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Title: Fluorine-programmed nanozipping to tailored nanographenes on rutile TiO2 surfaces

Abstract

The rational synthesis of nanographenes and carbon nanoribbons directly on nonmetallic surfaces has been an elusive goal for a long time. In this paper, we report that activation of the carbon (C)–fluorine (F) bond is a reliable and versatile tool enabling intramolecular aryl-aryl coupling directly on metal oxide surfaces. A challenging multistep transformation enabled by C–F bond activation led to a dominolike coupling that yielded tailored nanographenes directly on the rutile titania surface. Because of efficient regioselective zipping, we obtained the target nanographenes from flexible precursors. Fluorine positions in the precursor structure unambiguously dictated the running of the “zipping program,” resulting in the rolling up of oligophenylene chains. Finally, the high efficiency of the hydrogen fluoride zipping makes our approach attractive for the rational synthesis of nanographenes and nanoribbons directly on insulating and semiconducting surfaces.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]
  1. Jagiellonian University, Łojasiewicza (Poland); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Jagiellonian University, Łojasiewicza (Poland)
  3. Friedrich Alexander University Erlangen-Nuremberg, Erlangen (Germany)
  4. Espeem S.A.R.L., Esch-sur-Alzette (Luxembourg)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1489571
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Science
Additional Journal Information:
Journal Volume: 363; Journal Issue: 6422; Journal ID: ISSN 0036-8075
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Kolmer, Marek A., Zuzak, Rafal, Steiner, Ann Kristin, Zajac, Lukasz, Engelund, Mads, Godlewski, Szymon, Szymonski, Marek, and Amsharov, Konstantin. Fluorine-programmed nanozipping to tailored nanographenes on rutile TiO2 surfaces. United States: N. p., 2019. Web. doi:10.1126/science.aav4954.
Kolmer, Marek A., Zuzak, Rafal, Steiner, Ann Kristin, Zajac, Lukasz, Engelund, Mads, Godlewski, Szymon, Szymonski, Marek, & Amsharov, Konstantin. Fluorine-programmed nanozipping to tailored nanographenes on rutile TiO2 surfaces. United States. doi:10.1126/science.aav4954.
Kolmer, Marek A., Zuzak, Rafal, Steiner, Ann Kristin, Zajac, Lukasz, Engelund, Mads, Godlewski, Szymon, Szymonski, Marek, and Amsharov, Konstantin. Fri . "Fluorine-programmed nanozipping to tailored nanographenes on rutile TiO2 surfaces". United States. doi:10.1126/science.aav4954. https://www.osti.gov/servlets/purl/1489571.
@article{osti_1489571,
title = {Fluorine-programmed nanozipping to tailored nanographenes on rutile TiO2 surfaces},
author = {Kolmer, Marek A. and Zuzak, Rafal and Steiner, Ann Kristin and Zajac, Lukasz and Engelund, Mads and Godlewski, Szymon and Szymonski, Marek and Amsharov, Konstantin},
abstractNote = {The rational synthesis of nanographenes and carbon nanoribbons directly on nonmetallic surfaces has been an elusive goal for a long time. In this paper, we report that activation of the carbon (C)–fluorine (F) bond is a reliable and versatile tool enabling intramolecular aryl-aryl coupling directly on metal oxide surfaces. A challenging multistep transformation enabled by C–F bond activation led to a dominolike coupling that yielded tailored nanographenes directly on the rutile titania surface. Because of efficient regioselective zipping, we obtained the target nanographenes from flexible precursors. Fluorine positions in the precursor structure unambiguously dictated the running of the “zipping program,” resulting in the rolling up of oligophenylene chains. Finally, the high efficiency of the hydrogen fluoride zipping makes our approach attractive for the rational synthesis of nanographenes and nanoribbons directly on insulating and semiconducting surfaces.},
doi = {10.1126/science.aav4954},
journal = {Science},
number = 6422,
volume = 363,
place = {United States},
year = {2019},
month = {1}
}

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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
  • DOI: 10.1103/PhysRevLett.77.3865

Controlled synthesis of single-chirality carbon nanotubes
journal, August 2014

  • Sanchez-Valencia, Juan Ramon; Dienel, Thomas; Gröning, Oliver
  • Nature, Vol. 512, Issue 7512
  • DOI: 10.1038/nature13607

On-surface synthesis of graphene nanoribbons with zigzag edge topology
journal, March 2016

  • Ruffieux, Pascal; Wang, Shiyong; Yang, Bo
  • Nature, Vol. 531, Issue 7595
  • DOI: 10.1038/nature17151

On-Surface Synthesis of Atomically Precise Graphene Nanoribbons
journal, February 2016

  • Talirz, Leopold; Ruffieux, Pascal; Fasel, Roman
  • Advanced Materials, Vol. 28, Issue 29
  • DOI: 10.1002/adma.201505738

Theory and Application for the Scanning Tunneling Microscope
journal, June 1983


Facile Bucky-Bowl Synthesis by Regiospecific Cove-Region Closure by HF Elimination
journal, April 2012

  • Amsharov, K. Yu.; Kabdulov, M. A.; Jansen, Martin
  • Angewandte Chemie International Edition, Vol. 51, Issue 19
  • DOI: 10.1002/anie.201200516

Efficient Helicene Synthesis: Friedel–Crafts-type Cyclization of 1,1-Difluoro-1-alkenes
journal, June 2008

  • Ichikawa, Junji; Yokota, Misaki; Kudo, Takao
  • Angewandte Chemie International Edition, Vol. 47, Issue 26
  • DOI: 10.1002/anie.200801396

Efficient and reliable method for the simulation of scanning tunneling images and spectra with local basis sets
journal, April 2006


Controllable conversion of quasi-freestanding polymer chains to graphene nanoribbons
journal, March 2017

  • Ma, Chuanxu; Xiao, Zhongcan; Zhang, Honghai
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14815

Surface-assisted cyclodehydrogenation provides a synthetic route towards easily processable and chemically tailored nanographenes
journal, November 2010

  • Treier, Matthias; Pignedoli, Carlo Antonio; Laino, Teodoro
  • Nature Chemistry, Vol. 3, Issue 1
  • DOI: 10.1038/nchem.891

Short-channel field-effect transistors with 9-atom and 13-atom wide graphene nanoribbons
journal, September 2017

  • Llinas, Juan Pablo; Fairbrother, Andrew; Borin Barin, Gabriela
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/s41467-017-00734-x

Experimental and Theoretical Investigations of Surface-Assisted Graphene Nanoribbon Synthesis Featuring Carbon–Fluorine Bond Cleavage
journal, May 2017


Bottom-up graphene nanoribbon field-effect transistors
journal, December 2013

  • Bennett, Patrick B.; Pedramrazi, Zahra; Madani, Ali
  • Applied Physics Letters, Vol. 103, Issue 25
  • DOI: 10.1063/1.4855116

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

Mapping the Excited States of Single Hexa- peri -benzocoronene Oligomers
journal, March 2012

  • Soe, We-Hyo; Wong, Hon Seng; Manzano, Carlos
  • ACS Nano, Vol. 6, Issue 4
  • DOI: 10.1021/nn300110k

The SIESTA method for ab initio order- N materials simulation
journal, March 2002

  • Soler, José M.; Artacho, Emilio; Gale, Julian D.
  • Journal of Physics: Condensed Matter, Vol. 14, Issue 11
  • DOI: 10.1088/0953-8984/14/11/302

Fullerenes from aromatic precursors by surface-catalysed cyclodehydrogenation
journal, August 2008

  • Otero, Gonzalo; Biddau, Giulio; Sánchez-Sánchez, Carlos
  • Nature, Vol. 454, Issue 7206
  • DOI: 10.1038/nature07193

Forming Aromatic Hemispheres on Transition-Metal Surfaces
journal, October 2007

  • Rim, Kwang Taeg; Siaj, Mohamed; Xiao, Shengxiong
  • Angewandte Chemie International Edition, Vol. 46, Issue 41
  • DOI: 10.1002/anie.200701117

Atomically precise bottom-up fabrication of graphene nanoribbons
journal, July 2010

  • Cai, Jinming; Ruffieux, Pascal; Jaafar, Rached
  • Nature, Vol. 466, Issue 7305
  • DOI: 10.1038/nature09211

Adsorbate Induced Restructuring of TiO 2 ( 011 ) ( 2 × 1 ) Leads to One-Dimensional Nanocluster Formation
journal, March 2012


The Rolling-Up of Oligophenylenes to Nanographenes by a HF-Zipping Approach
journal, October 2017

  • Steiner, Ann-Kristin; Amsharov, Konstantin Y.
  • Angewandte Chemie International Edition, Vol. 56, Issue 46
  • DOI: 10.1002/anie.201707272

On-surface polymerization on a semiconducting oxide: aryl halide coupling controlled by surface hydroxyl groups on rutile TiO 2 (011)
journal, January 2015

  • Kolmer, Marek; Zuzak, Rafal; Ahmad Zebari, Amir A.
  • Chemical Communications, Vol. 51, Issue 56
  • DOI: 10.1039/C5CC02989A

Tailoring molecular self-organization by chemical synthesis: Hexaphenylbenzene, hexa- peri -hexabenzocoronene, and derivatives on Cu (111)
journal, April 2005


Surface Structure of TiO 2 Rutile (011) Exposed to Liquid Water
journal, November 2017

  • Balajka, Jan; Aschauer, Ulrich; Mertens, Stijn F. L.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 47
  • DOI: 10.1021/acs.jpcc.7b09674

Toward interfacing organic semiconductors with ferromagnetic transition metal substrates: enhanced stability via carboxylate anchoring
journal, January 2016

  • Han, R.; Blobner, F.; Bauer, J.
  • Chemical Communications, Vol. 52, Issue 63
  • DOI: 10.1039/C6CC05009C

XPS and NEXAFS study of fluorine modified TiO2 nano-ovoids reveals dependence of Ti3+ surface population on the modifying agent
journal, January 2014

  • Ruzicka, Jan-Yves; Bakar, Faridah Abu; Thomsen, Lars
  • RSC Advances, Vol. 4, Issue 40
  • DOI: 10.1039/c3ra47652a

Towards the Isomer-Specific Synthesis of Higher Fullerenes and Buckybowls by the Surface-Catalyzed Cyclodehydrogenation of Aromatic Precursors
journal, October 2010

  • Amsharov, Konstantin; Abdurakhmanova, Nasiba; Stepanow, Sebastian
  • Angewandte Chemie International Edition, Vol. 49, Issue 49
  • DOI: 10.1002/anie.201005000

Epitaxial Composite Layers of Electron Donors and Acceptors from Very Large Polycyclic Aromatic Hydrocarbons
journal, August 2002

  • Samorí, Paolo; Severin, Nikolai; Simpson, Christopher D.
  • Journal of the American Chemical Society, Vol. 124, Issue 32
  • DOI: 10.1021/ja020323q

Synthesis of Rationally Halogenated Buckybowls by Chemoselective Aromatic C−F Bond Activation
journal, March 2017

  • Papaianina, Olena; Akhmetov, Vladimir A.; Goryunkov, Alexey A.
  • Angewandte Chemie International Edition, Vol. 56, Issue 17
  • DOI: 10.1002/anie.201700814

Molecular Resonance Imaging and Manipulation of Hexabenzocoronene on NaCl(001) and KBr(001) on Ag(111)
journal, May 2018

  • Ardhuin, Thibault; Guillermet, Olivier; Gourdon, André
  • The Journal of Physical Chemistry C, Vol. 122, Issue 22
  • DOI: 10.1021/acs.jpcc.8b02959

Bottom up fabrication of (9, 0) zigzag and (6, 6) armchair carbon nanotube end-caps on the Rh(1 1 1) surface
journal, April 2015


Aluminium-mediated aromatic C–F bond activation: regioswitchable construction of benzene-fused triphenylene frameworks
journal, January 2016

  • Suzuki, Naoto; Fujita, Takeshi; Amsharov, Konstantin Yu.
  • Chemical Communications, Vol. 52, Issue 88
  • DOI: 10.1039/C6CC07199F

Aluminum oxide mediated C–F bond activation in trifluoromethylated arenes
journal, January 2016

  • Papaianina, O.; Amsharov, K. Yu.
  • Chemical Communications, Vol. 52, Issue 7
  • DOI: 10.1039/C5CC08747C

The Mechanism of Cyclodehydrofluorination on γ‐Alumina
journal, June 2018

  • Sharapa, Dmitry; Steiner, Ann‐Kristin; Amsharov, Konstantin
  • physica status solidi (b), Vol. 255, Issue 12
  • DOI: 10.1002/pssb.201800189

Adsorbate-induced lifting of substrate relaxation is a general mechanism governing titania surface chemistry
journal, September 2016

  • Silber, David; Kowalski, Piotr M.; Traeger, Franziska
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12888

Thiolate-Bonded Self-Assembled Monolayers on Ni(111): Bonding Strength, Structure, and Stability
journal, June 2015

  • Blobner, F.; Abufager, P. N.; Han, R.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 27
  • DOI: 10.1021/acs.jpcc.5b04351

Topological band engineering of graphene nanoribbons
journal, August 2018


Polymerization of Polyanthrylene on a Titanium Dioxide (011)-(2×1) Surface
journal, August 2013

  • Kolmer, Marek; Ahmad Zebari, Amir A.; Prauzner-Bechcicki, Jakub S.
  • Angewandte Chemie International Edition, Vol. 52, Issue 39
  • DOI: 10.1002/anie.201303657

Bond-Order Discrimination by Atomic Force Microscopy
journal, September 2012


Covalent-Bond Formation via On-Surface Chemistry
journal, January 2017

  • Held, Philipp Alexander; Fuchs, Harald; Studer, Armido
  • Chemistry - A European Journal, Vol. 23, Issue 25
  • DOI: 10.1002/chem.201604047

Closing the Nanographene Gap: Surface-Assisted Synthesis of Peripentacene from 6,6′-Bipentacene Precursors
journal, October 2015

  • Rogers, Cameron; Chen, Chen; Pedramrazi, Zahra
  • Angewandte Chemie International Edition, Vol. 54, Issue 50
  • DOI: 10.1002/anie.201507104

Building a 22-ring nanographene by combining in-solution and on-surface syntheses
journal, January 2018

  • Zuzak, Rafal; Castro-Esteban, Jesus; Brandimarte, Pedro
  • Chemical Communications, Vol. 54, Issue 73
  • DOI: 10.1039/C8CC05353G

Π Band Dispersion along Conjugated Organic Nanowires Synthesized on a Metal Oxide Semiconductor
journal, April 2016

  • Vasseur, Guillaume; Abadia, Mikel; Miccio, Luis A.
  • Journal of the American Chemical Society, Vol. 138, Issue 17
  • DOI: 10.1021/jacs.6b02151