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

Myers, Thomas W.; Bjorgaard, Josiah; Brown, Kathryn E.; Chávez, David E.; Hanson, Susan K.; Scharff, R. Jason; Tretiak, Sergei; Veauthier, Jacqueline M.

doi:10.1021/jacs.6b02155

Cited by 137 publications

(106 citation statements)

References 36 publications

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“…In recent years, more and more research groups all over the world have been working intensively on new laser ignitable energetic materials . The laser initiation shows many advantages compared to conventional methods like mechanical stimuli or heat and investigated compounds do not require high sensitivities toward the customary stimuli.…”

Section: Resultsmentioning

confidence: 99%

Methylsemicarbazide as a Ligand in Late 3d Transition Metal Complexes

Szimhardt

Stierstorfer

2018

Chemistry A European J

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Most ignition and initiation systems nowadays still contain poisonous chemicals such as lead styphnate and lead azide but also chromates and other compounds of high concern. Therefore, methylsemicarbazide (1, MSC), which can be prepared in a one-step reaction and in an extraordinary high yield of 95 %, has been evaluated as ligand in energetic coordination compounds. For the first time 25 new transition metal complexes (Mn , Ni , Co , Cu , and Zn ) using methylsemicarbazide (1) as the ligand were prepared and comprehensively analyzed by, for example, XRD, IR, EA, UV/Vis and DSC/DTA/TGA. Many show a strong energetic character, which can be tuned by using different anions such as Cl , SO , NO , ClO , picrate or styphnate. Selected compounds were additionally evaluated as lead-free primary explosives in initiation tests (nitropenta filled detonators) and in laser ignition systems. Especially compound 7 showed very promising results during these tests and could be a potential candidate for future applications.

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Section: Resultsmentioning

confidence: 99%

Methylsemicarbazide as a Ligand in Late 3d Transition Metal Complexes

Szimhardt

Stierstorfer

2018

Chemistry A European J

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“…Energetic materials can be ignited by a variety of different initiation methods (e.g., mechanical, heat, electrical). In particular, the initiation by optical means such as laser has attracted increasing attention in recent years . Most of the ignition mechanisms currently in use still involve traditional techniques due to their great simplicity.…”

Section: Resultsmentioning

confidence: 99%

“…The most significant advantage of this concept is the possible alteration of the three different components, namely 1) the metal, 2) the anion, and 3) the ligand, which allows an exact adjustment of the optical and energetic properties (Figure ). In recent years, a large number of different combinations have been reported in the literature . Another benefit of this approach, in addition to the ease of manufacture, includes the possibility of moving away from toxic heavy metals like lead or mercury to more environmentally friendly alternatives such as copper, iron, manganese, or zinc, which exhibit significantly lower toxicity .…”

Section: Introductionmentioning

confidence: 99%

1‐AminoTriazole Transition‐Metal Complexes as Laser‐Ignitable and Lead‐Free Primary Explosives

Szimhardt

Wurzenberger

Zeisel

et al. 2018

Chemistry A European J

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This unique complex study describes two isomeric aminotriazoles as auspicious nitrogen-rich ligands for energetic coordination compounds (ECCs) to replace the commonly used highly poisonous and environmentally harmful lead-based primary explosives. The triazoles were obtained by easily scalable and convenient synthetic routes starting solely from commercially available starting materials. 1-Amino-1,2,3-triazole (1, 1-ATRI) and, for the first time, 1-amino-1,2,4-triazole (2, 1A-1,2,4-TRI) were employed as ligands to form highly energetic transition-metal(II) complexes. The desired characteristics could be altered successively by using various nonpoisonous metal(II) centers (Cu , Mn , Fe , and Zn ) and anions (Cl , NO , ClO , ClO , picrate, styphnate, 2,4,6-trinitro-3-hydroxyphenolate, and 2,4,6-trinitro-3,5-dihydroxyphenolate). The 14 synthesized coordination compounds were characterized comprehensively by XRD, IR and UV/Vis spectroscopy, elemental analysis, and differential thermal and thermogravimetric analyses. Ball-drop impact, electrostatic discharge (ESD), and mechanical (impact and friction) sensitivities were determined according to BAM standard methods. In addition to laser ignition experiments, selected ECCs were evaluated in classical secondary explosive initiation tests (detonators filled with pentaerythritol tetranitrate (nitropenta)), which revealed their enormous potential and proved them to be very attractive for future applications in explosives.

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“…Recent efforts have focused on photoactive energetic materials with absorption within the range of conventional lasers. [10][11][12][13][14][15][16][17][18][19][20][21][22][23] Introducing a fiber optic cable for direct optical initiation eliminates sensitivity to electrical insults, while replacing primary explosives with less sensitive secondary explosives reduces sensitivity to mechanical insults. A class of energetic materials that exhibit the optical, electrical, and mechanical properties suitable for this application are conjugated energetic molecules (CEMs).…”

Section: Introductionmentioning

confidence: 99%

Cooperative enhancement of the nonlinear optical response in conjugated energetic materials: A TD-DFT study

Sifain

Tadesse

Bjorgaard

et al. 2017

The Journal of Chemical Physics

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Conjugated energetic molecules (CEMs) are a class of explosives with high nitrogen content that posses both enhanced safety and energetic performance properties and are ideal for direct optical initiation. As isolated molecules, they absorb within the range of conventional lasers. Crystalline CEMs are used in practice, however, and their properties can differ due to intermolecular interaction. Herein, time-dependent density functional theory was used to investigate one-photon absorption (OPA) and two-photon absorption (TPA) of monomers and dimers obtained from experimentally determined crystal structures of CEMs. OPA scales linearly with the number of chromophore units, while TPA scales nonlinearly, where a more than 3-fold enhancement in peak intensity, per chromophore unit, is calculated. Cooperative enhancement depends on electronic delocalization spanning both chromophore units. An increase in sensitivity to nonlinear laser initiation makes these materials suitable for practical use. This is the first study predicting a cooperative enhancement of the nonlinear optical response in energetic materials composed of relatively small molecules. The proposed model quantum chemistry is validated by comparison to crystal structure geometries and the optical absorption of these materials dissolved in solution.

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

Cited by 137 publications

References 36 publications

Methylsemicarbazide as a Ligand in Late 3d Transition Metal Complexes

Methylsemicarbazide as a Ligand in Late 3d Transition Metal Complexes

1‐AminoTriazole Transition‐Metal Complexes as Laser‐Ignitable and Lead‐Free Primary Explosives

Cooperative enhancement of the nonlinear optical response in conjugated energetic materials: A TD-DFT study

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