December 2008
  • O’Keeffe, Michael; Peskov, Maxim A.; Ramsden, Stuart J.
  • Accounts of Chemical Research, Vol. 41, Issue 12, p. 1782-1789
  • DOI: 10.1021/ar800124u

Ultrahigh Porosity in Metal-Organic Frameworks
journal, July 2010

Metal–organic framework materials as catalysts
journal, January 2009
  • Lee, JeongYong; Farha, Omar K.; Roberts, John
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1450-1459
  • DOI: 10.1039/b807080f

Reticular synthesis and the design of new materials
journal, June 2003
  • Yaghi, Omar M.; O'Keeffe, Michael; Ockwig, Nathan W.
  • Nature, Vol. 423, Issue 6941, p. 705-714
  • DOI: 10.1038/nature01650

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

Selective gas adsorption and separation in metal–organic frameworks
journal, January 2009
  • Li, Jian-Rong; Kuppler, Ryan J.; Zhou, Hong-Cai
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1477-1504
  • DOI: 10.1039/b802426j

Enantioselective catalysis with homochiral metal–organic frameworks
journal, January 2009
  • Ma, Liqing; Abney, Carter; Lin, Wenbin
  • Chemical Society Reviews, Vol. 38, Issue 5, p. 1248-1256
  • DOI: 10.1039/b807083k

Vapor-Phase Metalation by Atomic Layer Deposition in a Metal–Organic Framework
journal, May 2013
  • Mondloch, Joseph E.; Bury, Wojciech; Fairen-Jimenez, David
  • Journal of the American Chemical Society, Vol. 135, Issue 28, p. 10294-10297
  • DOI: 10.1021/ja4050828

Multiple Functional Groups of Varying Ratios in Metal-Organic Frameworks
journal, February 2010

Perfluoroalkane Functionalization of NU-1000 via Solvent-Assisted Ligand Incorporation: Synthesis and CO2 Adsorption Studies
journal, October 2013
  • Deria, Pravas; Mondloch, Joseph E.; Tylianakis, Emmanuel
  • Journal of the American Chemical Society, Vol. 135, Issue 45, p. 16801-16804
  • DOI: 10.1021/ja408959g

Synthesis and Characterization of Metal–Organic Framework-74 Containing 2, 4, 6, 8, and 10 Different Metals
journal, May 2014
  • Wang, Lisa J.; Deng, Hexiang; Furukawa, Hiroyasu
  • Inorganic Chemistry, Vol. 53, Issue 12, p. 5881-5883
  • DOI: 10.1021/ic500434a

High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO2 Capture
journal, February 2008

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

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

A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area
journal, September 2005
  • Ferey, G.; Mellot-Draznieks, C.; Serre, C.
  • Science, Vol. 309, Issue 5743, p. 2040-2042
  • DOI: 10.1126/science.1116275

Engineering Metal Organic Frameworks for Heterogeneous Catalysis
journal, August 2010
  • Corma, A.; García, H.; Llabrés i Xamena, F. X.
  • Chemical Reviews, Vol. 110, Issue 8, p. 4606-4655
  • DOI: 10.1021/cr9003924

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

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