Comprehensive End-to-End Design of Novel High Energy Density Materials: I. Synthesis and Characterization of Oxadiazole Based Heterocycles

doi:10.1021/acs.jpcc.7b07584

Title: Comprehensive End-to-End Design of Novel High Energy Density Materials: I. Synthesis and Characterization of Oxadiazole Based Heterocycles

Abstract

A methodology to design novel energetic materials by means of a holistic approach that links synthesis, experimental characterization, quantum-chemical modeling, and statistical empirical evaluation is proposed. An analysis of the revealed structure–property–function correlations in the LLM compound series (oxadiazole-based heterocyclic energetics), BNFF, BNFF-1, LLM-172, LLM-191, and LLM-192, led us to predict, obtain, and characterize a new member in the materials family, LLM-200, which exhibits attractive energetic characteristics compared to known conventional high energy density materials. Finally, while the applied strategy convincingly demonstrated feasibility of the end-to-end design of high energy density materials, there are certain limitations in parallel improvements of sensitivity and performance within a single compound.

Authors:

Tsyshevsky, Roman ^[1]; Pagoria, Philip ^[2]; Zhang, Maoxi ^[2]; Racoveanu, Ana ^[2]; Parrish, Damon A. ^[3]; Smirnov, Aleksandr S. ^[4];

^[1]

Univ. of Maryland, College Park, MD (United States). Materials Science and Engineering Dept.
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Energetic Materials Center
Naval Research Lab. (NRL), Washington, DC (United States)
Bakhirev Scientific Research Inst. of Mechanical Engineering, Dzerzhinsk, Nizhny Novgorod (Russia)

Publication Date:: 2017-10-02

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Org.:: USDOE; National Science Foundation (NSF)

OSTI Identifier:: 1483296

Grant/Contract Number:: AC52-07NA27344; AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Physical Chemistry. C

Additional Journal Information:: Journal Volume: 121; Journal Issue: 43; Journal ID: ISSN 1932-7447

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Tsyshevsky, Roman, Pagoria, Philip, Zhang, Maoxi, Racoveanu, Ana, Parrish, Damon A., Smirnov, Aleksandr S., and Kuklja, Maija M. Comprehensive End-to-End Design of Novel High Energy Density Materials: I. Synthesis and Characterization of Oxadiazole Based Heterocycles.  United States: N. p., 2017. 
        Web.  doi:10.1021/acs.jpcc.7b07584.

Copy to clipboard


                    Tsyshevsky, Roman, Pagoria, Philip, Zhang, Maoxi, Racoveanu, Ana, Parrish, Damon A., Smirnov, Aleksandr S., & Kuklja, Maija M. Comprehensive End-to-End Design of Novel High Energy Density Materials: I. Synthesis and Characterization of Oxadiazole Based Heterocycles.  United States.  doi:https://doi.org/10.1021/acs.jpcc.7b07584

Copy to clipboard


                    Tsyshevsky, Roman, Pagoria, Philip, Zhang, Maoxi, Racoveanu, Ana, Parrish, Damon A., Smirnov, Aleksandr S., and Kuklja, Maija M. Mon .  
        "Comprehensive End-to-End Design of Novel High Energy Density Materials: I. Synthesis and Characterization of Oxadiazole Based Heterocycles".  United States.  doi:https://doi.org/10.1021/acs.jpcc.7b07584.  https://www.osti.gov/servlets/purl/1483296.

Copy to clipboard


                    
@article{osti_1483296,

  title        = {Comprehensive End-to-End Design of Novel High Energy Density Materials: I. Synthesis and Characterization of Oxadiazole Based Heterocycles},

  author       = {Tsyshevsky, Roman and Pagoria, Philip and Zhang, Maoxi and Racoveanu, Ana and Parrish, Damon A. and Smirnov, Aleksandr S. and Kuklja, Maija M.},

  abstractNote = {A methodology to design novel energetic materials by means of a holistic approach that links synthesis, experimental characterization, quantum-chemical modeling, and statistical empirical evaluation is proposed. An analysis of the revealed structure–property–function correlations in the LLM compound series (oxadiazole-based heterocyclic energetics), BNFF, BNFF-1, LLM-172, LLM-191, and LLM-192, led us to predict, obtain, and characterize a new member in the materials family, LLM-200, which exhibits attractive energetic characteristics compared to known conventional high energy density materials. Finally, while the applied strategy convincingly demonstrated feasibility of the end-to-end design of high energy density materials, there are certain limitations in parallel improvements of sensitivity and performance within a single compound.},

  doi          = {10.1021/acs.jpcc.7b07584},

  journal      = {Journal of Physical Chemistry. C},

  number       = 43,

  volume       = 121,

  place        = {United States},

  year         = {2017},

  month        = {10}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: https://doi.org/10.1021/acs.jpcc.7b07584

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 16 works

Citation information provided by
Web of Science

Figures / Tables:

Figure 1: Sketch representation of 3,4-Bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole-2- oxide (BNFF), 3,4-Bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (BNFF-1) and 3-(4- amino-1,2,5-oxadiazol-3-yl)-4-(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (ANFF-1), 3,5- Bis-(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,4-oxadiazole (LLM-191), 3-(4-amino-1,2,5-oxadiazol-3- yl)-5-(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,4-oxadiazole (LLM-192), and 3,3’-Bis(3-nitro-1,2,5- oxadiazol-4-yl)-5,5’-bi-1,2,4-oxadiazole (LLM-200) shows molecular building blocks in each compound. The color-coded circles are introduced to indicate a particular oxadiazole fragment: the red circle indicates the 1,2,5-oxadiazole-2-oxide ring; themore »

All figures and tables (9 total)

Save / Share:

Export Metadata

Save to My Library

Works referencing / citing this record:

An unexpected method to synthesise 1,2,4-oxadiazolone derivatives: a class of insensitive energetic materials
journal, January 2018

Wang, Bohan; Xiong, Hualin; Cheng, Guangbin
New Journal of Chemistry, Vol. 42, Issue 24
DOI: 10.1039/c8nj04428g

Boosting energetic performance by trimerizing furoxan
journal, January 2018

He, Chunlin; Gao, Haixiang; Imler, Gregory H.
Journal of Materials Chemistry A, Vol. 6, Issue 20
DOI: 10.1039/c8ta02274g

An unexpected method to synthesise 1,2,4-oxadiazolone derivatives: a class of insensitive energetic materials
journal, January 2018

Wang, Bohan; Xiong, Hualin; Cheng, Guangbin
New Journal of Chemistry, Vol. 42, Issue 24
DOI: 10.1039/c8nj04428g

Boosting energetic performance by trimerizing furoxan
journal, January 2018

He, Chunlin; Gao, Haixiang; Imler, Gregory H.
Journal of Materials Chemistry A, Vol. 6, Issue 20
DOI: 10.1039/c8ta02274g

Energetic N -azidomethyl derivatives of polynitro hexaazaisowurtzitanes series: CL-20 analogues having the highest enthalpy
journal, January 2020

Luk′yanov, Oleg A.; Parakhin, Vladimir V.; Shlykova, Nina I.
New Journal of Chemistry
DOI: 10.1039/d0nj01453b

1,2,4‐Oxadiazole‐Bridged Polynitropyrazole Energetic Materials with Enhanced Thermal Stability and Low Sensitivity
journal, October 2019

Yan, Tingou; Cheng, Guangbin; Yang, Hongwei
ChemPlusChem, Vol. 84, Issue 10
DOI: 10.1002/cplu.201900454

Figures / Tables found in this record:

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

Similar Records in DOE PAGES and OSTI.GOV collections:

Comprehensive End-to-End Design of Novel High Energy Density Materials: II. Computational Modeling and Predictions

Journal Article Tsyshevsky, Roman ; Pagoria, Philip ; Smirnov, Aleksandr S. ; ... - Journal of Physical Chemistry. C

In this work, we have proposed a holistic approach to design novel energetic materials by bridging synthesis, experimental characterization, computational modeling, and validation. Multiscale computational modeling that combines first-principles calculations, analytical theory, and empirical statistical analysis served to further advance the proposed methodology. The established materials design guiding principles led to development of a set of new energetic molecules, PHE-1, PHE-2, and PHE-3, that represent improved variations of the heterocyclic energetics and are predicted to be superior to the existing conventional energetic materials. Molecular mechanisms of the enhanced performance and sensitivity of the proposed energetic materials as a function ofmore »« less
Cited by 9
DOI: https://doi.org/10.1021/acs.jpcc.7b07585

Full Text Available
Comprehensive End-To-End Design of Novel High Energy Density Materials: III. Fused Heterocyclic Energetic Compounds

Journal Article Tsyshevsky, Roman ; Smirnov, Aleksandr S. ; Kuklja, Maija M. - Journal of Physical Chemistry. C

In contrast to synthesis and experimental characterization that are usually expensive and time-consuming, a coupled combination of ab initio and group additive theoretical methods represents a powerful alternative to computationally design and characterize new materials with targeted properties. Heterocyclic energetic materials are considered attractive candidates to replace conventional high explosives, such as PETN, RDX, HMX, and TNT. Heterocycles enable an intriguing opportunity for combinatorial design of new classes of energetic materials with targeted performance and sensitivity properties and offer ways for an accurate analysis of structure–property correlations of the materials. By using a computational strategy that links methods of quantummore »« less
Cited by 4
DOI: https://doi.org/10.1021/acs.jpcc.9b00863

Full Text Available
Synthesis and characterization of multicyclic oxadiazoles and 1-hydroxytetrazoles as energetic materials

Journal Article Pagoria, Philip F. ; Zhang, Mao-Xi ; Zuckerman, Nathaniel B. ; ... - Chemistry of Heterocyclic Compounds

Synthesis and characterization of several multicyclic oxadiazoles, 3,5-bis(4-nitrofurazan-3-yl)-1,2,4-oxadiazole, 3,3'-bis(4-nitrofurazan-3-yl)-5,5'-bi(1,2,4-oxadiazole), 3-(4-nitrofurazan-3-yl)-1,2,4-oxadiazol-5-amine, and salts of 1-hydroxytetrazoles, ammonium 5,5'-(1,2,4-oxadiazole-3,5-diyl)bis(1H-tetrazol-1-olate) and hydroxylammonium 5,5'-{[3,3'-bi(1,2,4-oxadiazole)]-5,5'-diyl}bis(1H-tetrazol-1-olate), as energetic materials are reported here. Two of the compounds, 3,5-bis(4-nitrofurazan-3-yl)-1,2,4-oxadiazole and 3,3'-bis(4-nitrofurazan-3-yl)-5,5'-bi(1,2,4-oxadiazole), have attractive single crystal densities of 1.91 and 1.94 g·cm^–3 (at 20°C), respectively. The design of these materials has been based on the idea that these multicyclic compounds with a 1,2,4-oxadiazole core will have good thermal stability and high density because of their 3,5-substitution pattern and the possibility of achieving a planar conformation. The various synthetic approaches and interesting chemistry observed during the construction of these new heterocyclesmore » has been described.« less
Cited by 30
DOI: https://doi.org/10.1007/s10593-017-2122-9

Full Text Available
Synthesis of Amino- and Nitro-Substituted Heterocycles as Insensitive Energetic Materials

Conference Pagoria, P F ; Lee, G S ; Mitchell, A R ; ...

In this paper we will describe the synthesis of several amino- and nitro-substituted heterocycles, examples from a continuing research project targeted at the synthesis of new, insensitive energetic materials that possess at least 80% the power of HMX (28% more power than TATB). Recently we reported the synthesis and scale-up of the insensitive energetic material, 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105). The energy content (81% the power of HMX) and thermal stability of LLM-105 make it a viable candidate material for insensitive boosters and deep oil perforation. We will report on recent synthetic improvements and several performance and safety tests performed on LLM-105, includingmore »« less
Full Text Available
Decomposition Mechanisms and Kinetics of Novel Energetic Molecules BNFF-1 and ANFF-1: Quantum-Chemical Modeling

Journal Article Tsyshevsky, Roman ; Kuklja, Maija - Molecules

Decomposition mechanisms, activation barriers, Arrhenius parameters, and reaction kinetics of the novel explosive compounds, 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl)- 1,2,5-oxadiazole (BNFF-1), and 3-(4-amino-1,2,5-oxadiazol-3-yl)-4-(4-nitro-1,2,5- oxadiazol-3-yl)-1,2,5-oxadiazole (ANFF-1) were explored by means of density functional theory with a range of functionals combined with variational transition state theory. BNFF1 and ANFF-1 were recently suggested to be good candidates for insensitive high energy density materials. Our modeling reveals that the decomposition initiation in both BNFF-1 and ANFF-1 molecules is triggered by ring cleavage reactions while the further process is defined by a competition between two major pathways, the fast C-NO2 homolysis and slow nitro-nitrite isomerization releasing NO. We discussmore »« less
DOI: https://doi.org/10.3390/molecules18078500

Full Text Available

Similar Records

Title: Comprehensive End-to-End Design of Novel High Energy Density Materials: I. Synthesis and Characterization of Oxadiazole Based Heterocycles

Abstract

Citation Formats

Figures / Tables:

An unexpected method to synthesise 1,2,4-oxadiazolone derivatives: a class of insensitive energetic materials journal, January 2018

Boosting energetic performance by trimerizing furoxan journal, January 2018

An unexpected method to synthesise 1,2,4-oxadiazolone derivatives: a class of insensitive energetic materials journal, January 2018

Boosting energetic performance by trimerizing furoxan journal, January 2018

Energetic N -azidomethyl derivatives of polynitro hexaazaisowurtzitanes series: CL-20 analogues having the highest enthalpy journal, January 2020

1,2,4‐Oxadiazole‐Bridged Polynitropyrazole Energetic Materials with Enhanced Thermal Stability and Low Sensitivity journal, October 2019

An unexpected method to synthesise 1,2,4-oxadiazolone derivatives: a class of insensitive energetic materials
journal, January 2018

Boosting energetic performance by trimerizing furoxan
journal, January 2018

An unexpected method to synthesise 1,2,4-oxadiazolone derivatives: a class of insensitive energetic materials
journal, January 2018

Boosting energetic performance by trimerizing furoxan
journal, January 2018

Energetic N -azidomethyl derivatives of polynitro hexaazaisowurtzitanes series: CL-20 analogues having the highest enthalpy
journal, January 2020

1,2,4‐Oxadiazole‐Bridged Polynitropyrazole Energetic Materials with Enhanced Thermal Stability and Low Sensitivity
journal, October 2019