2,4,4,6,8,8-Hexanitro-2,6-diazaadamantane: A High-Energy Density Compound with High Stability

Zhang, Jian; Hou, Tianjiao; Lin, Zhongqin; Luo, Jun

doi:10.1021/acs.orglett.8b03107

Cited by 27 publications

(13 citation statements)

References 53 publications

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“…2,6-Diazaadamantane (DZD) is a promising framework for a spin label as it provides the possibility of maintaining small molecular size with the required functionalization. The construction of the adamantane framework requires laborious synthesis, , and the synthesis of adamantane nitroxide spin label is complicated by the substituent group required for SDSL.…”

Section: Resultsmentioning

confidence: 99%

Supramolecular Approach to Electron Paramagnetic Resonance Distance Measurement of Spin-Labeled Proteins

et al. 2020

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We demonstrate a host–guest molecular recognition approach to advance double electron–electron resonance (DEER) distance measurements of spin-labeled proteins. We synthesized an iodoacetamide derivative of 2,6-diazaadamantane nitroxide (DZD) spin label that could be doubly incorporated into T4 Lysozyme (T4L) by site-directed spin labeling with efficiency up to 50% per cysteine. The rigidity of the fused ring structure and absence of mobile methyl groups increase the spin echo dephasing time (T m) at temperatures above 80 K. This enables DEER measurements of distances >4 nm in DZD-labeled T4L in glycerol/water at temperatures up to 150 K with increased sensitivity compared to that of a common spin label such as MTSL. Addition of β-cyclodextrin reduces the rotational correlation time of the label, slightly increases T m, and most importantly, narrows (and slightly lengthens) the interspin distance distributions. The distance distributions are in good agreement with simulated distance distributions obtained by rotamer libraries. These results provide a foundation for developing supramolecular recognition to facilitate long-distance DEER measurements at near physiological temperatures.

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Section: Resultsmentioning

confidence: 99%

Supramolecular Approach to Electron Paramagnetic Resonance Distance Measurement of Spin-Labeled Proteins

et al. 2020

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“…Therefore, these high-nitrogen compounds are considered to be promising candidates as energetic materials. Also, there are few known examples of polynitro substituted carbocyclic cage derivatives 1-8 [60][61][62][63][64][65][66] that exhibit high energetic performance which are listed in Figure 1. Among nitro-rich cage compounds 1-8, octanitrocubane (ONC, 2) [17,24] reported by Eaton and co-workers shows high energetic performance as well as superior explosive nature over presently used most powerful explosive CL-20 (1).…”

Section: Introductionmentioning

confidence: 99%

Pentacycloundecane (PCUD)‐Based Cage Frameworks as Potential Energetic Materials: Syntheses and Characterization

et al. 2020

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A new variety of cage frameworks containing pentacycloundecane (PCUD) were synthesized. These compounds contain azide and triazole units. Four new cage frameworks were designed and constructed starting from easily accessible starting materials such as 2,3-dimethylhydroquinone, 1,4-dimethoxybenzene, and dicyclopentadiene using [2 + 2] photocycloaddition as the key step. The structures of these symmetrical cage bis-azide and cage bistriazole compounds have been confirmed by single-crystal X-ray diffraction studies. DFT analysis at different levels of theory were used to optimize the geometries and compute the heats of formation of the title compounds. Their propulsive and explosive properties were also calculated using suitable computational methods. The thermodynamic stability of the title compounds was theoretically analysed based on their bond dissociation energies. The thermal stability was evaluated by TGA-coupled FTIR analysis.

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“…We studied several representative caged polynitroamino energetic compounds, including CL-20, TEX, and ONC. Additionally, for the sake of completeness, we also considered representative polynitro species containing gem-dinitro groups, viz., 2,2,4,4,6,6-hexanitroadamantane (HNA, 4 , Chart ), , and two very recently reported nitramino derivatives: 2,4,4,8,8-pentanitro-2-azaadamantane ( 5 ) and 2,4,4,6,8,8-hexanitro-2,6-diazaadamantane (HNDAA, 6 ) containing mixed dintro- and nitroamino functionalities. , Ultimately, we considered the radical and molecular primary decomposition reactions of all species studied at the DLPNO-CCSD(T)/jun-cc-pVQZ level of theory and obtained the most accurate values of bond energies and activation barriers of molecular channels among those reported up to date.…”

Section: Introductionmentioning

confidence: 99%

Accurate Prediction of Bond Dissociation Energies and Barrier Heights for High-Energy Caged Nitro and Nitroamino Compounds Using a Coupled Cluster Theory

Kiselev

Goldsmith

2019

J. Phys. Chem. A

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Highly accurate theoretical values of bond energies and activation barriers of primary decomposition reactions are crucial for reliable predictions of thermal decomposition and detonation-related phenomena of energetic materials (EM). However, due to the prohibitive computational cost, high-level ab initio calculations had been impractical for a large number of important EMs, including, e.g., hexanitrohexaazaisowurtzitane (CL-20). In the present work, we obtained accurate bond dissociation energies and the activation barriers for primary decomposition reactions for a series of novel promising caged polynitroamino and polynitro EMs, viz., CL-20, TEX, octanitrocubane (ONC), and hexanitro derivatives of adamantane, using the recently proposed domain-localized pair natural orbitals (DLPNO) modifications of coupled cluster techniques. DLPNO-CCSD(T) allows for routine quadruple-ζ basis set quality coupled cluster calculations for the species comprised of ∼30 non-H atoms. The benchmarks on a number of simpler congeners of CL-20 and ONC revealed that the DLPNO approach does not deteriorate the quality of the quadruple-ζ coupled cluster procedure. With the aid of this technique, the full set of gas-phase primary decomposition reactions for all 9 conformers of CL-20 was considered. For all species studied, C−NO 2 or N−NO 2 radical decomposition channels dominate over molecular counterparts. The best theoretical results reported in the literature so far, viz., density functional theory energies of nitro group radical elimination in CL-20 and ONC, underestimate the value by ∼10 kcal mol −1 . We also present reliable and accurate gas-phase formation enthalpies for CL-20, ONC, and related species. In a more general sense, these results offer a new level of predictive computational kinetics for polynitro-caged energetic materials.

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2,4,4,6,8,8-Hexanitro-2,6-diazaadamantane: A High-Energy Density Compound with High Stability

Cited by 27 publications

References 53 publications

Supramolecular Approach to Electron Paramagnetic Resonance Distance Measurement of Spin-Labeled Proteins

Supramolecular Approach to Electron Paramagnetic Resonance Distance Measurement of Spin-Labeled Proteins

Pentacycloundecane (PCUD)‐Based Cage Frameworks as Potential Energetic Materials: Syntheses and Characterization

Accurate Prediction of Bond Dissociation Energies and Barrier Heights for High-Energy Caged Nitro and Nitroamino Compounds Using a Coupled Cluster Theory

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