skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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:
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 = {2018},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Processing of giant graphene molecules by soft-landing mass spectrometry
journal, March 2006

  • Räder, Hans Joachim; Rouhanipour, Ali; Talarico, Anna Maria
  • Nature Materials, Vol. 5, Issue 4, p. 276-280
  • DOI: 10.1038/nmat1597

On the Oxidation of the Three-Dimensional Aromatics [B 12 X 12 ] 2− (X=F, Cl, Br, I)
journal, March 2014

  • Boeré, René T.; Derendorf, Janis; Jenne, Carsten
  • Chemistry - A European Journal, Vol. 20, Issue 15
  • DOI: 10.1002/chem.201304405

Electronic Structure Controls Reactivity of Size-Selected Pd Clusters Adsorbed on TiO2 Surfaces
journal, November 2009


Gas-assisted focused electron beam and ion beam processing and fabrication
journal, January 2008

  • Utke, Ivo; Hoffmann, Patrik; Melngailis, John
  • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 26, Issue 4
  • DOI: 10.1116/1.2955728

Pressure Dependence of the Contact Angle
journal, June 2007

  • Wu, Jiyu; Farouk, T.; Ward, C. A.
  • The Journal of Physical Chemistry B, Vol. 111, Issue 22
  • DOI: 10.1021/jp071372y

Catalysis by clusters with precise numbers of atoms
journal, July 2015


Wetting and spreading
journal, May 2009


Bombardment induced ion transport – part IV: ionic conductivity of ultra-thin polyelectrolyte multilayer films
journal, January 2016

  • Wesp, Veronika; Hermann, Matthias; Schäfer, Martin
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 6
  • DOI: 10.1039/C5CP04004C

Electronic Structure and Stability of [B 12 X 12 ] 2– (X = F–At): A Combined Photoelectron Spectroscopic and Theoretical Study
journal, October 2017

  • Warneke, Jonas; Hou, Gao-Lei; Aprà, Edoardo
  • Journal of the American Chemical Society, Vol. 139, Issue 41
  • DOI: 10.1021/jacs.7b08598

Charge retention of soft-landed phosphotungstate Keggin anions on self-assembled monolayers
journal, January 2016

  • Gunaratne, K. Don D.; Prabhakaran, Venkateshkumar; Andersen, Amity
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 13
  • DOI: 10.1039/C5CP06954H

Helical Peptide Arrays on Self-Assembled Monolayer Surfaces through Soft and Reactive Landing of Mass-Selected Ions
journal, August 2008

  • Wang, Peng; Laskin, Julia
  • Angewandte Chemie International Edition, Vol. 47, Issue 35, p. 6678-6680
  • DOI: 10.1002/anie.200801366

Surface Chemistry for Molecular Layer Deposition of Organic and Hybrid Organic−Inorganic Polymers
journal, April 2009

  • George, Steven M.; Yoon, Byunghoon; Dameron, Arrelaine A.
  • Accounts of Chemical Research, Vol. 42, Issue 4
  • DOI: 10.1021/ar800105q

Anisotropic spinodal dewetting as a route to self-assembly of patterned surfaces
journal, March 2000

  • Higgins, A. M.; Jones, R. A. L.
  • Nature, Vol. 404, Issue 6777
  • DOI: 10.1038/35006597

A soft-landing experiment on organometallic cluster ions: infrared spectroscopy of V(benzene)2 in Ar matrix
journal, February 2001


Synthesis, Crystal Structure, and Reactivity of the Strong Methylating Agent Me2B12Cl12
journal, April 2010

  • Bolli, Christoph; Derendorf, Janis; Keßler, Mathias
  • Angewandte Chemie International Edition, Vol. 49, Issue 20
  • DOI: 10.1002/anie.200906627

Evidence for an intrinsic binding force between dodecaborate dianions and receptors with hydrophobic binding pockets
journal, January 2016

  • Warneke, Jonas; Jenne, Carsten; Bernarding, Johannes
  • Chemical Communications, Vol. 52, Issue 37
  • DOI: 10.1039/C6CC01233G

Applications of dewetting in micro and nanotechnology
journal, January 2012

  • Gentili, Denis; Foschi, Giulia; Valle, Francesco
  • Chemical Society Reviews, Vol. 41, Issue 12
  • DOI: 10.1039/c2cs35040h

Electrowetting: from basics to applications
journal, July 2005


Charge Retention by Gold Clusters on Surfaces Prepared Using Soft Landing of Mass Selected Ions
journal, December 2011

  • Johnson, Grant E.; Priest, Thomas; Laskin, Julia
  • ACS Nano, Vol. 6, Issue 1
  • DOI: 10.1021/nn2039565

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018

Microwave-Assisted Iodination: Synthesis of Heavily Iodinated 10-Vertex and 12-Vertex Boron Clusters
journal, July 2015

  • Juhasz, Marcus A.; Matheson, Graham R.; Chang, Paul S.
  • Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, Vol. 46, Issue 4
  • DOI: 10.1080/15533174.2014.988819

Self-Assembly at All Scales
journal, March 2002

  • Whitesides, George M.; Grzybowski, Bartosz
  • Science, Vol. 295, Issue 5564, p. 2418-2421
  • DOI: 10.1126/science.1070821

Preparing Protein Microarrays by Soft-Landing of Mass-Selected Ions
journal, September 2003


Electrospray Ion Beam Deposition: Soft-Landing and Fragmentation of Functional Molecules at Solid Surfaces
journal, September 2009

  • Rauschenbach, Stephan; Vogelgesang, Ralf; Malinowski, N.
  • ACS Nano, Vol. 3, Issue 10
  • DOI: 10.1021/nn900022p

In situ Studies of Soft- and Reactive Landing of Mass-Selected Ions Using Infrared Reflection Absorption Spectroscopy
journal, September 2009

  • Hu, Qichi; Wang, Peng; Gassman, Paul L.
  • Analytical Chemistry, Vol. 81, Issue 17
  • DOI: 10.1021/ac901149s

Dewetting of conducting polymer inkjet droplets on patterned surfaces
journal, February 2004

  • Wang, J. Z.; Zheng, Z. H.; Li, H. W.
  • Nature Materials, Vol. 3, Issue 3, p. 171-176
  • DOI: 10.1038/nmat1073

Templated dewetting: designing entirely self-organized platforms for photocatalysis
journal, January 2016

  • Altomare, Marco; Nguyen, Nhat Truong; Schmuki, Patrik
  • Chemical Science, Vol. 7, Issue 12
  • DOI: 10.1039/C6SC02555B

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

Cluster–surface interaction: From soft landing to implantation
journal, October 2011


A hydrodynamically optimized nano-electrospray ionization source and vacuum interface
journal, January 2014


Chemistry of Boranes. IX. Halogenation of B 10 H 10 -2 and B 12 H 12 -2
journal, February 1964

  • Knoth, W. H.; Miller, H. C.; Sauer, J. C.
  • Inorganic Chemistry, Vol. 3, Issue 2
  • DOI: 10.1021/ic50012a002

Theory of Metal Surfaces: Induced Surface Charge and Image Potential
journal, April 1973


Controlling the Charge State and Redox Properties of Supported Polyoxometalates via Soft Landing of Mass-Selected Ions
journal, October 2014

  • Gunaratne, K. Don D.; Johnson, Grant E.; Andersen, Amity
  • The Journal of Physical Chemistry C, Vol. 118, Issue 48
  • DOI: 10.1021/jp505050m

Long-Range Repulsive Interaction between Molecules on a Metal Surface Induced by Charge Transfer
journal, October 2007


Design and performance of a high-flux electrospray ionization source for ion soft landing
journal, January 2015

  • Gunaratne, K. Don D.; Prabhakaran, Venkateshkumar; Ibrahim, Yehia M.
  • The Analyst, Vol. 140, Issue 9
  • DOI: 10.1039/C5AN00220F

Plasticizer contamination from vacuum system o-rings in a quadrupole ion trap mass spectrometer
journal, August 2002


Charging Effects on Bonding and Catalyzed Oxidation of CO on Au8 Clusters on MgO
journal, January 2005

  • Yoon, Bokwon; Häkkinen, Hannu; Landman, Uzi
  • Science, Vol. 307, Issue 5708, p. 403-407
  • DOI: 10.1126/science.1104168

Active Conformation Control of Unfolded Proteins by Hyperthermal Collision with a Metal Surface
journal, September 2014

  • Rinke, Gordon; Rauschenbach, Stephan; Harnau, Ludger
  • Nano Letters, Vol. 14, Issue 10
  • DOI: 10.1021/nl502122j

Activating technology of SnO2 layers by metal particles from ultrathin metal films
journal, October 1993


Thin Film Instability Induced by Long-Range Forces
journal, March 1999

  • Reiter, Günter; Sharma, Ashutosh; Casoli, Alain
  • Langmuir, Vol. 15, Issue 7
  • DOI: 10.1021/la981470y

A combined discrete/continuum solvation model: Application to glycine
journal, July 2000

  • Bandyopadhyay, Pradipta; Gordon, Mark S.
  • The Journal of Chemical Physics, Vol. 113, Issue 3
  • DOI: 10.1063/1.481889

Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999

  • Adamo, Carlo; Barone, Vincenzo
  • The Journal of Chemical Physics, Vol. 110, Issue 13
  • DOI: 10.1063/1.478522

Engineering atomic and molecular nanostructures at surfaces
journal, September 2005

  • Barth, Johannes V.; Costantini, Giovanni; Kern, Klaus
  • Nature, Vol. 437, Issue 7059
  • DOI: 10.1038/nature04166

Toward Self-Organization and Complex Matter
journal, March 2002


Fundamental aspects of catalysis on supported metal clusters
journal, January 2004

  • Heiz, U.; Bullock, E. L.
  • Journal of Materials Chemistry, Vol. 14, Issue 4
  • DOI: 10.1039/b313560h

Water Structure Recovery in Chaotropic Anion Recognition: High-Affinity Binding of Dodecaborate Clusters to γ-Cyclodextrin
journal, May 2015

  • Assaf, Khaleel I.; Ural, Merve S.; Pan, Fangfang
  • Angewandte Chemie International Edition, Vol. 54, Issue 23
  • DOI: 10.1002/anie.201412485

Catalysis Applications of Size-Selected Cluster Deposition
journal, November 2015


Functional Liquid-Crystalline Assemblies: Self-Organized Soft Materials
journal, January 2006

  • Kato, Takashi; Mizoshita, Norihiro; Kishimoto, Kenji
  • Angewandte Chemie International Edition, Vol. 45, Issue 1
  • DOI: 10.1002/anie.200501384

Mass-Selective Soft-Landing of Protein Assemblies with Controlled Landing Energies
journal, July 2014

  • Mikhailov, Victor A.; Mize, Todd H.; Benesch, Justin L. P.
  • Analytical Chemistry, Vol. 86, Issue 16
  • DOI: 10.1021/ac5018327

Bombardment induced ion transport—Part II. Experimental potassium ion conductivities in borosilicate glass
journal, January 2011

  • Menezes, P. V.; Martin, J.; Schäfer, M.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 45
  • DOI: 10.1039/c1cp21216h

Interaction of B 12 F 12 2– with All- cis 1,2,3,4,5,6 Hexafluorocyclohexane in the Gas Phase
journal, December 2016

  • Lecours, Michael J.; Marta, Rick A.; Steinmetz, Vincent
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 1
  • DOI: 10.1021/acs.jpclett.6b02629

A Close Look at Proteins: Submolecular Resolution of Two- and Three-Dimensionally Folded Cytochrome c at Surfaces
journal, April 2012

  • Deng, Zhitao; Thontasen, Nicha; Malinowski, Nikola
  • Nano Letters, Vol. 12, Issue 5
  • DOI: 10.1021/nl3005385

Coverage-Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-Selected Ions
journal, November 2012

  • Johnson, Grant E.; Priest, Thomas; Laskin, Julia
  • The Journal of Physical Chemistry C, Vol. 116, Issue 47, p. 24977-24986
  • DOI: 10.1021/jp308795r

Nanofluidics: what is it and what can we expect from it?
journal, April 2005


Anomalous Coarsening Driven by Reversible Charge Transfer at Metal–Organic Interfaces
journal, November 2014

  • Della Pia, Ada; Riello, Massimo; Floris, Andrea
  • ACS Nano, Vol. 8, Issue 12
  • DOI: 10.1021/nn505063w

Hard and Soft Acids and Bases
journal, November 1963

  • Pearson, Ralph G.
  • Journal of the American Chemical Society, Vol. 85, Issue 22
  • DOI: 10.1021/ja00905a001

Soft- and reactive landing of ions onto surfaces: Concepts and applications: CONCEPTS AND APPLICATIONS
journal, April 2015

  • Johnson, Grant E.; Gunaratne, Don; Laskin, Julia
  • Mass Spectrometry Reviews, Vol. 35, Issue 3
  • DOI: 10.1002/mas.21451

Direct Perfluorination of K 2 B 12 H 12 in Acetonitrile Occurs at the Gas Bubble−Solution Interface and Is Inhibited by HF. Experimental and DFT Study of Inhibition by Protic Acids and Soft, Polarizable Anions
journal, December 2009

  • Peryshkov, Dmitry V.; Popov, Alexey A.; Strauss, Steven H.
  • Journal of the American Chemical Society, Vol. 131, Issue 51
  • DOI: 10.1021/ja9069437

Rational design of efficient electrode–electrolyte interfaces for solid-state energy storage using ion soft landing
journal, April 2016

  • Prabhakaran, Venkateshkumar; Mehdi, B. Layla; Ditto, Jeffrey J.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11399

Dewetting Patterns and Molecular Forces: A Reconciliation
journal, June 2001


Influence of Cluster–Support Interactions on Reactivity of Size-Selected Nb x O y Clusters
journal, April 2015

  • Nakayama, Miki; Xue, Meng; An, Wei
  • The Journal of Physical Chemistry C, Vol. 119, Issue 26
  • DOI: 10.1021/acs.jpcc.5b00691

Soft landing of ions as a means of surface modification
journal, January 1977

  • Franchetti, V.; Solka, B. H.; Baitinger, W. E.
  • International Journal of Mass Spectrometry and Ion Physics, Vol. 23, Issue 1
  • DOI: 10.1016/0020-7381(77)80004-1

Note: Proof of principle of a new type of cluster beam source with potential for scale-up
journal, April 2016

  • Palmer, R. E.; Cao, L.; Yin, F.
  • Review of Scientific Instruments, Vol. 87, Issue 4
  • DOI: 10.1063/1.4947229

Control of chemical reactions and synthesis by low-energy electrons
journal, January 2013

  • Böhler, Esther; Warneke, Jonas; Swiderek, Petra
  • Chemical Society Reviews, Vol. 42, Issue 24
  • DOI: 10.1039/c3cs60180c

Solid-State Dewetting of Thin Films
journal, August 2012


Soft Landing of Complex Molecules on Surfaces
journal, July 2011


Synthesis and characterization of synthetically useful salts of the weakly-coordinating dianion [B12Cl12]2−
journal, January 2009

  • Geis, Vanessa; Guttsche, Kristin; Knapp, Carsten
  • Dalton Transactions, Issue 15
  • DOI: 10.1039/b821030f