TY - JOUR
T1 - Redox-Dependent Transformation of a Hydrazinobuckybowl between Curved and Planar Geometries
AU - Higashibayashi, Shuhei
AU - Pandit, Palash
AU - Haruki, Rie
AU - Adachi, Shin Ichi
AU - Kumai, Reiji
N1 - Funding Information:
This research was supported by the Japan Society for the Promotion of Science (JSPS; KAKENHI Grant Numbers 25410124 (S.H.), 26102002 (S.H.), and 26102014 (R.H., S.A., R.K.)) and JST ACT-C (S.H., P.P.). The X-ray diffraction study of 1 a was performed under the approval of the Photon Factory Program Advisory Committee (Proposal No. 2014S2-001). The computations were performed in part by using the Research Center for Computational Science, Okazaki, Japan.
Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2016/8/26
Y1 - 2016/8/26
N2 - A red-fluorescent heterobuckybowl with an embedded hydrazine structure was synthesized from a cyclobiphenothiazine derivative via a strained cyclobicarbazole. The hydrazinobuckybowl was found to possess bowl and twist structures in the neutral state, a shallow bowl structure in the monocation state, and a planar structure in the dication state by means of X-ray crystallographic analysis, DFT calculations, and a comparison of experimental and calculated13C NMR chemical shifts. The hydrazinobuckybowl is the first buckybowl that changes its geometry between curved bowl/twist structures and a planar structure depending on the oxidation state. The drastic geometrical change was possible as a result of the presence of two heteroatoms in the bowl skeleton and the multiple reversible redox reactions of the compound. Owing to the two kinds of bowl and twist conformations, the bowl-inversion dynamics of the hydrazinobuckybowl were found to follow a triple-well potential model.
AB - A red-fluorescent heterobuckybowl with an embedded hydrazine structure was synthesized from a cyclobiphenothiazine derivative via a strained cyclobicarbazole. The hydrazinobuckybowl was found to possess bowl and twist structures in the neutral state, a shallow bowl structure in the monocation state, and a planar structure in the dication state by means of X-ray crystallographic analysis, DFT calculations, and a comparison of experimental and calculated13C NMR chemical shifts. The hydrazinobuckybowl is the first buckybowl that changes its geometry between curved bowl/twist structures and a planar structure depending on the oxidation state. The drastic geometrical change was possible as a result of the presence of two heteroatoms in the bowl skeleton and the multiple reversible redox reactions of the compound. Owing to the two kinds of bowl and twist conformations, the bowl-inversion dynamics of the hydrazinobuckybowl were found to follow a triple-well potential model.
KW - cations
KW - conformation analysis
KW - heterobuckybowls
KW - heterocycles
KW - redox chemistry
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U2 - 10.1002/anie.201605340
DO - 10.1002/anie.201605340
M3 - Article
AN - SCOPUS:84983499672
SN - 1433-7851
VL - 55
SP - 10830
EP - 10834
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
IS - 36
ER -