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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.
@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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