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Title: Supramolecular architectures of molecularly thin yet robust free-standing layers

Abstract

Stable, single-nanometer thin, and free-standing two-dimensional layers with controlled molecular architectures are desired for several applications ranging from (opto-)electronic devices to nanoparticle and single-biomolecule characterization. It is, however, challenging to construct these stable single molecular layers via self-assembly, as the cohesion of those systems is ensured only by in-plane bonds. We herein demonstrate that relatively weak noncovalent bonds of limited directionality such as dipole-dipole (–CN NC–) interactions act in a synergistic fashion to stabilize crystalline monomolecular layers of tetrafunctional calixarenes. The monolayers produced, demonstrated to be free-standing, display a well-defined atomic structure on the single-nanometer scale and are robust under a wide range of conditions including photon and electron radiation. This work opens up new avenues for the fabrication of robust, single-component, and free-standing layers via bottom-up self-assembly.

Authors:
 [1]; ORCiD logo [2];  [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [7];  [8]; ORCiD logo [7]; ORCiD logo [9]; ORCiD logo [10]; ORCiD logo [11]; ORCiD logo [7];  [3]; ORCiD logo [7];  [3]
  1. Univ. of Applied Sciences and Arts Northwestern Switzerland (Switzerland); Paul Scherrer Inst. (Switzerland). Lab. for Micro- and Nano-technology
  2. Paul Scherrer Inst. (Switzerland). Lab. for Micro- and Nano-technology; Univ. of Basel (Switzerland). Center for Cellular Imaging and NanoAnalytics
  3. Univ. of Applied Sciences and Arts Northwestern Switzerland (Switzerland)
  4. Empa–Swiss Federal Labs for Materials Science and Technology, Dübendorf (Switzerland)
  5. Heriot-Watt Univ., Edinburgh (Scotland). Inst. of Chemical Sciences
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  7. Paul Scherrer Inst. (Switzerland). Lab. for Micro- and Nano-technology
  8. Univ. of Basel (Switzerland)
  9. Paul Scherrer Inst., (Switzerland). Swiss Light Source
  10. Univ. of Basel (Switzerland). Center for Cellular Imaging and NanoAnalytics
  11. Univ. of Basel (Switzerland); Paul Scherrer Inst., Villigen (Switzerland). and Lab. of Biomolecular Research; Leiden Univ. (Netherlands). Inst. of Biology Leiden
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1572801
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 5; Journal Issue: 2; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Moradi, Mina, Opara, Nadia L., Tulli, Ludovico G., Wäckerlin, Christian, Dalgarno, Scott J., Teat, Simon J., Baljozovic, Milos, Popova, Olha, van Genderen, Eric, Kleibert, Armin, Stahlberg, Henning, Abrahams, Jan Pieter, Padeste, Celestino, Corvini, Philippe F. -X., Jung, Thomas A., and Shahgaldian, Patrick. Supramolecular architectures of molecularly thin yet robust free-standing layers. United States: N. p., 2019. Web. doi:10.1126/sciadv.aav4489.
Moradi, Mina, Opara, Nadia L., Tulli, Ludovico G., Wäckerlin, Christian, Dalgarno, Scott J., Teat, Simon J., Baljozovic, Milos, Popova, Olha, van Genderen, Eric, Kleibert, Armin, Stahlberg, Henning, Abrahams, Jan Pieter, Padeste, Celestino, Corvini, Philippe F. -X., Jung, Thomas A., & Shahgaldian, Patrick. Supramolecular architectures of molecularly thin yet robust free-standing layers. United States. doi:10.1126/sciadv.aav4489.
Moradi, Mina, Opara, Nadia L., Tulli, Ludovico G., Wäckerlin, Christian, Dalgarno, Scott J., Teat, Simon J., Baljozovic, Milos, Popova, Olha, van Genderen, Eric, Kleibert, Armin, Stahlberg, Henning, Abrahams, Jan Pieter, Padeste, Celestino, Corvini, Philippe F. -X., Jung, Thomas A., and Shahgaldian, Patrick. Fri . "Supramolecular architectures of molecularly thin yet robust free-standing layers". United States. doi:10.1126/sciadv.aav4489. https://www.osti.gov/servlets/purl/1572801.
@article{osti_1572801,
title = {Supramolecular architectures of molecularly thin yet robust free-standing layers},
author = {Moradi, Mina and Opara, Nadia L. and Tulli, Ludovico G. and Wäckerlin, Christian and Dalgarno, Scott J. and Teat, Simon J. and Baljozovic, Milos and Popova, Olha and van Genderen, Eric and Kleibert, Armin and Stahlberg, Henning and Abrahams, Jan Pieter and Padeste, Celestino and Corvini, Philippe F. -X. and Jung, Thomas A. and Shahgaldian, Patrick},
abstractNote = {Stable, single-nanometer thin, and free-standing two-dimensional layers with controlled molecular architectures are desired for several applications ranging from (opto-)electronic devices to nanoparticle and single-biomolecule characterization. It is, however, challenging to construct these stable single molecular layers via self-assembly, as the cohesion of those systems is ensured only by in-plane bonds. We herein demonstrate that relatively weak noncovalent bonds of limited directionality such as dipole-dipole (–CN…NC–) interactions act in a synergistic fashion to stabilize crystalline monomolecular layers of tetrafunctional calixarenes. The monolayers produced, demonstrated to be free-standing, display a well-defined atomic structure on the single-nanometer scale and are robust under a wide range of conditions including photon and electron radiation. This work opens up new avenues for the fabrication of robust, single-component, and free-standing layers via bottom-up self-assembly.},
doi = {10.1126/sciadv.aav4489},
journal = {Science Advances},
number = 2,
volume = 5,
place = {United States},
year = {2019},
month = {2}
}

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Works referenced in this record:

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    Works referencing / citing this record:

    Synthesis of Free-Standing, Monolayered Organometallic Sheets at the Air/Water Interface
    journal, July 2011

    • Bauer, Thomas; Zheng, Zhikun; Renn, Alois
    • Angewandte Chemie International Edition, Vol. 50, Issue 34
    • DOI: 10.1002/anie.201100669

    Large-Area, Free-Standing, Two-Dimensional Supramolecular Polymer Single-Layer Sheets for Highly Efficient Electrocatalytic Hydrogen Evolution
    journal, August 2015

    • Dong, Renhao; Pfeffermann, Martin; Liang, Haiwei
    • Angewandte Chemie International Edition, Vol. 54, Issue 41
    • DOI: 10.1002/anie.201506048

    Smart Organic Two-Dimensional Materials Based on a Rational Combination of Non-covalent Interactions
    journal, August 2016

    • Bai, Wei; Jiang, Ziwen; Ribbe, Alexander E.
    • Angewandte Chemie International Edition, Vol. 55, Issue 36
    • DOI: 10.1002/anie.201605050

    Two-Dimensional Calix[4]arene-based Metal-Organic Coordination Networks of Tunable Crystallinity
    journal, October 2017

    • Moradi, Mina; Tulli, Ludovico G.; Nowakowski, Jan
    • Angewandte Chemie International Edition, Vol. 56, Issue 46
    • DOI: 10.1002/anie.201703825

    Timepix, a 65k programmable pixel readout chip for arrival time, energy and/or photon counting measurements
    journal, October 2007

    • Llopart, X.; Ballabriga, R.; Campbell, M.
    • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 581, Issue 1-2
    • DOI: 10.1016/j.nima.2007.08.079

    Upper rim tetrathiafulvalene-bridged calix[4]arenes
    journal, June 2011

    • Düker, Matthias H.; Gómez, Rafael; Vande Velde, Christophe M. L.
    • Tetrahedron Letters, Vol. 52, Issue 22
    • DOI: 10.1016/j.tetlet.2011.03.140

    A method of imaging ultrathin foils with very low energy electrons
    journal, August 2012


    Interface-Assisted Synthesis of 2D Materials: Trend and Challenges
    journal, June 2018


    Calixarenes. 22. Synthesis, properties, and metal complexation of aminocalixarenes
    journal, August 1988

    • Gutsche, C. David.; Nam, Kye Chun.
    • Journal of the American Chemical Society, Vol. 110, Issue 18
    • DOI: 10.1021/ja00226a034

    Free-Standing, Single-Monomer-Thick Two-Dimensional Polymers through Covalent Self-Assembly in Solution
    journal, April 2013

    • Baek, Kangkyun; Yun, Gyeongwon; Kim, Youngkook
    • Journal of the American Chemical Society, Vol. 135, Issue 17
    • DOI: 10.1021/ja4002019

    Controlling the Dimensionality of On-Surface Coordination Polymers via Endo- or Exoligation
    journal, June 2014

    • Shchyrba, Aneliia; Wäckerlin, Christian; Nowakowski, Jan
    • Journal of the American Chemical Society, Vol. 136, Issue 26
    • DOI: 10.1021/ja5020103

    Free-Standing Monolayer Two-Dimensional Supramolecular Organic Framework with Good Internal Order
    journal, November 2015

    • Pfeffermann, Martin; Dong, Renhao; Graf, Robert
    • Journal of the American Chemical Society, Vol. 137, Issue 45
    • DOI: 10.1021/jacs.5b09638

    Controlling on-surface polymerization by hierarchical and substrate-directed growth
    journal, January 2012

    • Lafferentz, L.; Eberhardt, V.; Dri, C.
    • Nature Chemistry, Vol. 4, Issue 3
    • DOI: 10.1038/nchem.1242

    Nano-architectures by covalent assembly of molecular building blocks
    journal, October 2007

    • Grill, Leonhard; Dyer, Matthew; Lafferentz, Leif
    • Nature Nanotechnology, Vol. 2, Issue 11
    • DOI: 10.1038/nnano.2007.346

    Trianionic calix[4]arene monoalkoxy derivatives: synthesis, solid-state structures and self-assembly properties
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    • Suwinska, Kinga; Shkurenko, Oleksandr; Mbemba, Cyrille
    • New Journal of Chemistry, Vol. 32, Issue 11
    • DOI: 10.1039/b806342g

    Supramolecular stacking in a high Z ′ calix[8]arene–porphyrin assembly
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    Performance measurements at the SLS SIM beamline
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    • Flechsig, U.; Nolting, F.; Fraile Rodríguez, A.
    • SRI 2009, 10TH INTERNATIONAL CONFERENCE ON RADIATION INSTRUMENTATION, AIP Conference Proceedings
    • DOI: 10.1063/1.3463200

    Adsorption geometry, molecular interaction, and charge transfer of triphenylamine-based dye on rutile TiO 2 (110)
    journal, December 2010

    • Yu, Shun; Ahmadi, Sareh; Zuleta, Marcelo
    • The Journal of Chemical Physics, Vol. 133, Issue 22
    • DOI: 10.1063/1.3509389

    Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage
    journal, January 2002

    • Eddaoudi, Mohamed; Kim, Jaheon; Rosi, Nathaniel
    • Science, Vol. 295, Issue 5554, p. 469-472
    • DOI: 10.1126/science.1067208

    Designed Synthesis of 3D Covalent Organic Frameworks
    journal, April 2007

    • El-Kaderi, Hani M.; Hunt, Joseph R.; Mendoza-Cortes, Jose L.
    • Science, Vol. 316, Issue 5822, p. 268-272
    • DOI: 10.1126/science.1139915

    Beyond crystallography: Diffractive imaging using coherent x-ray light sources
    journal, April 2015


    Nature of the empty states and signature of the charge density wave instability and upper Peierls transition of TTF-TCNQ by temperature-dependent NEXAFS spectroscopy
    journal, January 2015

    • Chernenkaya, Alisa; Medjanik, Katerina; Nagel, Peter
    • The European Physical Journal B, Vol. 88, Issue 1
    • DOI: 10.1140/epjb/e2014-50481-9