Independent Control of Optical and Explosive Properties: Pyrazole–Tetrazine Complexes of First Row Transition Metals
Abstract
In this study, complexes of 3-amino-6-(3,5-dimethylpyrazole)tetrazine) (NH2TzDMP, 1) and 3-(3,3'-dinitroazetidine)-6-(3,5-dimethylpyrazole)tetrazine) (DNAZTzDMP, 2) with first row transition metal centers were synthesized. Reactions of FeII(H2O)6(BF4)2 and Fe(NO3)3·9H2O with 1 and 2 both led to complexes of the form [(RTzDMP)3Fe]X2 (X = BF4, R = NH2 (3), DNAZ (4); X = NO3, R = NH2 (5), DNAZ (6)), which showed intense MLCT bands in the visible region of the spectrum. Ligands 1 and 2 also reacted with CuII(NO3)2·5/2H2O to form [(RTzDMP)2Cu(NO3)][NO3] (R = NH2 (7), DNAZ (8)) in addition to reacting with CuI(CH3CN)4(PF6) to form [(RTzDMP)2Cu][PF6] (R = NH2 (9), DNAZ (10)). Finally, reactions of 1 and 2 with Co(NO3)2·6H2O and Ni(NO3)2·6H2O led to [(NH2TzDMP)2Co(H2O) (NO3)][NO3] (11), [(DNAZTzDMP)2Co(H2O)2][NO3]2 (12), [(NH2TzDMP)3Ni][NO3]2 (13), and [(DNAZTzDMP)2Ni(H2O)2][NO3]2 (14). The complexes display rich electrochemical and photophysical properties that are unaffected by derivation with explosive groups.
- Authors:
-
- 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 Laboratory Directed Research and Development (LDRD) Program
- OSTI Identifier:
- 1492647
- Report Number(s):
- LA-UR-15-24236
Journal ID: ISSN 0020-1669
- Grant/Contract Number:
- 89233218CNA000001
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 54; Journal Issue: 16; 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, Chavez, David E., Hanson, Susan Kloek, Scharff, Robert Jason, Scott, Brian Lindley, Veauthier, Jacqueline Marie, and Wu, Ruilian. Independent Control of Optical and Explosive Properties: Pyrazole–Tetrazine Complexes of First Row Transition Metals. United States: N. p., 2015.
Web. doi:10.1021/acs.inorgchem.5b01313.
Myers, Thomas Winfield, Chavez, David E., Hanson, Susan Kloek, Scharff, Robert Jason, Scott, Brian Lindley, Veauthier, Jacqueline Marie, & Wu, Ruilian. Independent Control of Optical and Explosive Properties: Pyrazole–Tetrazine Complexes of First Row Transition Metals. United States. https://doi.org/10.1021/acs.inorgchem.5b01313
Myers, Thomas Winfield, Chavez, David E., Hanson, Susan Kloek, Scharff, Robert Jason, Scott, Brian Lindley, Veauthier, Jacqueline Marie, and Wu, Ruilian. Mon .
"Independent Control of Optical and Explosive Properties: Pyrazole–Tetrazine Complexes of First Row Transition Metals". United States. https://doi.org/10.1021/acs.inorgchem.5b01313. https://www.osti.gov/servlets/purl/1492647.
@article{osti_1492647,
title = {Independent Control of Optical and Explosive Properties: Pyrazole–Tetrazine Complexes of First Row Transition Metals},
author = {Myers, Thomas Winfield and Chavez, David E. and Hanson, Susan Kloek and Scharff, Robert Jason and Scott, Brian Lindley and Veauthier, Jacqueline Marie and Wu, Ruilian},
abstractNote = {In this study, complexes of 3-amino-6-(3,5-dimethylpyrazole)tetrazine) (NH2TzDMP, 1) and 3-(3,3'-dinitroazetidine)-6-(3,5-dimethylpyrazole)tetrazine) (DNAZTzDMP, 2) with first row transition metal centers were synthesized. Reactions of FeII(H2O)6(BF4)2 and Fe(NO3)3·9H2O with 1 and 2 both led to complexes of the form [(RTzDMP)3Fe]X2 (X = BF4, R = NH2 (3), DNAZ (4); X = NO3, R = NH2 (5), DNAZ (6)), which showed intense MLCT bands in the visible region of the spectrum. Ligands 1 and 2 also reacted with CuII(NO3)2·5/2H2O to form [(RTzDMP)2Cu(NO3)][NO3] (R = NH2 (7), DNAZ (8)) in addition to reacting with CuI(CH3CN)4(PF6) to form [(RTzDMP)2Cu][PF6] (R = NH2 (9), DNAZ (10)). Finally, reactions of 1 and 2 with Co(NO3)2·6H2O and Ni(NO3)2·6H2O led to [(NH2TzDMP)2Co(H2O) (NO3)][NO3] (11), [(DNAZTzDMP)2Co(H2O)2][NO3]2 (12), [(NH2TzDMP)3Ni][NO3]2 (13), and [(DNAZTzDMP)2Ni(H2O)2][NO3]2 (14). The complexes display rich electrochemical and photophysical properties that are unaffected by derivation with explosive groups.},
doi = {10.1021/acs.inorgchem.5b01313},
journal = {Inorganic Chemistry},
number = 16,
volume = 54,
place = {United States},
year = {Mon Aug 03 00:00:00 EDT 2015},
month = {Mon Aug 03 00:00:00 EDT 2015}
}
Web of Science
Works referenced in this record:
Laser initiation of energetic materials: a historical overview
conference, September 2007
- Bowden, M. D.; Cheeseman, M.; Knowles, S. L.
- Photonic Devices + Applications, SPIE Proceedings
Initiation of chemistry in molecular solids by processes involving electronic excited states
journal, February 2002
- Barry Kunz, A.; Kuklja, Maija M.; Botcher, T. R.
- Thermochimica Acta, Vol. 384, Issue 1-2
Ultrafast photodissociation dynamics of HMX and RDX from their excited electronic states via femtosecond laser pump–probe techniques
journal, October 2006
- Greenfield, M.; Guo, Y. Q.; Bernstein, E. R.
- Chemical Physics Letters, Vol. 430, Issue 4-6
Nonadiabatic Decomposition of Gas-Phase RDX through Conical Intersections: An ONIOM-CASSCF Study
journal, May 2011
- Bhattacharya, A.; Bernstein, E. R.
- The Journal of Physical Chemistry A, Vol. 115, Issue 17
Understanding Limits of the Thermal Mechanism of Laser Initiation of Energetic Materials
journal, November 2012
- Aluker, Edward D.; Krechetov, Alexander G.; Mitrofanov, Anatoliy Y.
- The Journal of Physical Chemistry C, Vol. 116, Issue 46
Design and Combustion Behaviour of Explosive Coordination Compounds.
journal, January 1996
- Sinditskii, V. P.; Serushkin, V. V.
- Defence Science Journal, Vol. 46, Issue 5
Green primary explosives: 5-Nitrotetrazolato-N2-ferrate hierarchies
journal, June 2006
- Huynh, M. H. V.; Coburn, M. D.; Meyer, T. J.
- Proceedings of the National Academy of Sciences, Vol. 103, Issue 27
Green primaries: Environmentally friendly energetic complexes
journal, March 2006
- Huynh, M. H. V.; Hiskey, M. A.; Meyer, T. J.
- Proceedings of the National Academy of Sciences, Vol. 103, Issue 14
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
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
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
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
Ultralow-Density Nanostructured Metal Foams: Combustion Synthesis, Morphology, and Composition
journal, May 2006
- Tappan, B. C.; Huynh, M. H.; Hiskey, M. A.
- Journal of the American Chemical Society, Vol. 128, Issue 20
Nanoporous Metal Foams
journal, May 2010
- Tappan, Bryce C.; Steiner, Stephen A.; Luther, Erik P.
- Angewandte Chemie International Edition, Vol. 49, Issue 27
Energetic Nitrogen-Rich Cu(II) and Cd(II) 5,5′-Azobis(tetrazolate) Complexes
journal, September 2009
- Tao, Guo-Hong; Twamley, Brendan; Shreeve, Jean’ne M.
- Inorganic Chemistry, Vol. 48, Issue 20
Nitrogen-Rich 5-(1-Methylhydrazinyl)tetrazole and its Copper and Silver Complexes
journal, April 2012
- Tao, Guo-Hong; Parrish, Damon A.; Shreeve, Jean’ne M.
- Inorganic Chemistry, Vol. 51, Issue 9
Synthesis and Characterization of Various Photosensitive Copper(II) Complexes with 5-(1-Methylhydrazinyl)-1 H -tetrazole as Ligand and Perchlorate, Nitrate, Dinitramide, and Chloride as Anions
journal, June 2013
- Joas, Manuel; Klapötke, Thomas M.; Stierstorfer, Jörg
- Chemistry - A European Journal, Vol. 19, Issue 30
Energetic Salts of 5-(5-Azido-1 H -1,2,4-triazol-3-yl)tetrazole
journal, February 2014
- Huber, Stefan; Izsák, Dániel; Karaghiosoff, Konstantin
- Propellants, Explosives, Pyrotechnics, Vol. 39, Issue 6
Recent Advances in the Chemistry of N5+, N5− and High-Oxygen Compounds
journal, June 2007
- Christe, Karl O.
- Propellants, Explosives, Pyrotechnics, Vol. 32, Issue 3
Bistetrazoles: Nitrogen-Rich, High-Performing, Insensitive Energetic Compounds
journal, June 2008
- Klapötke, Thomas M.; Sabaté, Carles Miró
- Chemistry of Materials, Vol. 20, Issue 11
Polyazidopyrimidines: High-Energy Compounds and Precursors to Carbon Nanotubes
journal, November 2006
- Ye, Chengfeng; Gao, Haixiang; Boatz, Jerry A.
- Angewandte Chemie International Edition, Vol. 45, Issue 43
Tetrazine Explosives
journal, August 2004
- Chavez, David E.; Hiskey, Michael A.; Naud, Darren L.
- Propellants, Explosives, Pyrotechnics, Vol. 29, Issue 4
New High-Nitrogen Materials Based on Nitroguanyl-Tetrazines: Explosive Properties, Thermal Decomposition and Combustion Studies
journal, December 2005
- Chavez, David E.; Tappan, Bryce C.; Hiskey, Michael A.
- Propellants, Explosives, Pyrotechnics, Vol. 30, Issue 6
3,3′-Azobis(6-amino-1,2,4,5-tetrazine): A Novel High-Nitrogen Energetic Material
journal, May 2000
- Chavez, David E.; Hiskey, Michael A.; Gilardi, Richard D.
- Angewandte Chemie International Edition, Vol. 39, Issue 10
s -Tetrazines as Building Blocks for New Functional Molecules and Molecular Materials
journal, June 2010
- Clavier, Gilles; Audebert, Pierre
- Chemical Reviews, Vol. 110, Issue 6
Synthesis of 3,6-bis(3-azido-1,2,4-triazol-1-yl)-1,2,4,5-tetrazine
journal, January 2009
- Chavez, David E.; Gilardi, Richard D.
- Journal of Energetic Materials, Vol. 27, Issue 2
New energetic materials from triazoles and tetrazines
journal, December 1994
- Licht, Hans-Heinrich; Ritter, Helmut
- Journal of Energetic Materials, Vol. 12, Issue 4
Synthesis of Azido Heterocycles
journal, February 2008
- Duddu, Raja; Dave, Paritosh R.; Damavarapu, Reddy
- Synthetic Communications, Vol. 38, Issue 5
3,6-Di(azido)-1,2,4,5-Tetrazine: A Precursor for the Preparation of Carbon Nanospheres and Nitrogen-Rich Carbon Nitrides
journal, October 2004
- Huynh, My Hang V.; Hiskey, Michael A.; Archuleta, Jose G.
- Angewandte Chemie International Edition, Vol. 43, Issue 42
Preparation of 1-substituted-3,3-dinitroazetidines
journal, June 1999
- Hiskey, Micheal A.; Johnson, M. Catherine; Chavez, David E.
- Journal of Energetic Materials, Vol. 17, Issue 2-3
1,2,4,5-tetrazine based energetic materials
journal, December 1999
- Chavez, David E.; Hiskey, Michael A.
- Journal of Energetic Materials, Vol. 17, Issue 4
An improved synthesis of 5-amino-3-nitro-1 H -1,2,4-triazole (ANTA), a useful intermediate for the preparation of insensitive high explosives
journal, December 1991
- Lee, K. -Y.; Storm, C. B.; Hiskey, M. A.
- Journal of Energetic Materials, Vol. 9, Issue 5
Electroactive Explosives: Nitrate Ester-Functionalized 1,2,4,5-Tetrazines
journal, May 2013
- Chavez, David E.; Hanson, Susan K.; Veauthier, Jacqueline M.
- Angewandte Chemie International Edition, Vol. 52, Issue 27
Paramagnetic copper(I) dimers
journal, May 1987
- Kaim, Wolfgang; Kohlmann, Stephan
- Inorganic Chemistry, Vol. 26, Issue 10
The First Crystal Structure of a Metal-Stabilized Tetrazine Anion Radical: Formation of a Dicopper Complex through Self-Assembly in a Comproportionation Reaction
journal, May 1999
- Schwach, Manuela; Hausen, Hans-Dieter; Kaim, Wolfgang
- Inorganic Chemistry, Vol. 38, Issue 10
Dicopper(I) Complexes with Reduced States of 3,6-Bis(2‘-pyrimidyl)-1,2,4,5-tetrazine: Crystal Structures and Spectroscopic Properties of the Free Ligand, a Radical Species, and a Complex of the 1,4-Dihydro Form
journal, May 2001
- Glöckle, Markus; Hübler, Klaus; Kümmerer, Hans-Jürgen
- Inorganic Chemistry, Vol. 40, Issue 10
Reduction of a Redox-Active Ligand Drives Switching in a Cu(I) Pseudorotaxane by a Bimolecular Mechanism
journal, January 2009
- McNitt, Kristy A.; Parimal, Kumar; Share, Andrew I.
- Journal of the American Chemical Society, Vol. 131, Issue 3
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
The Fe III /Fe II vs Fe 2 2.5 Formulation in Mixed-Valent Species [(NC) 4 Fe(BL)Fe(CN) 4 ] 3 - , BL = 2,2‘-Bipyrimidine and 3,6-Bis(2-pyridyl)-1,2,4,5-tetrazine. Distance and Size Do Not Always Matter
journal, June 1999
- Glöckle, Markus; Kaim, Wolfgang; Katz, Néstor E.
- Inorganic Chemistry, Vol. 38, Issue 14
Qualitatively and quantitatively different solvatochromism of the MLCT and MMCT absorption bands of centrosymmetric acceptor-bridged diiron(II,II) and diiron(III,II) cyanide complexes
journal, July 2002
- Glöckle, Markus; Katz, Néstor E.; Ketterle, Michael
- Inorganica Chimica Acta, Vol. 336
Nano-sized octa-nuclear nickel cationic complex: self-assembly on supramolecular level
journal, May 2002
- Eremenko, Igor L.; Malkov, Aleksei E.; Sidorov, Aleksei A.
- Inorganica Chimica Acta, Vol. 334
Pentanuclear pivalate Ni(II) and Co(II) clusters: modulation of molecular structures and magnetic properties
journal, August 2003
- Malkov, A. E.; Fomina, I. G.; Sidorov, A. A.
- Journal of Molecular Structure, Vol. 656, Issue 1-3
Synthesis, structures, and magnetic properties of crystals of dinuclear copper(II) and cobalt(II) complexes with 3-(3,5-dimethylpyrazol-1-yl)-6-R-1,2,4,5-tetrazines
journal, April 2010
- Cherdantseva, E. V.; Starichenko, D. V.; Slepukhin, P. A.
- Russian Chemical Bulletin, Vol. 59, Issue 4
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
Tetrazine derived mononuclear RuII(acac)2(L) (1), [RuII(bpy)2(L)](ClO4)2 (2) and [RuII(bpy)(L)2](ClO4)2 (3) (L=3-amino-6-(3,5-dimethylpyrazol-1-yl)-1,2,4,5-tetrazine, acac=acetylacetonate, bpy=2,2′-bipyridine): syntheses, structures, spectra and redox properties
journal, January 2005
- Nayak, Animesh; Patra, Srikanta; Sarkar, Biprajit
- Polyhedron, Vol. 24, Issue 2
Anion−π Interactions in Supramolecular Architectures
journal, June 2012
- Chifotides, Helen T.; Dunbar, Kim R.
- Accounts of Chemical Research, Vol. 46, Issue 4
Anion−π Interactions as Controlling Elements in Self-Assembly Reactions of Ag(I) Complexes with π-Acidic Aromatic Rings
journal, May 2006
- Schottel, Brandi L.; Chifotides, Helen T.; Shatruk, Mikhail
- Journal of the American Chemical Society, Vol. 128, Issue 17
Transition metal pentacoordination
journal, February 1975
- Rossi, Angelo R.; Hoffmann, Roald.
- Inorganic Chemistry, Vol. 14, Issue 2
Iron( ii ) and cobalt( ii ) complexes of tris-azinyl analogues of 2,2′:6′,2′′-terpyridine
journal, January 2013
- Kershaw Cook, Laurence J.; Tuna, Floriana; Halcrow, Malcolm A.
- Dalton Trans., Vol. 42, Issue 6
Determination of nitrogen in organic compounds by combustion in oxygen: Elimination of errors due to absorption of nitrogen oxides in copper oxide
journal, June 1966
- Swift, H.
- Microchemical Journal, Vol. 11, Issue 2
Works referencing / citing this record:
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
New green energetic materials based on unsymmetrically substituted pyrazole-tetrazines and their hydroperchlorates
journal, January 2019
- Yang, Zhen-Li; Wang, Zhen; Cao, Wen-li
- New Journal of Chemistry, Vol. 43, Issue 47
Synthesis and Characterization of Tetrahedral Zinc(II) Complexes with 3, 6,7-Triamino-7 H -[1, 2,4]triazolo[4, 3- b ][1, 2,4]triazole as Nitrogen-Rich Ligand : Synthesis and Characterization of Tetrahedral
journal, February 2016
- Klapötke, Thomas M.; Schmid, Philipp C.; Stierstorfer, Jörg
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 642, Issue 5
Azido and Tetrazolo 1,2,4,5-Tetrazine N-Oxides
journal, February 2017
- Chavez, David E.; Parrish, Damon A.; Mitchell, Lauren
- Angewandte Chemie International Edition, Vol. 56, Issue 13
Synthesis and Electrochemical Behavior of Electron-Rich s-Tetrazine and Triazolo-tetrazine Nitrate Esters
journal, June 2016
- Myers, Thomas W.; Snyder, Christopher J.; Chavez, David E.
- Chemistry - A European Journal, Vol. 22, Issue 30
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
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