Structure of the Polymer Backbones in polyMOF Materials
Abstract
The molecular connectivity of polymer–metal–organic framework (polyMOF) hybrid materials was investigated using density functional theory calculations and solid-state NMR spectroscopy. The architectural constraints that dictate the formation of polyMOFs were assessed by examining poly(1,4-benzenedicarboxylic acid) (pbdc) polymers in two archetypical MOF lattices (UiO-66 and IRMOF-1). Modeling of the polyMOFs showed that in the IRMOF-1-type lattice, six, seven, and eight methylene (–CH2–) groups between 1,4-benzenedicarboxylate (terephthalate, bdc2–) units can be accommodated without significant distortions, while in the UiO-66-type lattice, an optimal spacing of seven methylene groups between bdc2– units is needed to minimize strain. Solid-state NMR supports these predictions and reveals pronounced spectral differences for the same polymer in the two polyMOF lattices. With seven methylene groups, polyUiO-66-7a shows 7 ± 3% of uncoordinated terephthalate linkers, while these are undetectable (<4%) in the corresponding polyIRMOF-1-7a. Additionally, NMR-detected backbone mobility is significantly higher in the polyIRMOF-1-7a than in the corresponding polyUiO-66-7a, again indicative of taut chains in the latter.
- Authors:
-
[1];
[3];
[2];
- Univ. Montpellier (France)
- Brandeis Univ., Waltham, MA (United States)
- Univ. of California, San Diego, La Jolla, CA (United States)
- Publication Date:
- Research Org.:
- Univ. of California, San Diego, La Jolla, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Science Foundation (NSF)
- OSTI Identifier:
- 1779734
- Grant/Contract Number:
- FG02-08ER46519; ECCS-1542148
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 142; Journal Issue: 24; 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; Chemical structure; Lattices; Materials; Polymers; Metal organic frameworks
Citation Formats
Mileo, Paulo G. M., Yuan, Shichen, Ayala, Sergio, Duan, Pu, Semino, Rocio, Cohen, Seth M., Schmidt-Rohr, Klaus, and Maurin, Guillaume. Structure of the Polymer Backbones in polyMOF Materials. United States: N. p., 2020.
Web. doi:10.1021/jacs.0c04546.
Mileo, Paulo G. M., Yuan, Shichen, Ayala, Sergio, Duan, Pu, Semino, Rocio, Cohen, Seth M., Schmidt-Rohr, Klaus, & Maurin, Guillaume. Structure of the Polymer Backbones in polyMOF Materials. United States. https://doi.org/10.1021/jacs.0c04546
Mileo, Paulo G. M., Yuan, Shichen, Ayala, Sergio, Duan, Pu, Semino, Rocio, Cohen, Seth M., Schmidt-Rohr, Klaus, and Maurin, Guillaume. Mon .
"Structure of the Polymer Backbones in polyMOF Materials". United States. https://doi.org/10.1021/jacs.0c04546. https://www.osti.gov/servlets/purl/1779734.
@article{osti_1779734,
title = {Structure of the Polymer Backbones in polyMOF Materials},
author = {Mileo, Paulo G. M. and Yuan, Shichen and Ayala, Sergio and Duan, Pu and Semino, Rocio and Cohen, Seth M. and Schmidt-Rohr, Klaus and Maurin, Guillaume},
abstractNote = {The molecular connectivity of polymer–metal–organic framework (polyMOF) hybrid materials was investigated using density functional theory calculations and solid-state NMR spectroscopy. The architectural constraints that dictate the formation of polyMOFs were assessed by examining poly(1,4-benzenedicarboxylic acid) (pbdc) polymers in two archetypical MOF lattices (UiO-66 and IRMOF-1). Modeling of the polyMOFs showed that in the IRMOF-1-type lattice, six, seven, and eight methylene (–CH2–) groups between 1,4-benzenedicarboxylate (terephthalate, bdc2–) units can be accommodated without significant distortions, while in the UiO-66-type lattice, an optimal spacing of seven methylene groups between bdc2– units is needed to minimize strain. Solid-state NMR supports these predictions and reveals pronounced spectral differences for the same polymer in the two polyMOF lattices. With seven methylene groups, polyUiO-66-7a shows 7 ± 3% of uncoordinated terephthalate linkers, while these are undetectable (<4%) in the corresponding polyIRMOF-1-7a. Additionally, NMR-detected backbone mobility is significantly higher in the polyIRMOF-1-7a than in the corresponding polyUiO-66-7a, again indicative of taut chains in the latter.},
doi = {10.1021/jacs.0c04546},
journal = {Journal of the American Chemical Society},
number = 24,
volume = 142,
place = {United States},
year = {Mon May 25 00:00:00 EDT 2020},
month = {Mon May 25 00:00:00 EDT 2020}
}
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