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Title: 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, asmore » 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.« less

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [4];  [4]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [4]
  1. Northwestern Univ., Evanston, IL (United States); Aramco Research Center-Houston, Houston, TX (United States)
  2. Univ. of California, Santa Cruz, CA (United States)
  3. King Abdulaziz City for Science and Technology (KACST), Riyadh (Saudi Arabia)
  4. Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States); Univ. of California, Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1460890
Alternate Identifier(s):
OSTI ID: 1508803
Grant/Contract Number:  
AC02-05CH11231; 1648815; FG02-08ER15967
Resource Type:
Published Article
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 30; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
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. 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, and Stoddart, J. Fraser. Tue . "Proton Conduction in Tröger’s Base-Linked Poly(crown ether)s". United States. doi: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 = {2018},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acsami.8b05532

Citation Metrics:
Cited by: 3 works
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Figures / Tables:

Figure 1. Figure 1.: Synthesis of trans-di(nitrobenzo)[18]crown-6, trans-di(aminobenzo)[18]crown-6, and poly(TBL-DB18C6)-t. See Supporting Information for the synthetic details. A film (inset) was obtained by the slow evaporation of a solution of poly(TBL-DB18C6)-t (200 mg) in CHCl3 (10 mL) from a Petri dish at room temperature overnight, followed by drying at 80 °C formore » 5 h. The dried film in the Petri dish was soaked in deionized water for 1 h and peeled off to obtain a freestanding membrane.« less

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Works referencing / citing this record:

Adjustable chiral self-sorting and self-discriminating behaviour between diamond-like Tröger's base-linked cryptands
journal, January 2019

  • Chen, Yuan; Qian, Cheng; Zhao, Qian
  • Chemical Communications, Vol. 55, Issue 56
  • DOI: 10.1039/c9cc03577j

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.