Issue 35, 2018

A difunctional azido-cobalt(ii) coordination polymer exhibiting slow magnetic relaxation behaviour and high-energy characteristics with good thermostability and insensitivity

Abstract

A novel one-dimensional azido-cobalt(II) compound, [Co2(1-mbt)2(N3)4]n (1) (1-mbt = 1-((2-propyl-imidazol-1-yl)methyl)-benzo[1,2,3]triazole), was solvothermally synthesized. X-ray crystal structure analysis demonstrates that two crystallographically independent Co(II) atoms in the asymmetrical unit of compound 1 exhibit a rectangular pyramid geometry. The 3D supermolecular network of 1 consists of well-isolated 1D metal chains in which the azido bridging ligands assume an unusual pattern of combination with the Co(II) centre as the sign of [–EE–EO–EO–EO–]n. The various coordination modes of the azido anion are responsible for different magnetic exchanges between the adjacent Co(II) ions. The end-to-end (EE) mode mediates the antiferromagnetic coupling, whereas the end-on (EO) manner contributes to the ferromagnetic interaction. Magneto-structural relationships are discussed with the aid of theoretical calculations which are employed to find the potential single-ion magnetic anisotropy and reproduce the observed magnetic coupling properly. Alternating current magnetic susceptibility measurements reveal that 1 features a typical behaviour of field-induced slow magnetic relaxation. Energetic characterization evidences that the resulting compound possesses satisfactory detonation properties, superior lack of sensitivity and thermostability owing to the high nitrogen content (N% = 40.10%) and a coherent intrachain configuration. The kinetic parameters of the exothermic processes for 1 are investigated by the Kissinger method and the Ozawa method. We note that 1 has potential application prospects as a new generation of environmentally friendly high-energy materials based on this nitrogen-rich and oxygen-free system. In addition, the compound is developed as a practical additive to promote the thermal decomposition of ammonium perchlorate (AP) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). The finding in this work highlights an example of effective development of advanced magneto-energetic materials.

Graphical abstract: A difunctional azido-cobalt(ii) coordination polymer exhibiting slow magnetic relaxation behaviour and high-energy characteristics with good thermostability and insensitivity

Supplementary files

Article information

Article type
Paper
Submitted
07 jun 2018
Accepted
20 jul 2018
First published
20 jul 2018

Dalton Trans., 2018,47, 12092-12104

A difunctional azido-cobalt(II) coordination polymer exhibiting slow magnetic relaxation behaviour and high-energy characteristics with good thermostability and insensitivity

X. Ma, Y. Liu, W. Song, Z. Wang, X. Liu, G. Xie, S. Chen and S. Gao, Dalton Trans., 2018, 47, 12092 DOI: 10.1039/C8DT02335B

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