TY - JOUR
T1 - Double aromaticity arising from σ- and π-rings
AU - Furukawa, Shunsuke
AU - Fujita, Masahiro
AU - Kanatomi, Yoshihiko
AU - Minoura, Mao
AU - Hatanaka, Miho
AU - Morokuma, Keiji
AU - Ishimura, Kazuya
AU - Saito, Masaichi
N1 - Funding Information:
This work was supported by a Grant-in-Aid for Scientific Research on Innovative Areas “π-System Figuration: Control of Electron and Structural Dynamism for Innovative Functions” from the Japan Society for the Promotion of Science (JSPS) (JP26102006 to M.S.) and “Stimuli-responsive Chemical Species for the Creation of Functional Molecules” (15H00918 to S.F. and 15H009382 to K.M.) from the Japanese Ministry of Education, Culture, Sports, Science, and Technology (MEXT). This work was also supported by a Challenging Research Exploratory JSPS KAKENHI grant (16K13945 to S.F.), a Grant-in-Aid for Scientific Research (C) (16K00175 to K.I.) and a Grant-in-Aid for Scientific Research (A) (18H03908 to M.S.). M.S. gratefully acknowledges a research grant from the Yamada Science Foundation. The authors thank Prof. Takashi Fujihara (Saitama Univ.) for assistance with solid-state NMR measurements.
Publisher Copyright:
© 2018, The Author(s).
PY - 2018/12/1
Y1 - 2018/12/1
N2 - Aromaticity has been a central concept in chemistry since the discovery of benzene in the 19th century and has impacted the science of delocalized π-electron systems. The aromaticity of conventional aromatic compounds usually originates from electron delocalization through a single ring that consists of π-symmetric orbitals. Although double aromaticity, i.e. aromaticity composed of two circularly delocalized orbitals, has been theoretically predicted for over 20 years, the double aromaticity of a bench-stable compound is not well explored by experiment. Here we report the synthesis and isolation of the dication of hexakis(phenylselenyl)benzene, as well as its double aromaticity based on structural, energetic, and magnetic criteria. In this dication, cyclic σ-symmetric and π-symmetric delocalized orbitals are formally occupied by ten and six electrons, respectively, and the aromaticity thus follows the 4n + 2 (n = 1, 2,…) electron Hückel rule, regardless of the σ-orbital or π-orbital symmetry.
AB - Aromaticity has been a central concept in chemistry since the discovery of benzene in the 19th century and has impacted the science of delocalized π-electron systems. The aromaticity of conventional aromatic compounds usually originates from electron delocalization through a single ring that consists of π-symmetric orbitals. Although double aromaticity, i.e. aromaticity composed of two circularly delocalized orbitals, has been theoretically predicted for over 20 years, the double aromaticity of a bench-stable compound is not well explored by experiment. Here we report the synthesis and isolation of the dication of hexakis(phenylselenyl)benzene, as well as its double aromaticity based on structural, energetic, and magnetic criteria. In this dication, cyclic σ-symmetric and π-symmetric delocalized orbitals are formally occupied by ten and six electrons, respectively, and the aromaticity thus follows the 4n + 2 (n = 1, 2,…) electron Hückel rule, regardless of the σ-orbital or π-orbital symmetry.
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U2 - 10.1038/s42004-018-0057-4
DO - 10.1038/s42004-018-0057-4
M3 - Article
AN - SCOPUS:85061902674
SN - 2399-3669
VL - 1
JO - Communications Chemistry
JF - Communications Chemistry
IS - 1
M1 - 60
ER -