Proton Conduction in Tröger’s Base-Linked Poly(crown ether)s
Abstract
Exactly 50 years ago, the ground-breaking discovery of dibenzo[18]crown-6 (DB18C6) by Charles Pedersen led to the use of DB18C6 as a receptor in supramolecular chemistry and a host in host–guest chemistry. We have demonstrated proton conductivity in Tröger’s base-linked polymers through hydrogen-bonded networks formed from adsorbed water molecules on the oxygen atoms of DB18C6 under humid conditions. Tröger’s base-linked polymers—poly(TBL-DB18C6)-t and poly(TBL-DB18C6)-c—synthesized by the in situ alkylation and cyclization of either trans- or cis-di(aminobenzo) [18]crown-6 at room temperature have been isolated as high-molecular-weight polymers. The macromolecular structures of the isomeric poly(TBL-DB18C6)s have been established by spectroscopic techniques and size-exclusion chromatography. The excellent solubility of these polymers in chloroform allows the formation of freestanding membranes, which are thermally stable and also show stability under aqueous conditions. The hydrophilic nature of the DB18C6 building blocks in the polymer facilitates retention of water as confirmed by water vapor adsorption isotherms, which show a 23 wt % water uptake. The adsorbed water is retained even after reducing the relative humidity to 25%. The proton conductivity of poly(TBL-DB18C6)-t, which is found to be 1.4 × 10–4 mS cm–1 in a humid environment, arises from the hydrogen bonding and the associated proton-hopping mechanism, as supported bymore »
- Authors:
-
- Department of Electrical Engineering, University of California Santa Cruz, Santa Cruz, California 95064, United States
- King Abdulaziz City for Science and Technology (KACST), Riyadh 11442, Saudi Arabia
- Publication Date:
- Research Org.:
- Northwestern Univ., Evanston, IL (United States); University of California, Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1460890
- Alternate Identifier(s):
- OSTI ID: 1508803
- Grant/Contract Number:
- FG02-08ER15967; AC02-05CH11231; 1648815
- Resource Type:
- Published Article
- Journal Name:
- ACS Applied Materials and Interfaces
- Additional Journal Information:
- Journal Name: ACS Applied Materials and Interfaces Journal Volume: 10 Journal Issue: 30; Journal ID: ISSN 1944-8244
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 42 ENGINEERING; fuel cell; membrane; poly(crown ether); proton conduction; Tröger’s base; water uptake
Citation Formats
Patel, Hasmukh A., Selberg, John, Salah, Dhafer, Chen, Haoyuan, Liao, Yijun, Mohan Nalluri, Siva Krishna, Farha, Omar K., Snurr, Randall Q., Rolandi, Marco, and Stoddart, J. Fraser. Proton Conduction in Tröger’s Base-Linked Poly(crown ether)s. United States: N. p., 2018.
Web. doi:10.1021/acsami.8b05532.
Patel, Hasmukh A., Selberg, John, Salah, Dhafer, Chen, Haoyuan, Liao, Yijun, Mohan Nalluri, Siva Krishna, Farha, Omar K., Snurr, Randall Q., Rolandi, Marco, & Stoddart, J. Fraser. Proton Conduction in Tröger’s Base-Linked Poly(crown ether)s. United States. https://doi.org/10.1021/acsami.8b05532
Patel, Hasmukh A., Selberg, John, Salah, Dhafer, Chen, Haoyuan, Liao, Yijun, Mohan Nalluri, Siva Krishna, Farha, Omar K., Snurr, Randall Q., Rolandi, Marco, and Stoddart, J. Fraser. Tue .
"Proton Conduction in Tröger’s Base-Linked Poly(crown ether)s". United States. https://doi.org/10.1021/acsami.8b05532.
@article{osti_1460890,
title = {Proton Conduction in Tröger’s Base-Linked Poly(crown ether)s},
author = {Patel, Hasmukh A. and Selberg, John and Salah, Dhafer and Chen, Haoyuan and Liao, Yijun and Mohan Nalluri, Siva Krishna and Farha, Omar K. and Snurr, Randall Q. and Rolandi, Marco and Stoddart, J. Fraser},
abstractNote = {Exactly 50 years ago, the ground-breaking discovery of dibenzo[18]crown-6 (DB18C6) by Charles Pedersen led to the use of DB18C6 as a receptor in supramolecular chemistry and a host in host–guest chemistry. We have demonstrated proton conductivity in Tröger’s base-linked polymers through hydrogen-bonded networks formed from adsorbed water molecules on the oxygen atoms of DB18C6 under humid conditions. Tröger’s base-linked polymers—poly(TBL-DB18C6)-t and poly(TBL-DB18C6)-c—synthesized by the in situ alkylation and cyclization of either trans- or cis-di(aminobenzo) [18]crown-6 at room temperature have been isolated as high-molecular-weight polymers. The macromolecular structures of the isomeric poly(TBL-DB18C6)s have been established by spectroscopic techniques and size-exclusion chromatography. The excellent solubility of these polymers in chloroform allows the formation of freestanding membranes, which are thermally stable and also show stability under aqueous conditions. The hydrophilic nature of the DB18C6 building blocks in the polymer facilitates retention of water as confirmed by water vapor adsorption isotherms, which show a 23 wt % water uptake. The adsorbed water is retained even after reducing the relative humidity to 25%. The proton conductivity of poly(TBL-DB18C6)-t, which is found to be 1.4 × 10–4 mS cm–1 in a humid environment, arises from the hydrogen bonding and the associated proton-hopping mechanism, as supported by a modeling study. In addition to proton conductivity, the Tröger’s base-linked polymers reported here promise a wide range of applications where the sub-nanometer-sized cavities of the crown ethers and the robust film-forming ability are the governing factors in dictating their properties.},
doi = {10.1021/acsami.8b05532},
journal = {ACS Applied Materials and Interfaces},
number = 30,
volume = 10,
place = {United States},
year = {Tue Jun 05 00:00:00 EDT 2018},
month = {Tue Jun 05 00:00:00 EDT 2018}
}
https://doi.org/10.1021/acsami.8b05532
Web of Science
Figures / Tables:
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