Abstract
The optoelectronic nature of two-dimensional sheets of sp2-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(CH3CN)4(SbF6)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.
| Original language | English |
|---|---|
| Article number | 6251 |
| Journal | Nature Communications |
| Volume | 6 |
| DOIs | |
| Publication status | Published - Feb 17 2015 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Biochemistry, Genetics and Molecular Biology(all)
- Chemistry(all)
- Physics and Astronomy(all)
Cite this
One-shot K-region-selective annulative π-extension for nanographene synthesis and functionalization. / Ozaki, Kyohei; Kawasumi, Katsuaki; Shibata, Mari; Ito, Hideto; Itami, Kenichiro.
In: Nature Communications, Vol. 6, 6251, 17.02.2015.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - One-shot K-region-selective annulative π-extension for nanographene synthesis and functionalization
AU - Ozaki, Kyohei
AU - Kawasumi, Katsuaki
AU - Shibata, Mari
AU - Ito, Hideto
AU - Itami, Kenichiro
PY - 2015/2/17
Y1 - 2015/2/17
N2 - The optoelectronic nature of two-dimensional sheets of sp2-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(CH3CN)4(SbF6)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.
AB - The optoelectronic nature of two-dimensional sheets of sp2-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(CH3CN)4(SbF6)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.
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U2 - 10.1038/ncomms7251
DO - 10.1038/ncomms7251
M3 - Article
AN - SCOPUS:84923329717
VL - 6
JO - Nature Communications
JF - Nature Communications
SN - 2041-1723
M1 - 6251
ER -