Derivatives of 3,6-Bis(3-aminofurazan-4-ylamino)-1,2,4,5-tetrazine: Excellent Energetic Properties with Lower Sensitivities

Qiong Yu; Hongwei Yang; Gregory H Imler; Damon A Parrish; Guangbin Cheng; Jean'ne M Shreeve

doi:10.1021/acsami.0c08526

Derivatives of 3,6-Bis(3-aminofurazan-4-ylamino)-1,2,4,5-tetrazine: Excellent Energetic Properties with Lower Sensitivities

ACS Appl Mater Interfaces. 2020 Jul 15;12(28):31522-31531. doi: 10.1021/acsami.0c08526. Epub 2020 Jun 30.

Authors

Qiong Yu¹, Hongwei Yang², Gregory H Imler³, Damon A Parrish³, Guangbin Cheng², Jean'ne M Shreeve¹

Affiliations

¹ Department of Chemistry, University of Idaho, Moscow, Idaho 83844-2343, United States.
² School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China.
³ Naval Research Laboratory, 4555 Overlook Avenue, Washington, District of Columbia 20375, United States.

PMID: 32545963
DOI: 10.1021/acsami.0c08526

Abstract

To find a balance between energy and safety, a series of compounds based on azo-, azoxy-, 1,4,2,5-dioxadiazene-, and 3,6-diamino-1,2,4,5-tetrazine-bridged bis(aminofurazan) were designed and synthesized. These compounds were analyzed by nitro group charges (Q_nitro) and bond dissociation energy (BDE) calculations, which are related to sensitivity and stability. Based on the calculated results, derivatives of 3,6-bis(3-aminofurazan-4-ylamino)-1,2,4,5-tetrazine have the largest values for -Q_nitro and BDE of all of the bis(aminofurazan) compounds. This shows that compounds based on 3,6-bis(3-aminofurazan-4-ylamino)-1,2,4,5-tetrazine have the lowest sensitivities and best stabilities, which has been substantiated by experiments. Additionally, their explosive properties remain essentially competitive with compounds based on azo-, azoxy-, and 1,4,2,5-dioxadiazene-bridged bis(aminofurazan). Hirshfeld surface calculations were also performed to better understand the relationship between the molecular structure and stability/sensitivity. This work highlights the value of 3,6-diamino-1,2,4,5-tetrazine as a linker to achieve good balance between safety and energy.

Keywords: energetic materials; explosive; furazan; nitrogen-rich compounds; tetrazine.