TY - JOUR
T1 - New Insight into the Aromaticity of cyclo-N5-by Constructing 3D Arrays in Crystal Structures
AU - Xia, Honglei
AU - Qi, Xiujuan
AU - Zhang, Wenquan
AU - Huang, Shiliang
AU - Song, Siwei
AU - Liu, Yuji
AU - Luo, Jin
AU - Zhang, Qinghua
N1 - Publisher Copyright:
© 2020 American Chemical Society.
PY - 2021/1/6
Y1 - 2021/1/6
N2 - Pentazole (HN5) has been actively pursued due to its intriguing aesthetic structure and potential applications as ultrahigh energetic materials. It is generally accepted that cyclo-N5- is a highly symmetric ring with good aromaticity. In this work, we designed two innovative pentazolate salts with 3D arrays in their crystal structures and found that the aromaticity of the cyclo-N5- anion could be damaged by specific weak interactions. In such fascinating crystal structures, multiple cyclo-N5- anions are regularly stacked with two modes ("antiparallel"and "vertical") in the parallelepiped spaces constructed by chain cations, forming 3D arrays of cations and anions, respectively. Notably, the aromaticity of "vertical"cyclo-N5- anions is damaged due to the geometric changes caused by strong local hydrogen bonds at room temperature; meanwhile, the unstable "vertical"cyclo-N5- can be stabilized by sufficiently strong π-πinteractions. This is the first time that the aromaticity of a pentazole ring has been damaged by weak interactions. Such findings not only widen the understanding of aromaticity but also deepen the fundamental understanding of cyclo-N5- and contribute to the emerging pentazole chemistry.
AB - Pentazole (HN5) has been actively pursued due to its intriguing aesthetic structure and potential applications as ultrahigh energetic materials. It is generally accepted that cyclo-N5- is a highly symmetric ring with good aromaticity. In this work, we designed two innovative pentazolate salts with 3D arrays in their crystal structures and found that the aromaticity of the cyclo-N5- anion could be damaged by specific weak interactions. In such fascinating crystal structures, multiple cyclo-N5- anions are regularly stacked with two modes ("antiparallel"and "vertical") in the parallelepiped spaces constructed by chain cations, forming 3D arrays of cations and anions, respectively. Notably, the aromaticity of "vertical"cyclo-N5- anions is damaged due to the geometric changes caused by strong local hydrogen bonds at room temperature; meanwhile, the unstable "vertical"cyclo-N5- can be stabilized by sufficiently strong π-πinteractions. This is the first time that the aromaticity of a pentazole ring has been damaged by weak interactions. Such findings not only widen the understanding of aromaticity but also deepen the fundamental understanding of cyclo-N5- and contribute to the emerging pentazole chemistry.
UR - http://www.scopus.com/inward/record.url?scp=85099104327&partnerID=8YFLogxK
U2 - 10.1021/acs.cgd.0c01458
DO - 10.1021/acs.cgd.0c01458
M3 - 文章
AN - SCOPUS:85099104327
SN - 1528-7483
VL - 21
SP - 33
EP - 39
JO - Crystal Growth and Design
JF - Crystal Growth and Design
IS - 1
ER -