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Title: Self-organizing layers from complex molecular anions

Abstract

The formation of traditional ionic materials occurs principally via joint accumulation of both anions and cations. Here in this paper, we describe a previously unreported phenomenon by which macroscopic liquid-like thin layers with tunable self-organization properties form through accumulation of stable complex ions of one polarity on surfaces. Using a series of highly stable molecular anions we demonstrate a strong influence of the internal charge distribution of the molecular ions, which is usually shielded by counterions, on the properties of the layers. Detailed characterization reveals that the intrinsically unstable layers of anions on surfaces are stabilized by simultaneous accumulation of neutral molecules from the background environment. Different phases, self-organization mechanisms and optical properties are observed depending on the molecular properties of the deposited anions, the underlying surface and the coadsorbed neutral molecules. This demonstrates rational control of the macroscopic properties (morphology and size of the formed structures) of the newly discovered anion-based layers.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3];  [1];  [4]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
  3. Bergische Univ. Wuppertal, Wuppertal (Germany). Fakultat fur Mathematik und Naturwissenschaften, Anorganische Chemie
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division; Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); Alexander von Humboldt Foundation
OSTI Identifier:
1438251
Report Number(s):
PNNL-SA-128240
Journal ID: ISSN 2041-1723; PII: 4228
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Warneke, Jonas, McBriarty, Martin E., Riechers, Shawn L., China, Swarup, Engelhard, Mark H., Apra, Edoardo, Young, Robert P., Washton, Nancy M., Jenne, Carsten, Johnson, Grant E., and Laskin, Julia. Self-organizing layers from complex molecular anions. United States: N. p., 2018. Web. doi:10.1038/s41467-018-04228-2.
Warneke, Jonas, McBriarty, Martin E., Riechers, Shawn L., China, Swarup, Engelhard, Mark H., Apra, Edoardo, Young, Robert P., Washton, Nancy M., Jenne, Carsten, Johnson, Grant E., & Laskin, Julia. Self-organizing layers from complex molecular anions. United States. doi:10.1038/s41467-018-04228-2.
Warneke, Jonas, McBriarty, Martin E., Riechers, Shawn L., China, Swarup, Engelhard, Mark H., Apra, Edoardo, Young, Robert P., Washton, Nancy M., Jenne, Carsten, Johnson, Grant E., and Laskin, Julia. Mon . "Self-organizing layers from complex molecular anions". United States. doi:10.1038/s41467-018-04228-2. https://www.osti.gov/servlets/purl/1438251.
@article{osti_1438251,
title = {Self-organizing layers from complex molecular anions},
author = {Warneke, Jonas and McBriarty, Martin E. and Riechers, Shawn L. and China, Swarup and Engelhard, Mark H. and Apra, Edoardo and Young, Robert P. and Washton, Nancy M. and Jenne, Carsten and Johnson, Grant E. and Laskin, Julia},
abstractNote = {The formation of traditional ionic materials occurs principally via joint accumulation of both anions and cations. Here in this paper, we describe a previously unreported phenomenon by which macroscopic liquid-like thin layers with tunable self-organization properties form through accumulation of stable complex ions of one polarity on surfaces. Using a series of highly stable molecular anions we demonstrate a strong influence of the internal charge distribution of the molecular ions, which is usually shielded by counterions, on the properties of the layers. Detailed characterization reveals that the intrinsically unstable layers of anions on surfaces are stabilized by simultaneous accumulation of neutral molecules from the background environment. Different phases, self-organization mechanisms and optical properties are observed depending on the molecular properties of the deposited anions, the underlying surface and the coadsorbed neutral molecules. This demonstrates rational control of the macroscopic properties (morphology and size of the formed structures) of the newly discovered anion-based layers.},
doi = {10.1038/s41467-018-04228-2},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {Mon May 14 00:00:00 EDT 2018},
month = {Mon May 14 00:00:00 EDT 2018}
}

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