Heterocyclic annelated di(perylene bisimide): constructing bowl-shaped perylene bisimides by the combination of steric congestion and ring strain.
In this paper, we present the synthesis of S- and N-heterocyclic annelated di(perylene bisimide) with extraordinary doubly bowl-shaped structures. The structures of fused PBI bowls confirmed by single-crystal X-ray structure analysis and temperature-dependent (1)H NMR are realized by the introduction of the steric congestion in nonbay regions and by the concurrent formation of the five-membered heterorings strain in bay regions. On the basis of the geometry obtained from the X-ray analysis, the maximum POAV1 pyramidalization angle is found in N-heterocyclic annelated diPBI 7, as large as 4.7 degrees , indicating the formation of two PBI bowls with significant curvatures. Furthermore, to assist the electrochemical and spectroscopic characterization of the two bowl-shaped derivatives and to assess the influence of heteroatoms on the bowl curvature, quantum-chemically optimized atomic structures, electronic properties, and optical signatures were computed with density functional theory.
Qian
Hualei
H
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Yue
Wan
W
Zhen
Yonggang
Y
Di Motta
Simone
S
Di Donato
Eugenio
E
Negri
Fabrizia
F
Qu
Jianqiang
J
Xu
Wei
W
Zhu
Daoben
D
Wang
Zhaohui
Z