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Title: Inside polyMOFs: layered structures in polymer-based metal–organic frameworks

Abstract

In this report, we explore the internal structural features of polyMOFs consisting of equal mass ratios of metal-coordinating poly(benzenedicarboxylic acid) blocks and non-coordinating poly(ethylene glycol) (PEG) blocks. The studies reveal alternating lamellae of metal-rich, crystalline regions and metal-deficient non-crystalline polymer, which span the length of hundreds of nanometers. Polymers consisting of random PEG blocks, PEG end-blocks, or non-coordinating poly(cyclooctadiene) (COD) show similar alternation of metal-rich and metal-deficient regions, indicating a universal self-assembly mechanism. A variety of techniques were employed to interrogate the internal structure of the polyMOFs, including transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and small-angle synchrotron X-ray scattering (SAXS). Independent of the copolymer architecture or composition, the internal structure of the polyMOF crystals showed similar lamellar self-assembly at single-nanometer length scales.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Chemistry and Biochemistry, University of California, La Jolla, USA
  2. Departments of Chemistry, Materials Science & Engineering, Biomedical Engineering, Pharmacology, International Institute for Nanotechnology, Simpson-Querrey Institute, Chemistry of Life Processes Institute, Lurie Cancer Center
Publication Date:
Research Org.:
Univ. of California, San Diego, CA (United States); Univ. of California, San Diego, La Jolla, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1664532
Alternate Identifier(s):
OSTI ID: 1684624; OSTI ID: 1779733; OSTI ID: 1784044
Grant/Contract Number:  
FG02-08ER46519; SC0003844
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 38; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Bentz, Kyle C., Gnanasekaran, Karthikeyan, Bailey, Jake B., Ayala, Sergio, Tezcan, F. Akif, Gianneschi, Nathan C., and Cohen, Seth M. Inside polyMOFs: layered structures in polymer-based metal–organic frameworks. United Kingdom: N. p., 2020. Web. https://doi.org/10.1039/D0SC03651J.
Bentz, Kyle C., Gnanasekaran, Karthikeyan, Bailey, Jake B., Ayala, Sergio, Tezcan, F. Akif, Gianneschi, Nathan C., & Cohen, Seth M. Inside polyMOFs: layered structures in polymer-based metal–organic frameworks. United Kingdom. https://doi.org/10.1039/D0SC03651J
Bentz, Kyle C., Gnanasekaran, Karthikeyan, Bailey, Jake B., Ayala, Sergio, Tezcan, F. Akif, Gianneschi, Nathan C., and Cohen, Seth M. Wed . "Inside polyMOFs: layered structures in polymer-based metal–organic frameworks". United Kingdom. https://doi.org/10.1039/D0SC03651J.
@article{osti_1664532,
title = {Inside polyMOFs: layered structures in polymer-based metal–organic frameworks},
author = {Bentz, Kyle C. and Gnanasekaran, Karthikeyan and Bailey, Jake B. and Ayala, Sergio and Tezcan, F. Akif and Gianneschi, Nathan C. and Cohen, Seth M.},
abstractNote = {In this report, we explore the internal structural features of polyMOFs consisting of equal mass ratios of metal-coordinating poly(benzenedicarboxylic acid) blocks and non-coordinating poly(ethylene glycol) (PEG) blocks. The studies reveal alternating lamellae of metal-rich, crystalline regions and metal-deficient non-crystalline polymer, which span the length of hundreds of nanometers. Polymers consisting of random PEG blocks, PEG end-blocks, or non-coordinating poly(cyclooctadiene) (COD) show similar alternation of metal-rich and metal-deficient regions, indicating a universal self-assembly mechanism. A variety of techniques were employed to interrogate the internal structure of the polyMOFs, including transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and small-angle synchrotron X-ray scattering (SAXS). Independent of the copolymer architecture or composition, the internal structure of the polyMOF crystals showed similar lamellar self-assembly at single-nanometer length scales.},
doi = {10.1039/D0SC03651J},
journal = {Chemical Science},
number = 38,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/D0SC03651J

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