Abstract
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.
| Original language | English |
|---|---|
| Pages (from-to) | 531-537 |
| Number of pages | 7 |
| Journal | Bulletin of the Chemical Society of Japan |
| Volume | 91 |
| Issue number | 4 |
| DOIs | |
| Publication status | Published - 2018 Jan 1 |
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ASJC Scopus subject areas
- Chemistry(all)
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Triazasumanene : An isoelectronic heteroanalogue of sumanene. / Tan, Qitao; Kaewmati, Patcharin; Higashibayashi, Shuhei; Kawano, Masaki; Yakiyama, Yumi; Sakurai, Hidehiro.
In: Bulletin of the Chemical Society of Japan, Vol. 91, No. 4, 01.01.2018, p. 531-537.Research output: Contribution to journal › Article
}
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
PY - 2018/1/1
Y1 - 2018/1/1
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.
UR - http://www.scopus.com/inward/record.url?scp=85045423570&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85045423570&partnerID=8YFLogxK
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 -