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:
-
[1];
[5];
- Swiss Federal Laboratories for Materials Science and Technology, Dubendorf (Switzerland); Instituto de Ciencia de Materiales de Madrid (ICMM-CSIC), Madrid (Spain)
- Swiss Federal Laboratories for Materials Science and Technology, Dubendorf (Switzerland)
- Rensselaer Polytechnic Inst., Troy, NY (United States); CNRS-Univ. Bourgogne Franche-Comte, Dijon Cedex (France)
- Rensselaer Polytechnic Inst., Troy, NY (United States)
- Rensselaer Polytechnic Inst., Troy, NY (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Technische Univ. Dresden, Dresden (Germany)
- Max Planck Institute for Polymer Research, Mainz (Germany)
- Swiss Federal Laboratories for Materials Science and Technology, Dubendorf (Switzerland); CSIC-Univ. de Sevilla, Sevilla (Spain)
- 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. https://doi.org/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. https://doi.org/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 = {Thu Jun 13 00:00:00 EDT 2019},
month = {Thu Jun 13 00:00:00 EDT 2019}
}
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Works referenced in this record:
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
On-Surface Covalent Coupling in Ultrahigh Vacuum
journal, September 2008
- Gourdon, André
- Angewandte Chemie International Edition, Vol. 47, Issue 37
First-principles calculations of the screening of electric fields at the aluminium (111) and (110) surfaces
journal, April 1993
- Lam, S. C.; Needs, R. J.
- Journal of Physics: Condensed Matter, Vol. 5, Issue 14
Coulomb-hole summations and energies for calculations with limited number of empty orbitals: A modified static remainder approach
journal, April 2013
- Deslippe, Jack; Samsonidze, Georgy; Jain, Manish
- Physical Review B, Vol. 87, Issue 16
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
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
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
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
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
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
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
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Graphene: Nanostructure engineering and applications
journal, January 2017
- Zhang, Tingting; Wu, Shuang; Yang, Rong
- Frontiers of Physics, Vol. 12, Issue 1
Electron correlation in semiconductors and insulators: Band gaps and quasiparticle energies
journal, October 1986
- Hybertsen, Mark S.; Louie, Steven G.
- Physical Review B, Vol. 34, Issue 8, p. 5390-5413
Width and Crystal Orientation Dependent Band Gap Renormalization in Substrate-Supported Graphene Nanoribbons
journal, April 2016
- Kharche, Neerav; Meunier, Vincent
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 8
Truncation of periodic image interactions for confined systems
journal, June 2006
- Ismail-Beigi, Sohrab
- Physical Review B, Vol. 73, Issue 23
Reading the ripples of confined surface-state electrons: Profiles of constant integrated local density of states
journal, May 2003
- Pivetta, Marina; Silly, Fabien; Patthey, François
- Physical Review B, Vol. 67, Issue 19
Raman spectroscopy as a versatile tool for studying the properties of graphene
journal, April 2013
- Ferrari, Andrea C.; Basko, Denis M.
- Nature Nanotechnology, Vol. 8, Issue 4
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
Purely Armchair or Partially Chiral: Noncontact Atomic Force Microscopy Characterization of Dibromo-Bianthryl-Based Graphene Nanoribbons Grown on Cu(111)
journal, July 2016
- Sánchez-Sánchez, Carlos; Dienel, Thomas; Deniz, Okan
- ACS Nano, Vol. 10, Issue 8
Optimal Hubbard Models for Materials with Nonlocal Coulomb Interactions: Graphene, Silicene, and Benzene
journal, July 2013
- Schüler, M.; Rösner, M.; Wehling, T. O.
- Physical Review Letters, Vol. 111, Issue 3
Empirical bond polarizability model for fullerenes
journal, May 1996
- Guha, S.; Menéndez, J.; Page, J. B.
- Physical Review B, Vol. 53, Issue 19
Perspectives on Carbon Nanotubes and Graphene Raman Spectroscopy
journal, March 2010
- Dresselhaus, Mildred S.; Jorio, Ado; Hofmann, Mario
- Nano Letters, Vol. 10, Issue 3
On-Surface Reactions
journal, May 2015
- Lindner, Robert; Kühnle, Angelika
- ChemPhysChem, Vol. 16, Issue 8
Efficient pseudopotentials for plane-wave calculations
journal, January 1991
- Troullier, N.; Martins, José Luriaas
- Physical Review B, Vol. 43, Issue 3
Surface-Catalyzed C–C Covalent Coupling Strategies toward the Synthesis of Low-Dimensional Carbon-Based Nanostructures
journal, July 2015
- Fan, Qitang; Gottfried, J. Michael; Zhu, Junfa
- Accounts of Chemical Research, Vol. 48, Issue 8
Theory of coherent phonons in carbon nanotubes and graphene nanoribbons
journal, March 2013
- Sanders, G. D.; Nugraha, A. R. T.; Sato, K.
- Journal of Physics: Condensed Matter, Vol. 25, Issue 14
The Chemical Structure of a Molecule Resolved by Atomic Force Microscopy
journal, August 2009
- Gross, L.; Mohn, F.; Moll, N.
- Science, Vol. 325, Issue 5944
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Carbon Tetragons as Definitive Spin Switches in Narrow Zigzag Graphene Nanoribbons
journal, January 2016
- Cui, Ping; Zhang, Qiang; Zhu, Hongbin
- Physical Review Letters, Vol. 116, Issue 2
Magnetism in Disordered Graphene and Irradiated Graphite
journal, July 2008
- Yazyev, Oleg V.
- Physical Review Letters, Vol. 101, Issue 3
Surface-confined [2 + 2] cycloaddition towards one-dimensional polymers featuring cyclobutadiene units
journal, January 2017
- Tran, Bay V.; Pham, Tuan Anh; Grunst, Michael
- Nanoscale, Vol. 9, Issue 46
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
First principles phonon calculations in materials science
journal, November 2015
- Togo, Atsushi; Tanaka, Isao
- Scripta Materialia, Vol. 108
Kovalente Kupplung auf Oberflächen im Ultrahochvakuum
journal, September 2008
- Gourdon, André
- Angewandte Chemie, Vol. 120, Issue 37
Surface-Activated Coupling Reactions Confined on a Surface
journal, August 2015
- Dong, Lei; Liu, Pei Nian; Lin, Nian
- Accounts of Chemical Research, Vol. 48, Issue 10
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
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
Steering a cycloaddition reaction via the surface structure
journal, December 2018
- Koch, Matthias; Gille, Marie; Hecht, Stefan
- Surface Science, Vol. 678
Linear optical properties in the projector-augmented wave methodology
journal, January 2006
- Gajdoš, M.; Hummer, K.; Kresse, G.
- Physical Review B, Vol. 73, Issue 4
Van der Waals Density Functional for General Geometries
journal, June 2004
- Dion, M.; Rydberg, H.; Schröder, E.
- Physical Review Letters, Vol. 92, Issue 24
Theoretical study of the vibrational edge modes in graphene nanoribbons
journal, November 2008
- Vandescuren, M.; Hermet, P.; Meunier, V.
- Physical Review B, Vol. 78, Issue 19
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
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
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
Controllable Fabrication of Nanostructured Graphene Towards Electronics
journal, March 2016
- Zeng, Mengqi; Xiao, Yao; Liu, Jinxin
- Advanced Electronic Materials, Vol. 2, Issue 4
Ullmann-type coupling of brominated tetrathienoanthracene on copper and silver
journal, January 2014
- Gutzler, Rico; Cardenas, Luis; Lipton-Duffin, Josh
- Nanoscale, Vol. 6, Issue 5
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021
- Chen, Ruyi; Cui, Qirui; Liao, Liyang
- Nature Communications, Vol. 12, Issue 1
High-resolution X-ray luminescence extension imaging
journal, February 2021
- Ou, Xiangyu; Qin, Xian; Huang, Bolong
- Nature, Vol. 590, Issue 7846
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect
journal, February 2020
- Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna
- Scientific Reports, Vol. 10, Issue 1
Raman spectroscopy as a versatile tool for studying the properties of graphene.
text, January 2013
- Ferrari, Andrea; Basko, Denis M.
- Apollo - University of Cambridge Repository
Coulomb-hole summations and energies for GW calculations with limited number of empty orbitals: a modified static remainder approach
text, January 2012
- Deslippe, Jack; Samsonidze, Georgy; Jain, Manish
- arXiv
Optimal Hubbard models for materials with nonlocal Coulomb interactions: graphene, silicene and benzene
text, January 2013
- Schüler, M.; Rösner, M.; Wehling, T. O.
- arXiv
First principles phonon calculations in materials science
preprint, January 2015
- Togo, Atsushi; Tanaka, Isao
- arXiv
Truncation of Periodic Image Interactions for Confined Systems
text, January 2006
- Ismail-Beigi, Sohrab
- arXiv
Purely Armchair or Partially Chiral: Noncontact Atomic Force Microscopy Characterization of Dibromo-Bianthryl-Based Graphene Nanoribbons Grown on Cu(111)
text, January 2016
- Dienel, Thomas; Deniz, Okan; Fasel, Roman
- American Chemical Society
Works referencing / citing this record:
Unusual stabilization of larger acenes and heteroacenes
journal, January 2019
- Müller, Matthias; Ahrens, Lukas; Brosius, Victor
- Journal of Materials Chemistry C, Vol. 7, Issue 45