TY - JOUR
T1 - Triazasumanene
T2 - An isoelectronic heteroanalogue of sumanene
AU - Tan, Qitao
AU - Kaewmati, Patcharin
AU - Higashibayashi, Shuhei
AU - Kawano, Masaki
AU - Yakiyama, Yumi
AU - Sakurai, Hidehiro
N1 - Funding Information:
This work was supported by a Grant-in-Aid for Scientific Research on Innovative Area “π Space Figuration” from MEXT (No. JP26102002), JSPS KAKENHI (No. JP26288020) and JST (ACT-C) (No. JPMJCR12YZ). Q.T. also thanks the Japan Society for the Promotion of Science (JSPS) for financial support in the form of a fellowship. M.K. gratefully acknowledges financial support from the WCU (World Class University) program (Project No. R31-10059), Korea. Y. Y. acknowledges Ogasawara Foundation for the Promotion of Science & Engineering and Iketani Science and Technology Foundation for the support. This work has been approved by the Photon Factory Program Advisory Committee (Proposal No. 2012G017) and Pohang Accelerator Laboratory (2017-1st-2D-024). We thank Dr. Yuki Morita for valuable discussions about photochemistry.
PY - 2018
Y1 - 2018
N2 - Buckybowls, which are represented by sumanene and corannulene, have attracted considerable attention for their unique bowl structures and interesting physicochemical properties. However, still few heteroatom-doped buckybowls have been reported to date. Here we show the successful synthesis of triazasumanene, an isoelectronic heteroanalogue of sumanene, which possesses a deeper bowl with stable bowl chirality and unique helical columnar packing in the crystal as an enantiopure form. In contrast, the crystal packing of the racemate shows a unidirectional columnar structure, which resembles that of the pristine sumanene. Doping of nitrogen atoms into the periphery of the sumanene framework also leads to perturbations of the electronic structure as shown by a significant decrease of the lowest unoccupied molecular orbital (LUMO) level and the optical band gap in comparison to all-carbon sumanene. The pyridine ring of triazasumanene shows unusual susceptibility towards acidic hydrolysis due to the highly strained curved structure.
AB - Buckybowls, which are represented by sumanene and corannulene, have attracted considerable attention for their unique bowl structures and interesting physicochemical properties. However, still few heteroatom-doped buckybowls have been reported to date. Here we show the successful synthesis of triazasumanene, an isoelectronic heteroanalogue of sumanene, which possesses a deeper bowl with stable bowl chirality and unique helical columnar packing in the crystal as an enantiopure form. In contrast, the crystal packing of the racemate shows a unidirectional columnar structure, which resembles that of the pristine sumanene. Doping of nitrogen atoms into the periphery of the sumanene framework also leads to perturbations of the electronic structure as shown by a significant decrease of the lowest unoccupied molecular orbital (LUMO) level and the optical band gap in comparison to all-carbon sumanene. The pyridine ring of triazasumanene shows unusual susceptibility towards acidic hydrolysis due to the highly strained curved structure.
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U2 - 10.1246/bcsj.20170384
DO - 10.1246/bcsj.20170384
M3 - Article
AN - SCOPUS:85045423570
VL - 91
SP - 531
EP - 537
JO - Bulletin of the Chemical Society of Japan
JF - Bulletin of the Chemical Society of Japan
SN - 0009-2673
IS - 4
ER -