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Title: On–Surface Synthesis and Characterization of Acene–Based Nanoribbons Incorporating Four–Membered Rings

Abstract

A bottom up method for the synthesis of unique tetracene–based nanoribbons, which incorporate cyclobutadiene moieties as linkers between the acene segments, is reported. These structures were achieved through the formal [2+2] cycloaddition reaction of ortho–functionalized tetracene precursor monomers. The formation mechanism and the electronic and magnetic properties of these nanoribbons were comprehensively studied by means of a multitechnique approach. Ultra–high vacuum scanning tunneling microscopy showed the occurrence of metal–coordinated nanostructures at room temperature and their evolution into nanoribbons through formal [2+2] cycloaddition at 475 K. Frequency–shift non–contact atomic force microscopy images clearly proved the presence of bridging cyclobutadiene moieties upon covalent coupling of activated tetracene molecules. Insight into the electronic and vibrational properties of the so–formed ribbons was obtained by scanning tunneling microscopy, Raman spectroscopy, and theoretical calculations. Magnetic properties were addressed from a computational point of view, allowing us to propose promising candidates to magnetic acene–based ribbons incorporating four–membered rings. Here, the reported findings will increase the understanding and availability of new graphene–based nanoribbons with high potential in future spintronics.

Authors:
ORCiD logo [1];  [2];  [3];  [4]; ORCiD logo [5];  [4];  [4];  [6];  [6];  [7];  [8];  [2];  [2];  [9]
  1. Swiss Federal Laboratories for Materials Science and Technology, Dubendorf (Switzerland); Instituto de Ciencia de Materiales de Madrid (ICMM-CSIC), Madrid (Spain)
  2. Swiss Federal Laboratories for Materials Science and Technology, Dubendorf (Switzerland)
  3. Rensselaer Polytechnic Inst., Troy, NY (United States); CNRS-Univ. Bourgogne Franche-Comte, Dijon Cedex (France)
  4. Rensselaer Polytechnic Inst., Troy, NY (United States)
  5. Rensselaer Polytechnic Inst., Troy, NY (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  6. Technische Univ. Dresden, Dresden (Germany)
  7. Max Planck Institute for Polymer Research, Mainz (Germany)
  8. Swiss Federal Laboratories for Materials Science and Technology, Dubendorf (Switzerland); CSIC-Univ. de Sevilla, Sevilla (Spain)
  9. Swiss Federal Laboratories for Materials Science and Technology, Dubendorf (Switzerland); Univ. of Bern, Bern (Switzerland)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1542237
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 25; Journal Issue: n/a; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 77 NANOSCIENCE AND NANOTECHNOLOGY; acene; cycloaddition; nanoribbons; on-surface chemistry; zigzag

Citation Formats

Sánchez‐Sánchez, Carlos, Dienel, Thomas, Nicolaï, Adrien, Kharche, Neerav, Liang, Liangbo, Daniels, Colin, Meunier, Vincent, Liu, Junzhi, Feng, Xinliang, Müllen, Klaus, Sánchez‐Valencia, Juan Ramón, Gröning, Oliver, Ruffieux, Pascal, and Fasel, Roman. On–Surface Synthesis and Characterization of Acene–Based Nanoribbons Incorporating Four–Membered Rings. United States: N. p., 2019. Web. doi:10.1002/chem.201901410.
Sánchez‐Sánchez, Carlos, Dienel, Thomas, Nicolaï, Adrien, Kharche, Neerav, Liang, Liangbo, Daniels, Colin, Meunier, Vincent, Liu, Junzhi, Feng, Xinliang, Müllen, Klaus, Sánchez‐Valencia, Juan Ramón, Gröning, Oliver, Ruffieux, Pascal, & Fasel, Roman. On–Surface Synthesis and Characterization of Acene–Based Nanoribbons Incorporating Four–Membered Rings. United States. doi:10.1002/chem.201901410.
Sánchez‐Sánchez, Carlos, Dienel, Thomas, Nicolaï, Adrien, Kharche, Neerav, Liang, Liangbo, Daniels, Colin, Meunier, Vincent, Liu, Junzhi, Feng, Xinliang, Müllen, Klaus, Sánchez‐Valencia, Juan Ramón, Gröning, Oliver, Ruffieux, Pascal, and Fasel, Roman. Thu . "On–Surface Synthesis and Characterization of Acene–Based Nanoribbons Incorporating Four–Membered Rings". United States. doi:10.1002/chem.201901410. https://www.osti.gov/servlets/purl/1542237.
@article{osti_1542237,
title = {On–Surface Synthesis and Characterization of Acene–Based Nanoribbons Incorporating Four–Membered Rings},
author = {Sánchez‐Sánchez, Carlos and Dienel, Thomas and Nicolaï, Adrien and Kharche, Neerav and Liang, Liangbo and Daniels, Colin and Meunier, Vincent and Liu, Junzhi and Feng, Xinliang and Müllen, Klaus and Sánchez‐Valencia, Juan Ramón and Gröning, Oliver and Ruffieux, Pascal and Fasel, Roman},
abstractNote = {A bottom up method for the synthesis of unique tetracene–based nanoribbons, which incorporate cyclobutadiene moieties as linkers between the acene segments, is reported. These structures were achieved through the formal [2+2] cycloaddition reaction of ortho–functionalized tetracene precursor monomers. The formation mechanism and the electronic and magnetic properties of these nanoribbons were comprehensively studied by means of a multitechnique approach. Ultra–high vacuum scanning tunneling microscopy showed the occurrence of metal–coordinated nanostructures at room temperature and their evolution into nanoribbons through formal [2+2] cycloaddition at 475 K. Frequency–shift non–contact atomic force microscopy images clearly proved the presence of bridging cyclobutadiene moieties upon covalent coupling of activated tetracene molecules. Insight into the electronic and vibrational properties of the so–formed ribbons was obtained by scanning tunneling microscopy, Raman spectroscopy, and theoretical calculations. Magnetic properties were addressed from a computational point of view, allowing us to propose promising candidates to magnetic acene–based ribbons incorporating four–membered rings. Here, the reported findings will increase the understanding and availability of new graphene–based nanoribbons with high potential in future spintronics.},
doi = {10.1002/chem.201901410},
journal = {Chemistry - A European Journal},
number = n/a,
volume = 25,
place = {United States},
year = {2019},
month = {6}
}

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    Works referencing / citing this record:

    Controllable Fabrication of Nanostructured Graphene Towards Electronics
    journal, March 2016

    • Zeng, Mengqi; Xiao, Yao; Liu, Jinxin
    • Advanced Electronic Materials, Vol. 2, Issue 4
    • DOI: 10.1002/aelm.201500456

    Kovalente Kupplung auf Oberflächen im Ultrahochvakuum
    journal, September 2008


    On-Surface Covalent Coupling in Ultrahigh Vacuum
    journal, September 2008


    On-Surface Reactions
    journal, May 2015


    Direct and indirect band gap types in one-dimensional conjugated or stacked organic materials
    journal, June 1999

    • Seo, Dong-Kyun; Hoffmann, Roald
    • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 102, Issue 1-6
    • DOI: 10.1007/s002140050469

    Graphene: Nanostructure engineering and applications
    journal, January 2017


    Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
    journal, July 1996


    BerkeleyGW: A massively parallel computer package for the calculation of the quasiparticle and optical properties of materials and nanostructures
    journal, June 2012

    • Deslippe, Jack; Samsonidze, Georgy; Strubbe, David A.
    • Computer Physics Communications, Vol. 183, Issue 6
    • DOI: 10.1016/j.cpc.2011.12.006

    First principles phonon calculations in materials science
    journal, November 2015


    Steering a cycloaddition reaction via the surface structure
    journal, December 2018


    Surface-Activated Coupling Reactions Confined on a Surface
    journal, August 2015


    Surface-Catalyzed C–C Covalent Coupling Strategies toward the Synthesis of Low-Dimensional Carbon-Based Nanostructures
    journal, July 2015


    Width and Crystal Orientation Dependent Band Gap Renormalization in Substrate-Supported Graphene Nanoribbons
    journal, April 2016


    From Graphene Nanoribbons on Cu(111) to Nanographene on Cu(110): Critical Role of Substrate Structure in the Bottom-Up Fabrication Strategy
    journal, August 2015

    • Simonov, Konstantin A.; Vinogradov, Nikolay A.; Vinogradov, Alexander S.
    • ACS Nano, Vol. 9, Issue 9
    • DOI: 10.1021/acsnano.5b03280

    Substrate-Independent Growth of Atomically Precise Chiral Graphene Nanoribbons
    journal, August 2016

    • de Oteyza, Dimas G.; García-Lekue, Aran; Vilas-Varela, Manuel
    • ACS Nano, Vol. 10, Issue 9
    • DOI: 10.1021/acsnano.6b05269

    6,12-Diarylindeno[1,2- b ]fluorenes: Syntheses, Photophysics, and Ambipolar OFETs
    journal, June 2012

    • Chase, Daniel T.; Fix, Aaron G.; Kang, Seok Ju
    • Journal of the American Chemical Society, Vol. 134, Issue 25
    • DOI: 10.1021/ja303402p

    On-Surface Cyclization of ortho -Dihalotetracenes to Four- and Six-Membered Rings
    journal, November 2017

    • Sánchez-Sánchez, Carlos; Nicolaï, Adrien; Rossel, Frédéric
    • Journal of the American Chemical Society, Vol. 139, Issue 48
    • DOI: 10.1021/jacs.7b10026

    Perspectives on Carbon Nanotubes and Graphene Raman Spectroscopy
    journal, March 2010

    • Dresselhaus, Mildred S.; Jorio, Ado; Hofmann, Mario
    • Nano Letters, Vol. 10, Issue 3
    • DOI: 10.1021/nl904286r

    Graphene-like nanoribbons periodically embedded with four- and eight-membered rings
    journal, March 2017

    • Liu, Meizhuang; Liu, Mengxi; She, Limin
    • Nature Communications, Vol. 8, Issue 1
    • DOI: 10.1038/ncomms14924

    Raman spectroscopy as a versatile tool for studying the properties of graphene
    journal, April 2013


    A new type of two-dimensional carbon crystal prepared from 1,3,5-trihydroxybenzene
    journal, January 2017

    • Du, Qi-Shi; Tang, Pei-Duo; Huang, Hua-Lin
    • Scientific Reports, Vol. 7, Issue 1
    • DOI: 10.1038/srep40796

    On-surface synthesis of cyclic organic molecules
    journal, January 2011

    • Méndez, Javier; López, M. Francisca; Martín-Gago, José A.
    • Chemical Society Reviews, Vol. 40, Issue 9
    • DOI: 10.1039/c0cs00161a

    QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
    journal, September 2009

    • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
    • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
    • DOI: 10.1088/0953-8984/21/39/395502

    Theory of coherent phonons in carbon nanotubes and graphene nanoribbons
    journal, March 2013


    First-principles calculations of the screening of electric fields at the aluminium (111) and (110) surfaces
    journal, April 1993


    Promising applications of graphene and graphene-based nanostructures
    journal, April 2016

    • Nguyen, Bich Ha; Nguyen, Van Hieu
    • Advances in Natural Sciences: Nanoscience and Nanotechnology, Vol. 7, Issue 2
    • DOI: 10.1088/2043-6262/7/2/023002

    Electron correlation in semiconductors and insulators: Band gaps and quasiparticle energies
    journal, October 1986


    Efficient pseudopotentials for plane-wave calculations
    journal, January 1991


    Projector augmented-wave method
    journal, December 1994


    Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
    journal, October 1996


    From ultrasoft pseudopotentials to the projector augmented-wave method
    journal, January 1999


    Linear optical properties in the projector-augmented wave methodology
    journal, January 2006


    Coulomb-hole summations and energies for G W calculations with limited number of empty orbitals: A modified static remainder approach
    journal, April 2013


    Generalized Gradient Approximation Made Simple
    journal, October 1996

    • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
    • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
    • DOI: 10.1103/physrevlett.77.3865

    Van der Waals Density Functional for General Geometries
    journal, June 2004


    The Chemical Structure of a Molecule Resolved by Atomic Force Microscopy
    journal, August 2009


    Resolving Intra- and Inter-Molecular Structure with Non-Contact Atomic Force Microscopy
    journal, August 2015

    • Jarvis, Samuel
    • International Journal of Molecular Sciences, Vol. 16, Issue 8
    • DOI: 10.3390/ijms160819936