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One-shot K-region-selective annulative π-extension for nanographene synthesis and functionalization
The optoelectronic nature of two-dimensional sheets of sp(2)-hydridized carbons (for example, graphenes and nanographenes) can be dramatically altered and tuned by altering the degree of π-extension, shape, width and edge topology. Among various approaches to synthesize nanographenes with atom-by-at...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Pub. Group
2015
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4339889/ https://www.ncbi.nlm.nih.gov/pubmed/25683787 http://dx.doi.org/10.1038/ncomms7251 |
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author | Ozaki, Kyohei Kawasumi, Katsuaki Shibata, Mari Ito, Hideto Itami, Kenichiro |
author_facet | Ozaki, Kyohei Kawasumi, Katsuaki Shibata, Mari Ito, Hideto Itami, Kenichiro |
author_sort | Ozaki, Kyohei |
collection | PubMed |
description | The optoelectronic nature of two-dimensional sheets of sp(2)-hydridized carbons (for example, graphenes and nanographenes) can be dramatically altered and tuned by altering the degree of π-extension, shape, width and edge topology. Among various approaches to synthesize nanographenes with atom-by-atom precision, one-shot annulative π-extension (APEX) reactions of polycyclic aromatic hydrocarbons hold significant potential not only to achieve a ‘growth from template’ synthesis of nanographenes, but also to fine-tune the properties of nanographenes. Here we describe one-shot APEX reactions that occur at the K-region (convex armchair edge) of polycyclic aromatic hydrocarbons by the Pd(CH(3)CN)(4)(SbF(6))(2)/o-chloranil catalytic system with silicon-bridged aromatics as π-extending agents. Density functional theory calculations suggest that the complete K-region selectivity stems from the olefinic (decreased aromatic) character of the K-region. The protocol is applicable to multiple APEX and sequential APEX reactions, to construct various nanographene structures in a rapid and programmable manner. |
format | Online Article Text |
id | pubmed-4339889 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2015 |
publisher | Nature Pub. Group |
record_format | MEDLINE/PubMed |
spelling | pubmed-43398892015-03-02 One-shot K-region-selective annulative π-extension for nanographene synthesis and functionalization Ozaki, Kyohei Kawasumi, Katsuaki Shibata, Mari Ito, Hideto Itami, Kenichiro Nat Commun Article The optoelectronic nature of two-dimensional sheets of sp(2)-hydridized carbons (for example, graphenes and nanographenes) can be dramatically altered and tuned by altering the degree of π-extension, shape, width and edge topology. Among various approaches to synthesize nanographenes with atom-by-atom precision, one-shot annulative π-extension (APEX) reactions of polycyclic aromatic hydrocarbons hold significant potential not only to achieve a ‘growth from template’ synthesis of nanographenes, but also to fine-tune the properties of nanographenes. Here we describe one-shot APEX reactions that occur at the K-region (convex armchair edge) of polycyclic aromatic hydrocarbons by the Pd(CH(3)CN)(4)(SbF(6))(2)/o-chloranil catalytic system with silicon-bridged aromatics as π-extending agents. Density functional theory calculations suggest that the complete K-region selectivity stems from the olefinic (decreased aromatic) character of the K-region. The protocol is applicable to multiple APEX and sequential APEX reactions, to construct various nanographene structures in a rapid and programmable manner. Nature Pub. Group 2015-02-16 /pmc/articles/PMC4339889/ /pubmed/25683787 http://dx.doi.org/10.1038/ncomms7251 Text en Copyright © 2015, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved. http://creativecommons.org/licenses/by/4.0/ This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ |
spellingShingle | Article Ozaki, Kyohei Kawasumi, Katsuaki Shibata, Mari Ito, Hideto Itami, Kenichiro One-shot K-region-selective annulative π-extension for nanographene synthesis and functionalization |
title | One-shot K-region-selective annulative π-extension for nanographene synthesis and functionalization |
title_full | One-shot K-region-selective annulative π-extension for nanographene synthesis and functionalization |
title_fullStr | One-shot K-region-selective annulative π-extension for nanographene synthesis and functionalization |
title_full_unstemmed | One-shot K-region-selective annulative π-extension for nanographene synthesis and functionalization |
title_short | One-shot K-region-selective annulative π-extension for nanographene synthesis and functionalization |
title_sort | one-shot k-region-selective annulative π-extension for nanographene synthesis and functionalization |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4339889/ https://www.ncbi.nlm.nih.gov/pubmed/25683787 http://dx.doi.org/10.1038/ncomms7251 |
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