TY - JOUR
T1 - Hexathioalkyl sumanenes
T2 - An electron-donating buckybowl as a building block for supramolecular materials
AU - Shoji, Yoshiaki
AU - Kajitani, Takashi
AU - Ishiwari, Fumitaka
AU - Ding, Qiang
AU - Sato, Hiroyasu
AU - Anetai, Hayato
AU - Akutagawa, Tomoyuki
AU - Sakurai, Hidehiro
AU - Fukushima, Takanori
N1 - Funding Information:
This work was supported by a Grant-in-Aid for Scientic Research on Innovative Areas “p-Figuration: Control of Electron and Structural Dynamism for Innovative Functions” (JP26102008 for T. F., JP26102002 for H. S. and JP26102007 for T. A.) from the Japan Society for the Promotion of Science (JSPS). This work was also supported in part by “Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials” from MEXT, Japan. The synchrotron XRD experiments were performed at the BL45XU beamline at SPring-8 with the approval of the RIKEN SPring-8 Center (proposal no. 20150068 and 20160027). Q. D. acknowledges the Program for Leading Graduate Schools “Academy for Co-Creative Education of Environment and Energy Science” from MEXT, Japan. The authors would like to thank Suzukakedai Materials Analysis Division, Technical Department, Tokyo Institute of Technology, for their support with the NMR measurements.
Publisher Copyright:
© 2017 The Royal Society of Chemistry.
PY - 2017
Y1 - 2017
N2 - Unlike planar aromatic compounds, bowl-shaped sumanene, which has concave and convex faces with different electrostatic potentials, tends to form a one-dimensional columnar assembly without causing slip-stacking in the crystal. Here we report the first successful synthesis of liquid-crystalline (LC) sumanenes, which was brought about by the incorporation of six thioalkyl groups (R = SC6H13 or SC12H25) into the aromatic part of sumanene. In contrast to the case of the mesophase formation of corannulene, which requires the presence of many dendritic side chains, sumanene derivatives with simple alkyl chains can exhibit a remarkably high-order columnar LC mesophase over a wide temperature range. While non-substituted sumanene inherently behaves as an electron acceptor, hexathioalkyl versions, such as hexathiomethyl sumanene, show electron-donating properties, resulting in complexation with C60. Considering its unique shape, electronic properties, and self-assembly behavior, the electron-donating sumanene may represent a new building block for constructing supramolecular materials, both by itself and in combination with fullerene derivatives.
AB - Unlike planar aromatic compounds, bowl-shaped sumanene, which has concave and convex faces with different electrostatic potentials, tends to form a one-dimensional columnar assembly without causing slip-stacking in the crystal. Here we report the first successful synthesis of liquid-crystalline (LC) sumanenes, which was brought about by the incorporation of six thioalkyl groups (R = SC6H13 or SC12H25) into the aromatic part of sumanene. In contrast to the case of the mesophase formation of corannulene, which requires the presence of many dendritic side chains, sumanene derivatives with simple alkyl chains can exhibit a remarkably high-order columnar LC mesophase over a wide temperature range. While non-substituted sumanene inherently behaves as an electron acceptor, hexathioalkyl versions, such as hexathiomethyl sumanene, show electron-donating properties, resulting in complexation with C60. Considering its unique shape, electronic properties, and self-assembly behavior, the electron-donating sumanene may represent a new building block for constructing supramolecular materials, both by itself and in combination with fullerene derivatives.
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U2 - 10.1039/c7sc03860g
DO - 10.1039/c7sc03860g
M3 - Article
AN - SCOPUS:85034768450
VL - 8
SP - 8405
EP - 8410
JO - Chemical Science
JF - Chemical Science
SN - 2041-6520
IS - 12
ER -