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

Title: A Tale of Two Trimers from Two Different Worlds: A COF-Inspired Synthetic Strategy for Pore-Space Partitioning of MOFs

Abstract

The introduction of a symmetry- and size-matching pore-partitioning agent in the form of either a molecular ligand, such as 2,4,6-tri(4-pyridinyl)-1,3,5-triazine (tpt), or a metal-complex cluster, into the hexagonal channels of MIL-88/MOF-235-type (the acs net) to create pacs-type (partitioned acs) crystalline porous materials is an effective strategy to develop high-performance gas adsorbents. We have developed here an integrated COF–MOF coassembly strategy as a new method for pore-space partitioning through the coassembly of [(M3(OH)1-x(O)x(COO)6] MOF-type and [B3O3(py)3] COF-type trimers. With this strategy, the coordination-driven assembly of the acs framework occurred concurrently and synergistically with the COF-1-type condensation of pyridine-4-boronic acid into a C3-symmetric trimeric boroxine molecule. Furthermore, the resulting boroxine-based pacs materials exhibited dramatically enhanced gas-sorption properties as compared to nonpartitioned acs-type materials and are among the most efficient NH3-sorption materials

Authors:
 [1];  [1];  [2];  [2];  [3];  [3];  [4]; ORCiD logo [1]
  1. Univ. of California, Riverside, CA (United States)
  2. California State Univ. (CalState), Long Beach, CA (United States)
  3. Univ. of California, Riverside, CA (United States); Taiyuan Univ. of Technology (China)
  4. Taiyuan Univ. of Technology (China)
Publication Date:
Research Org.:
Univ. of California, Riverside, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1596459
Alternate Identifier(s):
OSTI ID: 1504511
Grant/Contract Number:  
SC0010596
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 19; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; boronic acids; covalent organic frameworks; materials science; metal–organic frameworks; pore-space partitioning

Citation Formats

Wang, Yanxiang, Zhao, Xiang, Yang, Huajun, Bu, Xianhui, Wang, Yong, Jia, Xiaoxia, Li, Jinping, and Feng, Pingyun. A Tale of Two Trimers from Two Different Worlds: A COF-Inspired Synthetic Strategy for Pore-Space Partitioning of MOFs. United States: N. p., 2019. Web. doi:10.1002/anie.201901343.
Wang, Yanxiang, Zhao, Xiang, Yang, Huajun, Bu, Xianhui, Wang, Yong, Jia, Xiaoxia, Li, Jinping, & Feng, Pingyun. A Tale of Two Trimers from Two Different Worlds: A COF-Inspired Synthetic Strategy for Pore-Space Partitioning of MOFs. United States. https://doi.org/10.1002/anie.201901343
Wang, Yanxiang, Zhao, Xiang, Yang, Huajun, Bu, Xianhui, Wang, Yong, Jia, Xiaoxia, Li, Jinping, and Feng, Pingyun. Tue . "A Tale of Two Trimers from Two Different Worlds: A COF-Inspired Synthetic Strategy for Pore-Space Partitioning of MOFs". United States. https://doi.org/10.1002/anie.201901343. https://www.osti.gov/servlets/purl/1596459.
@article{osti_1596459,
title = {A Tale of Two Trimers from Two Different Worlds: A COF-Inspired Synthetic Strategy for Pore-Space Partitioning of MOFs},
author = {Wang, Yanxiang and Zhao, Xiang and Yang, Huajun and Bu, Xianhui and Wang, Yong and Jia, Xiaoxia and Li, Jinping and Feng, Pingyun},
abstractNote = {The introduction of a symmetry- and size-matching pore-partitioning agent in the form of either a molecular ligand, such as 2,4,6-tri(4-pyridinyl)-1,3,5-triazine (tpt), or a metal-complex cluster, into the hexagonal channels of MIL-88/MOF-235-type (the acs net) to create pacs-type (partitioned acs) crystalline porous materials is an effective strategy to develop high-performance gas adsorbents. We have developed here an integrated COF–MOF coassembly strategy as a new method for pore-space partitioning through the coassembly of [(M3(OH)1-x(O)x(COO)6] MOF-type and [B3O3(py)3] COF-type trimers. With this strategy, the coordination-driven assembly of the acs framework occurred concurrently and synergistically with the COF-1-type condensation of pyridine-4-boronic acid into a C3-symmetric trimeric boroxine molecule. Furthermore, the resulting boroxine-based pacs materials exhibited dramatically enhanced gas-sorption properties as compared to nonpartitioned acs-type materials and are among the most efficient NH3-sorption materials},
doi = {10.1002/anie.201901343},
journal = {Angewandte Chemie (International Edition)},
number = 19,
volume = 58,
place = {United States},
year = {2019},
month = {4}
}

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

Citation Metrics:
Cited by: 9 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

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

Gas Storage in Nanoporous Materials
journal, June 2008

  • Morris, Russell E.; Wheatley, Paul S.
  • Angewandte Chemie International Edition, Vol. 47, Issue 27
  • DOI: 10.1002/anie.200703934

Gasspeicherung in nanoporösen Materialien
journal, June 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

Tuning MOF CO 2 Adsorption Properties via Cation Exchange
journal, April 2010

  • An, Jihyun; Rosi, Nathaniel L.
  • Journal of the American Chemical Society, Vol. 132, Issue 16
  • DOI: 10.1021/ja1012992

Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic–hydrophobic metal–organic framework
journal, March 2011

  • Mohideen, M. Infas H.; Xiao, Bo; Wheatley, Paul S.
  • Nature Chemistry, Vol. 3, Issue 4
  • DOI: 10.1038/nchem.1003

Bimetallic Metal–Organic Frameworks for Gas Storage and Separation
journal, March 2017


Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene
journal, May 2016


Ethane/ethylene separation in a metal-organic framework with iron-peroxo sites
journal, October 2018


In Situ Modification of Metal-Organic Frameworks in Mixed-Matrix Membranes
journal, June 2015

  • Denny, Michael S.; Cohen, Seth M.
  • Angewandte Chemie International Edition, Vol. 54, Issue 31
  • DOI: 10.1002/anie.201504077

In Situ Modification of Metal-Organic Frameworks in Mixed-Matrix Membranes
journal, June 2015


Engineering chiral porous metal-organic frameworks for enantioselective adsorption and separation
journal, July 2014

  • Peng, Yongwu; Gong, Tengfei; Zhang, Kang
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5406

Liquid-phase epitaxial growth of a homochiral MOF thin film on poly( l -DOPA) functionalized substrate for improved enantiomer separation
journal, January 2016

  • Gu, Zhi-Gang; Fu, Wen-Qiang; Wu, Xin
  • Chemical Communications, Vol. 52, Issue 4
  • DOI: 10.1039/C5CC07614E

Water-Soluble and Ultrastable Ti 4 L 6 Tetrahedron with Coordination Assembly Function
journal, November 2017

  • He, Yan-Ping; Yuan, Lv-Bing; Chen, Guang-Hui
  • Journal of the American Chemical Society, Vol. 139, Issue 46
  • DOI: 10.1021/jacs.7b09463

Metal-Organic Frameworks for Separation
journal, March 2018

  • Zhao, Xiang; Wang, Yanxiang; Li, Dong-Sheng
  • Advanced Materials, Vol. 30, Issue 37
  • DOI: 10.1002/adma.201705189

Metal-Organic Frameworks as Platforms for Catalytic Applications
journal, November 2017


Metalation of a Thiocatechol-Functionalized Zr(IV)-Based Metal–Organic Framework for Selective C–H Functionalization
journal, February 2015

  • Fei, Honghan; Cohen, Seth M.
  • Journal of the American Chemical Society, Vol. 137, Issue 6
  • DOI: 10.1021/ja5126885

A Metal-Organic Framework with Exceptional Activity for C−H Bond Amination
journal, December 2017

  • Wang, Le; Agnew, Douglas W.; Yu, Xiao
  • Angewandte Chemie International Edition, Vol. 57, Issue 2
  • DOI: 10.1002/anie.201709420

A Metal-Organic Framework with Exceptional Activity for C−H Bond Amination
journal, December 2017


Exploring the Performance Improvement of the Oxygen Evolution Reaction in a Stable Bimetal-Organic Framework System
journal, May 2018

  • Wang, Xiao-Li; Dong, Long-Zhang; Qiao, Man
  • Angewandte Chemie International Edition, Vol. 57, Issue 31
  • DOI: 10.1002/anie.201803587

Exploring the Performance Improvement of the Oxygen Evolution Reaction in a Stable Bimetal-Organic Framework System
journal, May 2018

  • Wang, Xiao-Li; Dong, Long-Zhang; Qiao, Man
  • Angewandte Chemie, Vol. 130, Issue 31
  • DOI: 10.1002/ange.201803587

Creating Well-Defined Hexabenzocoronene in Zirconium Metal–Organic Framework by Postsynthetic Annulation
journal, January 2019

  • Qin, Jun-Sheng; Yuan, Shuai; Zhang, Lei
  • Journal of the American Chemical Society, Vol. 141, Issue 5
  • DOI: 10.1021/jacs.8b11042

Photocatalytic Metal–Organic Frameworks for Selective 2,2,2-Trifluoroethylation of Styrenes
journal, September 2016

  • Yu, Xiao; Cohen, Seth M.
  • Journal of the American Chemical Society, Vol. 138, Issue 38
  • DOI: 10.1021/jacs.6b06859

Rational Design of MOF/COF Hybrid Materials for Photocatalytic H 2 Evolution in the Presence of Sacrificial Electron Donors
journal, August 2018

  • Zhang, Feng-Ming; Sheng, Jing-Li; Yang, Zhao-Di
  • Angewandte Chemie International Edition, Vol. 57, Issue 37
  • DOI: 10.1002/anie.201806862

Rational Design of MOF/COF Hybrid Materials for Photocatalytic H 2 Evolution in the Presence of Sacrificial Electron Donors
journal, August 2018

  • Zhang, Feng-Ming; Sheng, Jing-Li; Yang, Zhao-Di
  • Angewandte Chemie, Vol. 130, Issue 37
  • DOI: 10.1002/ange.201806862

Acid and Base Resistant Zirconium Polyphenolate-Metalloporphyrin Scaffolds for Efficient CO 2 Photoreduction
journal, November 2017


Hierarchical Porous and High Surface Area Tubular Carbon as Dye Adsorbent and Capacitor Electrode
journal, May 2015

  • Chen, Long; Ji, Tuo; Brisbin, Logan
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 22
  • DOI: 10.1021/acsami.5b02697

Pore Space Partition in Metal–Organic Frameworks
journal, January 2017


An ultra-tunable platform for molecular engineering of high-performance crystalline porous materials
journal, December 2016

  • Zhai, Quan-Guo; Bu, Xianhui; Mao, Chengyu
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms13645

A Route to the Synthesis of Trivalent Transition-Metal Porous Carboxylates with Trimeric Secondary Building Units
journal, September 2004

  • Serre, Christian; Millange, Franck; Surblé, Suzy
  • Angewandte Chemie International Edition, Vol. 43, Issue 46
  • DOI: 10.1002/anie.200454250

A Route to the Synthesis of Trivalent Transition-Metal Porous Carboxylates with Trimeric Secondary Building Units
journal, September 2004

  • Serre, Christian; Millange, Franck; Surblé, Suzy
  • Angewandte Chemie, Vol. 116, Issue 46
  • DOI: 10.1002/ange.200454250

Metal-Organic Frameworks Based on Trigonal Prismatic Building Blocks and the New “acs” Topology
journal, May 2005

  • Sudik, Andrea C.; Côté, Adrien P.; Yaghi, Omar M.
  • Inorganic Chemistry, Vol. 44, Issue 9, p. 2998-3000
  • DOI: 10.1021/ic050064g

Entrapment of Metal Clusters in Metal–Organic Framework Channels by Extended Hooks Anchored at Open Metal Sites
journal, May 2013

  • Zheng, Shou-Tian; Zhao, Xiang; Lau, Samuel
  • Journal of the American Chemical Society, Vol. 135, Issue 28
  • DOI: 10.1021/ja4044642

Multivariable Modular Design of Pore Space Partition
journal, November 2016

  • Zhao, Xiang; Bu, Xianhui; Nguyen, Edward T.
  • Journal of the American Chemical Society, Vol. 138, Issue 46
  • DOI: 10.1021/jacs.6b07901

Pore Space Partition by Symmetry-Matching Regulated Ligand Insertion and Dramatic Tuning on Carbon Dioxide Uptake
journal, January 2015

  • Zhao, Xiang; Bu, Xianhui; Zhai, Quan-Guo
  • Journal of the American Chemical Society, Vol. 137, Issue 4
  • DOI: 10.1021/ja512137t

Coordination templated [2+2+2] cyclotrimerization in a porous coordination framework
journal, September 2015

  • Wei, Yong-Sheng; Zhang, Mei; Liao, Pei-Qin
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9348

Chemistry of Covalent Organic Frameworks
journal, November 2015


Covalent organic frameworks (COFs): from design to applications
journal, January 2013


Recent progress in covalent organic framework thin films: fabrications, applications and perspectives
journal, January 2019

  • Wang, Han; Zeng, Zhuotong; Xu, Piao
  • Chemical Society Reviews, Vol. 48, Issue 2
  • DOI: 10.1039/C8CS00376A

Porous, Crystalline, Covalent Organic Frameworks
journal, November 2005

  • Côté, Adrien P.; Benin, Annabelle I.; Ockwig, Nathan W.
  • Science, Vol. 310, Issue 5751, p. 1166-1170
  • DOI: 10.1126/science.1120411

Reticular Synthesis of Microporous and Mesoporous 2D Covalent Organic Frameworks
journal, October 2007

  • Côté, Adrien P.; El-Kaderi, Hani M.; Furukawa, Hiroyasu
  • Journal of the American Chemical Society, Vol. 129, Issue 43, p. 12914-12915
  • DOI: 10.1021/ja0751781

Designed Synthesis of 3D Covalent Organic Frameworks
journal, April 2007

  • El-Kaderi, Hani M.; Hunt, Joseph R.; Mendoza-Cortes, Jose L.
  • Science, Vol. 316, Issue 5822, p. 268-272
  • DOI: 10.1126/science.1139915

Boronic acid building blocks: tools for self assembly
journal, January 2011

  • Nishiyabu, Ryuhei; Kubo, Yuji; James, Tony D.
  • Chem. Commun., Vol. 47, Issue 4
  • DOI: 10.1039/C0CC02921A

Boroxine chemistry and applications: A perspective
journal, January 2010

  • Korich, Andrew L.; Iovine, Peter M.
  • Dalton Trans., Vol. 39, Issue 6
  • DOI: 10.1039/B917043J

A Crystalline Imine-Linked 3-D Porous Covalent Organic Framework
journal, April 2009

  • Uribe-Romo, Fernando J.; Hunt, Joseph R.; Furukawa, Hiroyasu
  • Journal of the American Chemical Society, Vol. 131, Issue 13, p. 4570-4571
  • DOI: 10.1021/ja8096256

3D Microporous Base-Functionalized Covalent Organic Frameworks for Size-Selective Catalysis
journal, February 2014

  • Fang, Qianrong; Gu, Shuang; Zheng, Jie
  • Angewandte Chemie International Edition, Vol. 53, Issue 11
  • DOI: 10.1002/anie.201310500

3D Microporous Base-Functionalized Covalent Organic Frameworks for Size-Selective Catalysis
journal, February 2014


Construction of Crystalline 2D Covalent Organic Frameworks with Remarkable Chemical (Acid/Base) Stability via a Combined Reversible and Irreversible Route
journal, November 2012

  • Kandambeth, Sharath; Mallick, Arijit; Lukose, Binit
  • Journal of the American Chemical Society, Vol. 134, Issue 48
  • DOI: 10.1021/ja308278w

A hydrazone-based covalent organic framework for photocatalytic hydrogen production
journal, January 2014

  • Stegbauer, Linus; Schwinghammer, Katharina; Lotsch, Bettina V.
  • Chem. Sci., Vol. 5, Issue 7
  • DOI: 10.1039/C4SC00016A

Porous, Covalent Triazine-Based Frameworks Prepared by Ionothermal Synthesis
journal, April 2008

  • Kuhn, Pierre; Antonietti, Markus; Thomas, Arne
  • Angewandte Chemie International Edition, Vol. 47, Issue 18
  • DOI: 10.1002/anie.200705710

Ionothermalsynthese von porösen kovalenten Triazin- Polymernetzwerken
journal, April 2008

  • Kuhn, Pierre; Antonietti, Markus; Thomas, Arne
  • Angewandte Chemie, Vol. 120, Issue 18
  • DOI: 10.1002/ange.200705710

An Azine-Linked Covalent Organic Framework
journal, November 2013

  • Dalapati, Sasanka; Jin, Shangbin; Gao, Jia
  • Journal of the American Chemical Society, Vol. 135, Issue 46
  • DOI: 10.1021/ja4103293

Targeted Synthesis of a Porous Aromatic Framework with High Stability and Exceptionally High Surface Area
journal, November 2009

  • Ben, Teng; Ren, Hao; Ma, Shengqian
  • Angewandte Chemie International Edition, Vol. 48, Issue 50, p. 9457-9460
  • DOI: 10.1002/anie.200904637

Targeted Synthesis of a Porous Aromatic Framework with High Stability and Exceptionally High Surface Area
journal, November 2009


Designed synthesis of large-pore crystalline polyimide covalent organic frameworks
journal, July 2014

  • Fang, Qianrong; Zhuang, Zhongbin; Gu, Shuang
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5503

Targeted synthesis of a porous borazine-linked covalent organic framework
journal, January 2012

  • Jackson, Karl T.; Reich, Thomas E.; El-Kaderi, Hani M.
  • Chemical Communications, Vol. 48, Issue 70
  • DOI: 10.1039/c2cc33583b

Porous Solids Arising from Synergistic and Competing Modes of Assembly: Combining Coordination Chemistry and Covalent Bond Formation
journal, February 2015

  • Dutta, Ananya; Koh, Kyoungmoo; Wong-Foy, Antek G.
  • Angewandte Chemie International Edition, Vol. 54, Issue 13
  • DOI: 10.1002/anie.201411735

Porous Solids Arising from Synergistic and Competing Modes of Assembly: Combining Coordination Chemistry and Covalent Bond Formation
journal, February 2015

  • Dutta, Ananya; Koh, Kyoungmoo; Wong-Foy, Antek G.
  • Angewandte Chemie, Vol. 127, Issue 13
  • DOI: 10.1002/ange.201411735

A new strategy for constructing a disulfide-functionalized ZIF-8 analogue using structure-directing ligand–ligand covalent interaction
journal, January 2018

  • Gai, Yanli; Chen, Xitong; Yang, Huajun
  • Chemical Communications, Vol. 54, Issue 85
  • DOI: 10.1039/C8CC07064D

Porphyrinic coordination lattices with fluoropillars
journal, January 2017

  • Lin, Qipu; Mao, Chengyu; Kong, Aiguo
  • J. Mater. Chem. A, Vol. 5, Issue 40
  • DOI: 10.1039/C7TA06658A

Very Large Swelling in Hybrid Frameworks:  A Combined Computational and Powder Diffraction Study
journal, November 2005

  • Mellot-Draznieks, Caroline; Serre, Christian; Surblé, Suzy
  • Journal of the American Chemical Society, Vol. 127, Issue 46
  • DOI: 10.1021/ja054900x

Site Partition: Turning One Site into Two for Adsorbing CO 2
journal, June 2016


Ammonia Storage by Reversible Host-Guest Site Exchange in a Robust Metal-Organic Framework
journal, October 2018

  • Godfrey, Harry G. W.; da Silva, Ivan; Briggs, Lydia
  • Angewandte Chemie International Edition, Vol. 57, Issue 45
  • DOI: 10.1002/anie.201808316

Ammonia Storage by Reversible Host-Guest Site Exchange in a Robust Metal-Organic Framework
journal, October 2018

  • Godfrey, Harry G. W.; da Silva, Ivan; Briggs, Lydia
  • Angewandte Chemie, Vol. 130, Issue 45
  • DOI: 10.1002/ange.201808316

Controlled Gas Uptake in Metal–Organic Frameworks with Record Ammonia Sorption
journal, February 2018

  • Rieth, Adam J.; Dincă, Mircea
  • Journal of the American Chemical Society, Vol. 140, Issue 9
  • DOI: 10.1021/jacs.8b00313

Works referencing / citing this record:

A Dual Threat: Redox‐Activity and Electronic Structures of Well‐Defined Donor–Acceptor Fulleretic Covalent‐Organic Materials
journal, February 2020

  • Leith, Gabrielle A.; Rice, Allison M.; Yarbrough, Brandon J.
  • Angewandte Chemie International Edition, Vol. 59, Issue 15
  • DOI: 10.1002/anie.201914233

Adjustment of the performance and stability of isostructural zeolitic tetrazolate-imidazolate frameworks
journal, January 2020

  • Li, Hai-Zhen; Du, Dong-Ying; Sun, Yayong
  • Dalton Transactions, Vol. 49, Issue 15
  • DOI: 10.1039/d0dt00791a

A Dual Threat: Redox‐Activity and Electronic Structures of Well‐Defined Donor–Acceptor Fulleretic Covalent‐Organic Materials
journal, February 2020

  • Leith, Gabrielle A.; Rice, Allison M.; Yarbrough, Brandon J.
  • Angewandte Chemie, Vol. 132, Issue 15
  • DOI: 10.1002/ange.201914233