DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Laser initiation of Fe(II) complexes of 4-nitro-pyrazolyl substituted tetrazine ligands

Abstract

Here, the synthesis and characterization of new 1,2,4-triazolyl and 4-nitro-pyrazolyl substituted tetrazine ligands has been achieved. The strongly electron deficient 1,2,4-triazolyl substituted ligands did not coordinate Fe(II) metal centers, while the mildly electron deficient 4-nitro-pyrazolyl substituted ligands did coordinate Fe(II) metal centers in a 2:1 ratio of ligand to metal. The thermal stability and mechanical sensitivity characteristics of the complexes are similar to the conventional explosive pentaerythritol tetranitrate. The complexes had strong absorption in the visible region of the spectrum that extended into the near-infrared. In spite of having improved oxygen balances, increased mechanical sensitivity, and similar absorption of NIR light to recently reported Fe(II) tetrazine complexes, these newly synthesized explosives were more difficult to initiate with Nd:YAG pulsed laser light. More specifically, the complexes required lower densities (0.9 g/cm3) to initiate at the same threshold utilized to initiate previous materials at higher densities (1.05 g/cm3).

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1351988
Report Number(s):
LA-UR-16-29289
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 56; Journal Issue: 4; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Myers, Thomas Winfield, Brown, Kathryn Elizabeth, Chavez, David E., Scharff, Robert Jason, and Veauthier, Jacqueline Marie. Laser initiation of Fe(II) complexes of 4-nitro-pyrazolyl substituted tetrazine ligands. United States: N. p., 2017. Web. doi:10.1021/acs.inorgchem.6b02998.
Myers, Thomas Winfield, Brown, Kathryn Elizabeth, Chavez, David E., Scharff, Robert Jason, & Veauthier, Jacqueline Marie. Laser initiation of Fe(II) complexes of 4-nitro-pyrazolyl substituted tetrazine ligands. United States. https://doi.org/10.1021/acs.inorgchem.6b02998
Myers, Thomas Winfield, Brown, Kathryn Elizabeth, Chavez, David E., Scharff, Robert Jason, and Veauthier, Jacqueline Marie. Wed . "Laser initiation of Fe(II) complexes of 4-nitro-pyrazolyl substituted tetrazine ligands". United States. https://doi.org/10.1021/acs.inorgchem.6b02998. https://www.osti.gov/servlets/purl/1351988.
@article{osti_1351988,
title = {Laser initiation of Fe(II) complexes of 4-nitro-pyrazolyl substituted tetrazine ligands},
author = {Myers, Thomas Winfield and Brown, Kathryn Elizabeth and Chavez, David E. and Scharff, Robert Jason and Veauthier, Jacqueline Marie},
abstractNote = {Here, the synthesis and characterization of new 1,2,4-triazolyl and 4-nitro-pyrazolyl substituted tetrazine ligands has been achieved. The strongly electron deficient 1,2,4-triazolyl substituted ligands did not coordinate Fe(II) metal centers, while the mildly electron deficient 4-nitro-pyrazolyl substituted ligands did coordinate Fe(II) metal centers in a 2:1 ratio of ligand to metal. The thermal stability and mechanical sensitivity characteristics of the complexes are similar to the conventional explosive pentaerythritol tetranitrate. The complexes had strong absorption in the visible region of the spectrum that extended into the near-infrared. In spite of having improved oxygen balances, increased mechanical sensitivity, and similar absorption of NIR light to recently reported Fe(II) tetrazine complexes, these newly synthesized explosives were more difficult to initiate with Nd:YAG pulsed laser light. More specifically, the complexes required lower densities (0.9 g/cm3) to initiate at the same threshold utilized to initiate previous materials at higher densities (1.05 g/cm3).},
doi = {10.1021/acs.inorgchem.6b02998},
journal = {Inorganic Chemistry},
number = 4,
volume = 56,
place = {United States},
year = {2017},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Laser-excited detonation of condensed explosives
journal, January 1969

  • Brish, A. A.; Galeev, I. A.; Zaitsev, B. N.
  • Combustion, Explosion, and Shock Waves, Vol. 2, Issue 3
  • DOI: 10.1007/BF00749034

Formation of local hot spots during the fracture of thin layers under shock
journal, April 1972

  • Afanas'ev, G. T.; Bobolev, V. K.; Kazarova, Yu. A.
  • Combustion, Explosion, and Shock Waves, Vol. 8, Issue 2
  • DOI: 10.1007/BF00740454

On the laser ignition and initiation of explosives
journal, June 2001

  • Bourne, N. K.
  • Proceedings of the Royal Society of London. Series A: Mathematical, Physical and Engineering Sciences, Vol. 457, Issue 2010
  • DOI: 10.1098/rspa.2000.0721

Low energy laser initiation of single crystals of ?-lead azide
journal, September 1981

  • Hagan, J. T.; Chaudhri, M. M.
  • Journal of Materials Science, Vol. 16, Issue 9
  • DOI: 10.1007/BF01113582

Photosensitive Metal(II) Perchlorates with 1,2-Bis[5-(1-methylhydrazinyl)tetrazol-1-yl]ethane as Ligand: Synthesis, Characterization and Laser Ignition: Photosensitive Metal(II) Perchlorates
journal, December 2013

  • Joas, Manuel; Klapötke, Thomas M.; Szimhardt, Norbert
  • European Journal of Inorganic Chemistry, Vol. 2014, Issue 3
  • DOI: 10.1002/ejic.201301283

Cocrystallization of Photosensitive Energetic Copper(II) Perchlorate Complexes with the Nitrogen-rich Ligand 1,2-Di(1 H -tetrazol-5-yl)ethane
journal, October 2014

  • Evers, Jürgen; Gospodinov, Ivan; Joas, Manuel
  • Inorganic Chemistry, Vol. 53, Issue 21
  • DOI: 10.1021/ic5020175

Copper Salts of Halo Tetrazoles: Laser-Ignitable Primary Explosives
journal, October 2011

  • Fischer, Dennis; Klapötke, Thomas M.; Piercey, Davin G.
  • Journal of Energetic Materials, Vol. 30, Issue 1
  • DOI: 10.1080/07370652.2010.539998

Laser Initiation of Tris(carbohydrazide)metal(II) Perchlorates and Bis(carbohydrazide)diperchlorato-copper(II)
journal, September 2014

  • Joas, Manuel; Klapötke, Thomas M.
  • Propellants, Explosives, Pyrotechnics, Vol. 40, Issue 2
  • DOI: 10.1002/prep.201400142

Effect of the laser radiation wavelength on the energy threshold of initiation of heavy metal azides
journal, September 2011

  • Lisitsyn, V. M.; Tsipilev, V. N.; Damamme, G.
  • Combustion, Explosion, and Shock Waves, Vol. 47, Issue 5
  • DOI: 10.1134/S0010508211050133

Energetic Chromophores: Low-Energy Laser Initiation in Explosive Fe(II) Tetrazine Complexes
journal, March 2016

  • Myers, Thomas W.; Bjorgaard, Josiah A.; Brown, Kathryn E.
  • Journal of the American Chemical Society, Vol. 138, Issue 13
  • DOI: 10.1021/jacs.6b02155

The influence of added aluminum nanoparticles on the sensitivity of pentaerythritol tetranitrate to laser irradiation
journal, April 2011


Explosive decomposition of PETN with nanoaluminum additives under the influence of pulsed laser radiation at different wavelengths
journal, July 2013

  • Aduev, B. P.; Nurmukhametov, D. R.; Furega, R. I.
  • Russian Journal of Physical Chemistry B, Vol. 7, Issue 4
  • DOI: 10.1134/S199079311304012X

Controlling pentaerythrite tetranitrate sensitivity to the laser effect through the addition of nickel and aluminum nanoparticles
journal, May 2014

  • Aduev, B. P.; Nurmukhametov, D. R.; Furega, R. I.
  • Russian Journal of Physical Chemistry B, Vol. 8, Issue 3
  • DOI: 10.1134/S1990793114030178

Characteristics of the initiation of the explosive decomposition of PETN by the second-harmonic pulsed radiation of a neodymium laser
journal, November 2015

  • Aduev, B. P.; Nurmukhametov, D. R.; Liskov, I. Yu.
  • Russian Journal of Physical Chemistry B, Vol. 9, Issue 6
  • DOI: 10.1134/S1990793115060020

Laser initiation of PETN–iron nanoparticle composites
journal, July 2016

  • Aduev, B. P.; Nurmukhametov, D. R.; Zvekov, A. A.
  • Russian Journal of Physical Chemistry B, Vol. 10, Issue 4
  • DOI: 10.1134/S1990793116040023

Plasmonic Enhancement of Direct Optical Initiation of Explosives
conference, January 2009

  • Moore, D. S.; Akinci, A. A.; Giambra, A. M.
  • SHOCK COMPRESSION OF CONDENSED MATTER 2009: Proceedings of the American Physical Society Topical Group on Shock Compression of Condensed Matter, AIP Conference Proceedings
  • DOI: 10.1063/1.3295092

Transition Metal Complexes of 3-Amino-1-nitroguanidine as Laser Ignitible Primary Explosives: Structures and Properties
journal, November 2013

  • Fischer, Niko; Joas, Manuel; Klapötke, Thomas M.
  • Inorganic Chemistry, Vol. 52, Issue 23
  • DOI: 10.1021/ic402038x

Thermally Stable 3,6-Disubstituted 1,2,4,5-Tetrazines
journal, December 2013

  • Klapötke, Thomas M.; Preimesser, Andreas; Stierstorfer, Jörg
  • Zeitschrift für Naturforschung B, Vol. 68, Issue 12
  • DOI: 10.5560/znb.2013-3237

N -Oxide 1,2,4,5-Tetrazine-Based High-Performance Energetic Materials
journal, October 2014

  • Wei, Hao; Gao, Haixiang; Shreeve, Jean'ne M.
  • Chemistry - A European Journal, Vol. 20, Issue 51
  • DOI: 10.1002/chem.201405122

Synthesis of the bi-heterocyclic parent ring system 1,2,4-triazolo[4,3- b ][1,2,4,5]tetrazine and some 3,6-disubstituted derivatives
journal, November 1998

  • Chavez, David E.; Hiskey, Michael A.
  • Journal of Heterocyclic Chemistry, Vol. 35, Issue 6
  • DOI: 10.1002/jhet.5570350616

Independent Control of Optical and Explosive Properties: Pyrazole–Tetrazine Complexes of First Row Transition Metals
journal, August 2015


Valence delocalisation in a strongly coupled (Kc = 1014) molecule-bridged cyanodiiron(III,II) species
journal, January 1998

  • Ketterle, Michael; Kaim, Wolfgang; Fiedler, Jan
  • Chemical Communications, Issue 16
  • DOI: 10.1039/a804279i

Laser initiation of PETN
journal, July 1996

  • Tarzhanov, V. I.; Zinchenko, A. D.; Sdobnov, V. I.
  • Combustion, Explosion, and Shock Waves, Vol. 32, Issue 4
  • DOI: 10.1007/BF01998499

Chemical modification of single walled carbon nanotubes with tetrazine-tethered gold nanoparticles via a Diels–Alder reaction
journal, January 2013

  • Zhu, Jun; Hiltz, Jonathan; Lennox, R. Bruce
  • Chemical Communications, Vol. 49, Issue 87
  • DOI: 10.1039/c3cc46325g

Works referencing / citing this record:

Comparison of 1‐Ethyl‐5 H ‐tetrazole and 1‐Azidoethyl‐5 H ‐tetrazole as Ligands in Energetic Transition Metal Complexes
journal, April 2019

  • Wurzenberger, Maximilian H. H.; Gruhne, Michael S.; Lommel, Marcus
  • Chemistry – An Asian Journal, Vol. 14, Issue 11
  • DOI: 10.1002/asia.201900269

2-Methyl-substituted monotetrazoles in copper( ii ) perchlorate complexes: manipulating coordination chemistry and derived energetic properties
journal, January 2019

  • Zeisel, Lukas; Szimhardt, Norbert; Wurzenberger, Maximilian H. H.
  • New Journal of Chemistry, Vol. 43, Issue 2
  • DOI: 10.1039/c8nj05375h

Synthesis and properties of insensitive [1,2,4]triazolo[4,3- b ]-1,2,4,5-tetrazine explosives
journal, January 2019

  • Wang, Guilong; Lu, Tian; Fan, Guijuan
  • New Journal of Chemistry, Vol. 43, Issue 4
  • DOI: 10.1039/c8nj05220d

Versatile coordination behaviour of the chloro-tetrazine-picolylamine ligand: mixed-valence binuclear Cu( i )/Cu( ii ) complexes
journal, January 2019

  • Stetsiuk, Oleh; Petrusenko, Svitlana R.; Sorace, Lorenzo
  • Dalton Transactions, Vol. 48, Issue 31
  • DOI: 10.1039/c9dt02379h

Identification and formation mechanism of the transient ion fragments produced in laser-induced dissociation of 1, 1-diamino-2, 2-dinitroethylene
journal, September 2018


Incorporation of a nitrogen-rich energetic ligand in a {YbIII2} complex exhibiting slow relaxation of the magnetisation under an applied field
journal, January 2020

  • Richardson, Paul; Gálico, Diogo Alves; Ovens, Jeffrey
  • Dalton Transactions, Vol. 49, Issue 30
  • DOI: 10.1039/d0dt00696c

Highly functional energetic complexes: stability tuning through coordination diversity of isomeric propyl-linked ditetrazoles
journal, January 2018

  • Szimhardt, Norbert; Wurzenberger, Maximilian H. H.; Klapötke, Thomas M.
  • Journal of Materials Chemistry A, Vol. 6, Issue 15
  • DOI: 10.1039/c8ta01412d

The Chemistry and Properties of Energetic Materials Bearing [1,2,4]Triazolo[4,3- b ][1,2,4,5]tetrazine Fused Rings
journal, October 2018

  • Wang, Guilong; Lu, Tian; Fan, Guijuan
  • Chemistry - An Asian Journal, Vol. 13, Issue 23
  • DOI: 10.1002/asia.201801145

Methylsemicarbazide as a Ligand in Late 3d Transition Metal Complexes
journal, January 2018

  • Szimhardt, Norbert; Stierstorfer, Jörg
  • Chemistry - A European Journal, Vol. 24, Issue 11
  • DOI: 10.1002/chem.201705030

Maximization of the energy capability level in transition metal complexes through application of 1-amino- and 2-amino-5 H -tetrazole ligands
journal, January 2018

  • Szimhardt, Norbert; Wurzenberger, Maximilian H. H.; Zeisel, Lukas
  • Journal of Materials Chemistry A, Vol. 6, Issue 33
  • DOI: 10.1039/c8ta06326e

Energetic π-conjugated vinyl bridged triazoles: a thermally stable and insensitive heterocyclic cation
journal, January 2017

  • Ma, Qing; chen, Ya; Liao, Longyu
  • Dalton Transactions, Vol. 46, Issue 23
  • DOI: 10.1039/c7dt01261f