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
N1 - Funding Information:
This work was supported by the ERATO programme from JST (K.I.), the Funding Program for Next Generation World-Leading Researchers from JSPS (220GR049 to K.I.) and KAKENHI from MEXT (26810057 to H.I.). K.O. and K.K. thank the Japan Society for the Promotion of Science (JSPS) for fellowships. We thank Dr Yasutomo Segawa (Nagoya University), Professor Cathleen M. Crudden (Queen’s University) and Dr Ayako Miyazaki (Nagoya University) for fruitful discussion and critical comments. Dr Keiko Kuwata (Nagoya University) is acknowledged for assistance in mass spectroscopy. Calculations were performed using the resources of the Research Center for Computational Science, Okazaki, Japan. ITbM is supported by the World Premier International Research Center (WPI) Initiative, Japan.
Publisher Copyright:
© 2015 Macmillan Publishers Limited. All rights reserved.
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 -