N-amination of nitrogen-rich scaffolds: From single N–N bond formation to diverse energetic functionalization strategies

Energetic Materials Frontiers, Год журнала: 2021, Номер 2(4), С. 306 - 316

Опубликована: Дек. 1, 2021

The bond-formation strategy associated with carbon and nitrogen atoms is one of the most vital fundamental techniques in construction organic molecules. In comparison to well-established methodologies C–C C–N bond formation general synthetic chemistry, development N–N single for nitrogen-rich compounds relatively rare. This paper summarizes advances made N-amination reagents reaction conditions over recent five years terms high-energy frameworks, such as pyrazoles, 1,2,4-triazoles, 1,2,3-triazoles, 1,3,4-oxadiazoles. Furthermore, this discusses physiochemical properties N-amino heterocyclic their energetic derivatives, thereby holding great promise a guideline rational structural modification materials. work aimed at providing an overall view access diversely functionalized

Язык: Английский

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Taming of trinitromethyl-oxadiazole to access high density and high oxygen balance via a dual modulation strategy

Defence Technology, Год журнала: 2024, Номер unknown

Опубликована: Июль 1, 2024

Energetic compounds bearing the trinitromethyl group are garnering broad attraction as potential candidates for a new generation of high energy dense oxidizers. In this work, an effective dual modulation strategy involving both molecular isomerization and crystal morphology control was employed to design optimize trinitromethyl-oxadiazole with improved comprehensive performance. Utilizing strategy, 3,5-bis(trinitromethyl)-1,2,4-oxadiazole (3) synthesized, resulting in formation two distinct morphologies (needle sheet) corresponding forms (3-a 3-b). Encouragingly, while maintaining ultra-high oxygen balance (21.73%), 3 achieves impressive densities (1.97–1.98 g/cm3). To our knowledge, density 1.98 g/cm3 3-a sets record among that nitrogen-rich monocyclic compounds. Notably, practical prediction creatively introduced guide experimental crystallization conditions 3, increasing impact sensitivity friction from 1 J 80 N (3-a) 10 240 (3-b), respectively. Additionally, structural analyses theoretical calculations were conducted elucidate reasons differences between 3-b stability. This work provides efficient enhance performance derivatives, broadening path expanding toolbox energetic materials.

Язык: Английский

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The preparation of higher performance solid form of DATNBI based on rapid in-situ solvate-mediated phase transition mechanism

Chemical Engineering Journal, Год журнала: 2022, Номер 456, С. 141052 - 141052

Опубликована: Дек. 21, 2022

Язык: Английский

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Imidazole‐Based Energetic Materials: A Promising Family of N‐Heterocyclic Framework

Chemistry - An Asian Journal, Год журнала: 2022, Номер 17(21)

Опубликована: Сен. 8, 2022

Abstract Imidazole represents a fascinating class of explosophoric units with exciting structures and unique properties. As compared to other nitrogen‐rich heterocycles, imidazole demonstrates great potential applications due economic effectiveness superior energetic performances. The field traditional chemistry has been extensively explored for imidazole, thus established bond‐building methods functionalization strategies promote further development as high‐energy density materials (HEDMs). This review addresses the compounds in past decade, summarizes their physiochemical properties, is divided into three parts (explosives, propellants, biocides) according application requirements. Various synthetic these molecules are highlighted, including construction heterocyclic frameworks following functionalization. selected discussed reactions illustrate versatility building blocks future design new HEDMs.

Язык: Английский

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Development Strategies of Polymorphs and Solvates for Enhancing Powder Properties: A Case Study of Thiothiamine

Crystal Growth & Design, Год журнала: 2023, Номер 23(10), С. 7482 - 7495

Опубликована: Сен. 25, 2023

Crystals with an acicular shape are a "nightmare" to many chemical engineers due their poor powder properties, posing numerous challenges in purification, filtration, washing, and subsequent processing. However, these may be circumvented by engineering new crystal forms better morphology using strategy. Herein, we demonstrated the validity of this strategy case thiothiamine, essential intermediate production vitamin B1, which exhibits needle-like polymorph I. Another two polymorphs (forms II III) 14 solvates were discovered developed combination computational prediction experimental screening X-ray diffraction, IR spectroscopy, thermal analysis. Crystal structures form six fully determined for first time single diffraction. First, compared I, notably larger grain size. Furthermore, desolvation can retain its original superior morphology. These optimization strategies targeting directly contribute enhancement performance. Specifically, filtration was significantly reduced over 70%, flowability also greatly improved. structure analysis reveals that inclusion small solvent molecules disordered manner contributes solvate formation, while hydrogen bonding interactions formation methanol solvate. This study serve as valuable reference addressing industry develop or alternatives.

Язык: Английский

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High-Density Energetic Materials with Low Mechanical Sensitivity and Twinning Derived from Nitroimidazole Fused Ring

Molecules, Год журнала: 2024, Номер 29(2), С. 353 - 353

Опубликована: Янв. 10, 2024

The innovative synthesis of 3,8-dibromo-2,9-dinitro-5,6-dihydrodiimidazo [1,2-a:2',1'-c]pyrazine and 3,9-dibromo-2,10-dinitro-6,7-dihydro-5

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Understanding the Relationship between Molecular Assembly and Polymorph Selection of 4,4′,5,5′-Tetranitro-1H,1′H-[2,2′-biimidazole]-1,1′-diamine in Solution

Crystal Growth & Design, Год журнала: 2024, Номер 24(8), С. 3430 - 3440

Опубликована: Март 25, 2024

The unpredictable occurrence and variation of polymorphs in solutions have sparked interest the study molecular mechanisms polymorphism with advancements experimental computational technologies. However, understanding behind solution remains incomplete. This research represents first exploration relationship between aggregation patterns for low-sensitivity highly energetic materials. A set order parameters 4,4′,5,5′-tetranitro-1H,1′H-[2,2′-biimidazole]-1,1′-diamine (DATNBI) was successfully established used to predict polymorph tendencies various systems, verifying that greater solute–solvent interactions are more favorable formation form α. Additionally, we analyze stability transformation relationships forms α β different monomers dimers gas phase solvents using density function theory. results were largely consistent predictions, except case antisolvent crystallization acetonitrile, which might be manipulated by rate lower energy barrier transformation. suggests DATNBI is likely determined dimer states solution, meaningful controlling explosive crystallization.

Язык: Английский

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Determining structure and origin of impurities in DATNBI by ultrahigh performance liquid chromatography coupled to q-orbitrap mass spectrometry

Microchemical Journal, Год журнала: 2024, Номер 202, С. 110668 - 110668

Опубликована: Май 1, 2024

Язык: Английский

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Tailoring Surface Defects to Enhance PBX Surface Adhesion through Autologous Surface Molecular Reconfiguration

Surfaces and Interfaces, Год журнала: 2024, Номер 49, С. 104448 - 104448

Опубликована: Май 7, 2024

Язык: Английский

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Identifying Possible Slip Systems of Molecular Crystals via a Geometry-Based Procedure

Crystal Growth & Design, Год журнала: 2024, Номер 24(11), С. 4342 - 4356

Опубликована: Май 15, 2024

Crystal plasticity is achieved primarily through slipping. Here, a geometry-based procedure developed to facilitate the identification of slip systems in arbitrarily oriented three-dimensional periodic molecular crystals. The requires crystal structure as only input, and steric hindrance parameter denoted maximum atom overlap factor (MAOF) used quantify experienced along specific direction. Slip direction with lowest MAOF considered be most favorable. Under constraint translational symmetry preservation, searching space directions low Miller indexes can readily covered by efficient loop searches. Since favorable planes predicted geometric analysis tool Cambridge Structural Database Python API, we easily obtain following basic geometry. validated structurally diverse set crystals comparison experimental theoretical calculation results. While highly efficient, it intended for coarse filtering due its simplicity. In cases where high accuracy desired, this should conjunction other methods further against accurate first-principles shear-slipping calculations. addition, crystal-level combination molecular-level dissociation energy weakest bond shown well correlated impact sensitivity variety energetic

Язык: Английский

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