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Title: 3D Covalent Organic Frameworks of Interlocking 1D Square Ribbons

Abstract

A new mode of mechanical entanglement in extended structures is described where 1D organic ribbons of corner-sharing squares are mutually interlocked to form 3D woven covalent organic framework-500, COF-500. Reaction of aldehyde-functionalized tetrahedral Cu(PDB) 2PO 2Ph 2 complexes (PDB = 4,4'-(1,10-phenanthroline-2,9-diyl)dibenzaldehyde) with rectangular tetratopic ETTBA (4',4''',4''''',4'''''''-(ethene-1,1,2,2-tetrayl)tetrakis([1,1'-biphenyl]-4-amine)) linkers through imine condensation, yielded a crystalline porous metalated COF, COF-500-Cu, with pts topology. Upon removal of the Cu(I) ions, the individual 1D square ribbons in the demetalated form (COF-500) are held together only by mechanical interlocking of rings, which allows their collective movement to produce a narrow-pore form, as evidenced by nitrogen adsorption and solid-state photoluminescence studies. When exposed to tetrahydrofuran vapor, the interlocking ribbons can dynamically move away from each other to reopen up the structure. Finally, the structural integrity of COF-500 is maintained during its dynamics because the constituent square ribbons cannot part company due to spatial confinement imparted by their interlocking nature.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [1];  [3];  [4];  [4]; ORCiD logo [5]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Shanghai Tech Univ., Shanghai (China)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. King Abdulaziz City for Science and Technology, Riyadh (Saudi Arabia)
  5. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); King Abdulaziz City for Science and Technology, Riyadh (Saudi Arabia)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1580351
Grant/Contract Number:  
[AC02-05CH11231; 21875140]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
[ Journal Volume: 141; Journal Issue: 1]; 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; crystal structure; ions; chemical structure; transmission electron microscopy macrocyles

Citation Formats

Liu, Yuzhong, Diercks, Christian S., Ma, Yanhang, Lyu, Hao, Zhu, Chenhui, Alshmimri, Sultan A., Alshihri, Saeed, and Yaghi, Omar M. 3D Covalent Organic Frameworks of Interlocking 1D Square Ribbons. United States: N. p., 2018. Web. doi:10.1021/jacs.8b12177.
Liu, Yuzhong, Diercks, Christian S., Ma, Yanhang, Lyu, Hao, Zhu, Chenhui, Alshmimri, Sultan A., Alshihri, Saeed, & Yaghi, Omar M. 3D Covalent Organic Frameworks of Interlocking 1D Square Ribbons. United States. doi:10.1021/jacs.8b12177.
Liu, Yuzhong, Diercks, Christian S., Ma, Yanhang, Lyu, Hao, Zhu, Chenhui, Alshmimri, Sultan A., Alshihri, Saeed, and Yaghi, Omar M. Tue . "3D Covalent Organic Frameworks of Interlocking 1D Square Ribbons". United States. doi:10.1021/jacs.8b12177. https://www.osti.gov/servlets/purl/1580351.
@article{osti_1580351,
title = {3D Covalent Organic Frameworks of Interlocking 1D Square Ribbons},
author = {Liu, Yuzhong and Diercks, Christian S. and Ma, Yanhang and Lyu, Hao and Zhu, Chenhui and Alshmimri, Sultan A. and Alshihri, Saeed and Yaghi, Omar M.},
abstractNote = {A new mode of mechanical entanglement in extended structures is described where 1D organic ribbons of corner-sharing squares are mutually interlocked to form 3D woven covalent organic framework-500, COF-500. Reaction of aldehyde-functionalized tetrahedral Cu(PDB)2PO2Ph2 complexes (PDB = 4,4'-(1,10-phenanthroline-2,9-diyl)dibenzaldehyde) with rectangular tetratopic ETTBA (4',4''',4''''',4'''''''-(ethene-1,1,2,2-tetrayl)tetrakis([1,1'-biphenyl]-4-amine)) linkers through imine condensation, yielded a crystalline porous metalated COF, COF-500-Cu, with pts topology. Upon removal of the Cu(I) ions, the individual 1D square ribbons in the demetalated form (COF-500) are held together only by mechanical interlocking of rings, which allows their collective movement to produce a narrow-pore form, as evidenced by nitrogen adsorption and solid-state photoluminescence studies. When exposed to tetrahydrofuran vapor, the interlocking ribbons can dynamically move away from each other to reopen up the structure. Finally, the structural integrity of COF-500 is maintained during its dynamics because the constituent square ribbons cannot part company due to spatial confinement imparted by their interlocking nature.},
doi = {10.1021/jacs.8b12177},
journal = {Journal of the American Chemical Society},
number = [1],
volume = [141],
place = {United States},
year = {2018},
month = {12}
}

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Works referencing / citing this record:

Squaramide-decorated covalent organic framework as a new platform for biomimetic hydrogen-bonding organocatalysis
journal, January 2019

  • Li, Xia; Wang, Zhifang; Sun, Jiaxing
  • Chemical Communications, Vol. 55, Issue 38
  • DOI: 10.1039/c9cc01317b