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Strategy for chemically riveting catenated nitrogen chains

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Abstract

Catenated nitrogen chains (CNCs) attract considerable attention because of their structural novelty, their high energy, and their potential as precursors for all-nitrogen materials. However, pure CNCs are unstable under ambient conditions, limiting their on-site or practical applications. Chemical riveting of a CNC involves the maintenance of the structure of a CNC and placing the CNC in a special chemical structure as a moiety of an entire molecule to stabilize it. Other structures, except from the CNC, are named rivets. In this study, the molecular geometry, bond order, natural bond orbital charge, and frontier orbital among the pure CNCs (Nx), Nx−, Nx+, and NxHy (x = 2–11) and CNCs riveted and implemented experimentally in several former studies are systematically analyzed and compared. The lone-pair repulsion between two neighboring N atoms is one of the primary factors for the low molecular stability of the pure CNCs and their derivatives. The riveted CNCs with rings are usually more stable than those with open chains. Moreover, the standard deviation of the bond orders or the bond lengths can be employed as an indicator for molecular stability, i.e., a lower standard deviation suggests higher molecular stability. Hence, electron-donating groups, groups with electronegativity within those of H and N atoms, as well as atoms or groups with empty orbitals are proposed to trap the lone pairs of CNCs as rivets to stabilize the CNCs. This strategy is expected to facilitate the creation of stable CNC-contained compounds with high structural novelty or high energy contents.

A strategy is proposed for chemically riveting instable CNCs to transform them into more stable ones.

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Funding

This study received financial support from the National Natural Science Foundation of China (No. 11602239), the Science and Technology Fund of CAEP (2015B0302052), and Horizontal project (18zh005604, 18zh0006).

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  1. Co-Innovation Center for New Energetic Materials, Southwest University of Science and Technology, Mianyang, 621010, Sichuan, China

    Xianfeng Wei, Ruihao Wang & Min Liu

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  1. Xianfeng Wei
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Correspondence to Xianfeng Wei.

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Supplementary Information SI.

It contains bond lengths, bond orders and NBO charges of related CNC species, and molecular orbitals of some CNCs and their relatives. (DOC 2092 kb)

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Wei, X., Wang, R. & Liu, M. Strategy for chemically riveting catenated nitrogen chains. J Mol Model 25, 345 (2019). https://doi.org/10.1007/s00894-019-4228-8

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