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Thirteen tetranitro-diazinodiazines have been designed and investigated to find the importance of diazinodiazine fused-heterocyclic backbone for energetic materials. The positional influence of four nitrogen atoms in the diazinodiazine backbone on the heat of formation, performance, and stability has been investigated by density functional theory. It is observed that diazinodiazine is an efficient backbone to improve energy content in the designed derivatives. The energy contribution from the diazinodiazine backbone varies from 352–558 kJ/mol. Introducing four –NO2 groups into the diazinodiazine backbone resulted in new energetic molecules with acceptable detonation performance and stability. Their densities, detonation velocities, and detonation pressures were 1.87–1.89 g/cm3, 8.36–8.68 km/s, and 31.72–34.42 GPa, respectively. The bond dissociation energies for the longer C–NO2 bonds fall in the range of 207–233 kJ/mol, reveals the stable nature of tetranitro-diazinodiazines. Thus, diazinodiazine isomers may be regarded as promising aromatic heterocyclic backbone, and tetranitro-diazinodiazines appear to be potential candidates for energetic materials.

A rapid practical process has been developed for synthesis of 2,4,5-trisubstituted-imidazoles in excellent yields up to 95% from readily available starting materials. In this CuI catalyzed synthesis, trisubstituted imidazoles were afforded in short reaction times, wherein the substrate scope is well explored with benzoin as well as benzil reacting with different aldehydes in the presence of ammonium acetate as the nitrogen source.

Background: The present research work is focused on the development of alternative antioxidant and anti-inflammatory agents. The review of the literature reveals that many benzofused thiazole analogues have been used as lead molecules for the design and development of therapeutic agent, including anticancer, anti-inflammatory, antioxidant and antiviral. The synthesized benzofused thiazole derivatives are evaluated for in vitro antioxidant, anti-inflammatory activities and molecular docking study. Thus, the present research work aims to synthesize benzofused thiazole derivatives and to test their antioxidant and antiinflammatory activities. Objective: To design and synthesize an alternative antioxidant and anti-inflammatory agents. Methods: The substituted benzofused thiazoles 3a-g were prepared by cyclocondensation reaction of appropriate carboxylic acid with 2-aminothiophenol in POCl3 and heated for about 2-3 h to offer benzofused thiazole derivatives 3a-g. All the newly synthesized compounds were in vitro screened for their anti-inflammatory and antioxidant activities by using a known literature method. Results: At the outset, the study of in vitro indicated that the compounds code 3c, 3d and 3e possessed distinct anti-inflammatory activity as compared to a standard reference. All the tested compounds show potential antioxidant activity against one or more reactive (H2O2, DPPH, SO and NO) radical scavenging species. Additionally, docking simulation is further performed to the position of compounds 3d & 3e into the anti-inflammatory active site to determine the probable binding model. Conclusion: New anti-inflammatory and antioxidant agents were needed; it has been proved that benzofused thiazole derivatives were 3c, 3d and 3e constituted as an interesting template for the evaluation of new anti-inflammatory agents and an antioxidant’s work also may provide an interesting template for further development.

A new series of 1-Thiazolyl-2-Pyrazolines 5a-g was accomplished by reacting pyrazolealdehyde with an appropriate aromatic ketone in the presence of PEG-300 as a solvent to yield chalcone. The chalc...

A trichloromethyl ester devoid of suitably substituted C C bond, any leaving group or a H-atom at the β-position to the radical, which are otherwise known for ATRA/ATRC, 1,2-rearrangement/fragmentation or simple 1,2-H shift respectively, in a reaction of trichloro-acetic acid phenyl ester with 2 mol equiv CuCl/bpy in reflux DCE or benzene under inert N2 condition resulted to stereoselective synthesis of Z-2,3-dichloro-but-2-enedioic acid diphenyl ester and/or formation of reductive de-chlorination side product. The Z-stereochemistry of the product was confirmed by X-ray diffraction spectroscopy of Z-2,3-dichloro-but-2-enedioic acid dinaphthalen-1-yl ester which crystalizes in monoclinic system of P21/c symmetry elements. Hirshfeld surface analysis of experimentally established structure of Z-2,3-dichloro-but-2-enedioic acid diphenyl ester unrevealed the intermolecular interactions showing both H-bonding and short contacts. The stereochemistry was also interpreted computationally using Density Functional Theory at B3LYP/6-311G(d,p) level of theory. The calculated energies, energy gap and balance between the electrostatic potential on the molecular surface were computed which revealed unusual formation of less stable Z-isomer.

An efficient multicomponent approach has been developed in the environmentally green aqueous medium for synthesis of substituted polyfunctionalized pyrazoles. The simple and readily available aldehydes, malononitrile and phenylhydrazines substrates afforded polysubstituted imidazoles (15 examples) up to 96 % yield. The polyethylene glycol is playing the dual role of solvent and promoter with water in this reaction catalyzed by ceric ammonium nitrate.

This article describes the syntheses, characterization, and energetic properties of 4, 6-diazido-N, N-dimethyl-1, 3, 5-triazin-2-amine and 2, 4, 6-tris (5-(3, 5-dinitrophenyl)-1H-tetrazol-1-yl)-1, 3, 5-triazine. Also, this paper emphasizes the insensitive and thermally stable energetic molecules like melem, melem-ammonium perchlorate mixture, and hydrazinium cyamelurate. All these compounds possess good energetic properties viz., the heat of formation and heat of combustion. Synthesis and characterizations and energetic properties of 4, 6-diazido-N, N-dimethyl-1, 3, 5-triazin-2-amine (3); 2, 4, 6-tris (5-(3, 5-dinitrophenyl)-1H-tetrazol-1-yl)-1, 3, 5-triazine (4) and hydrazinium cyamelurate (10) are described. The thermal stabilities, energetic properties and sensitivity parameters are compared with standard high-energy materials. (i) Syntheses and characterization of 4, 6-diazido-N, N-dimethyl-1, 3, 5-triazin-2-amine (3); 2, 4, 6-tris (5-(3, 5-dinitrophenyl)-1H-tetrazol-1-yl)-1, 3, 5-triazine (4) and hydrazinium cyamelurate (10) are described. (ii) Experimental energetic properties and sensitivity parameters of these compounds were discussed.

Exploring a new multi-responsive pyranone chemosensor capable of sensing copper ions specifically and selectively through colorimetric, UV–Vis absorption and fluorescence methods is of great importance. In this piece of work, a novel pyranone based Schiff base ligand 4-Hydroxy-6-methyl-3-[1-(2-morpholin-4-yl-ethylimino)-ethyl]-pyran-2-one (DM) was synthesized by the condensation of dehydroacetic acid and 4-(2-aminoethyl) morpholine. The structural determination of ligand DM was executed using distinct spectral techniques i.e., 1H NMR, 13C NMR, FT-IR and HR-MS techniques. The reported Schiff base DM showed an immediate colorimetric change from pale yellow to colorless accompanied by a strong change in the UV–Vis absorption band onto the addition of Cu (II) ions. This metal ligand chelation leads a decrease in ICT process. Also the decrease in fluorescence emission intensity of Schiff base DM with Cu (II) ions addition showed its turn-off behavior towards copper ions. Further absorption/ emission titration studies, Job’s plot, HR-MS and 1H NMR titration data designated 2:1 stoichiometric ratio between DM and Cu (II) ions respectively. Density functional theory studies were also performed to authenticate the binding mechanism theoretically. The sensitivity of Schiff base DM towards Cu (II) ions was applicable at every pH conditions and at the same time DM exhibited selectivity towards Cu (II) ions with a negligible interference of other metal ions. DM showed a detection limit of 7.7 nM towards copper ions via fluorescence emission studies. The best part about DM is that it has good stability but showed an instant chemical reversibility when titrated with EDTA solution.

There is broad interest in engineering phenylalanine ammonia-lyase (PAL) for its biocatalytic applications in industry (fine-chemicals and natural product synthesis) and medicine (phenylketoruria/PKU and cancer treatment). While site-specific mutagenesis has been employed to improve PAL stability or substrate specificity, a more comprehensive mutational landscape has yet to be explored for this class of enzymes. Here, we report development of a directed evolution technique to engineer PAL enzymes. Central to this approach is a high-throughput enrichment that couples E. coli growth to PAL activity. Using the clinically-relevant PAL from Anabaena variabilis, which is used on the formulation of pegvaliase for PKU therapy, we identified mutations at residues previously unknown as relevant for function that increase turnover frequency almost twofold after only a single round of engineering. This work demonstrates the power our technique for ammonia-lyase enzyme engineering.

We compared the effectiveness of different forcefields for computing the density of CHNO explosives using crystal packing methodology. Densities obtained for 68 CHNO explosives of various sizes vary in chemical nature, contain different functionalities, and are compared with the experimental data. The predicted densities with Dreiding forcefield for 84% explosives without an aromatic ring in the structure (NonAr-Explosives) gave deviation within 5%. While the predicted densities with PCFF forcefield for 83% of explosives containing aromatic ring in the structure (Ar-Explosives) found within 4% deviation, the computed densities using various forcefields judged with experimental data indicate that choice of forcefield is crucial for precise density prediction. This study will be valuable in selecting forcefield for crystal packing calculations and directing research efforts towards the design of denser CHNO energetic materials. Please be informed that Graphical Abstract is not allowed per journal style. Thus, the graphical abstract provided was not captured.Author agrees with the comment.

This paper describes the synthesis, characterization and energetic properties of tetrazole and triazine-based thermally stable, insensitive nitrogen-rich high energy density materials of N, N’, N”-(1,3,5-triazine-2,4,6-triyl) tris(N-cyanocyanamide) [1] and 2,4,6-tris[bis(1H-tetrazol-5-yl)amino]-1,3,5-triazine [2]. The compound 2 is the first example for compounds having six tetrazole units on a triazine ring. Synopsis Synthesis, characterization and energetic properties of the molecule, $$\hbox {N}_{2},\hbox {N}_{2},\hbox {N}_{4},\hbox {N}_{4},\hbox {N}_{6},\hbox {N}_{6}$$ -hexa(1H-tetrazol-5-yl)-1,3,5-triazine-2,4,6-triamine (2) having 79% nitrogen content with high HOF value is discussed. The high nitrogen content associated with high positive heat of formation of the compound 2 underline the structural importance of six tetrazole groups in a molecule.

A workable cost-efficient synthetic method for the construction of nitro substituted tetrazole-N-aryl/heteroaryl derivatives is discussed here. The energetic functional groups –NO2, –NHNO2 and –N3 are reliably inserted into the molecular backbone, making the tetrazole-N-aryl derivatives highly energetic and insensitive to heat and impact. For example, the tetrazole derivatives 7 and 8, bearing a –NO2 or a –NHNO2 group, exhibit energetic properties close to RDX, but with enhanced insensitivity. Most of the synthesized compounds show exothermic decomposition and are consequently useful for energetic material applications.

A new chromone based Schiff base ligand L was synthesized by the condensation of 3-formyl chromone and pyrazine-2-carbohydrazide as a colorimetric probe to detect Cu (II) ions selectively. An instant visual colour change from colourless to yellow was obtained on addition of Cu2+ ions to the probe L solution, while other metal ions found ineffective. The ligand L was characterized by 1H NMR, FTIR and HRMS spectral techniques. UV-Visible spectroscopic technique was used to study the sensing ability of probe L for copper ions above other metal ions. The Job's plot obtained from absorption studies and HRMS data confirmed that the Cu2+ ions bind with ligand L in 1:1 stoichiometric ratio. DFT computations were also supported the binding framework between L and Cu (II) ions. The LOD value and the association constant were obtained 3.9 × 10−7 M and 2.3 × 105 M−1 respectively, via Benesi-Hildebrand equation. Selectivity of L towards Cu2+ ions was also studied and it was found that the probe L worked specifically for copper ions without any considerable influence of other intruding metal ions. In addition, in real water samples, the ligand L was fully implemented for identification and quantification of Cu2+ ions.

An organic molecule-based sensor 4-((4-(dimethylamino)phenyl)diazenyl)-N-(quinolin-8-yl)benzenesulfonamide(MASP)able to detect multiple analytes such as moisture, warfare reagent (phosgene), divalent (Cu2+), and trivalent (Fe3+) has been reported. These analytes belong to the different classes of chemicals and barely interfere in the real sample. Fluorescence emission of MASP was observed due to the ESIPT mechanism, but it was inhibited by water. This phenomenon was utilized for moisture detection in DMSO and THF with the detection limit of 0.0032 % w/w and 0.0014 % w/w, respectively. The MASP was also employed for the colorimetric sensing (yellow to red) of phosgene in solution and gas with good selectivity and high sensitivity (LOD = 23 nM). The naked eye detection of MASP was incorporated with RGB color value to make use of MASP for the practical application using a smartphone as a portable analytical device. The distinct color change of divalent Cu2+ (yellow to colorless) and trivalent Fe3+ (yellow to red) observed with MASP also helps discriminate Cu2+ and Fe3+ among various cations.

Based on the backbone of the nitrogen-rich triazole and tetrazole structure, their N–OH derivatives were designed to improve the properties of energetic materials. This work introduces five novel nitrogen-rich derivatives and their energetic salts as high-performance compounds. Reliable methods and correlations are used to predict the heat of formation, density, detonation, and combustion properties and explosive power. The predicted energetic properties are also compared with well-known explosives, TNT, TATB, RDX, and HMX, to evaluate the performance. A majority of the designed salts exhibited high positive heats of formation, good detonation properties, and high explosive power. Ammonium, hydrazinium, and hydroxylammonium salts (1–3), which have relatively high densities (over 1.86 g/cm3), resulted in good detonation velocities (above 9.0 km/s) and pressures (above 35 GPa), making them competitive energetic materials.

New derivatives of 5,5′,5″-tris(tetrazolyl)amine (H3tta) are designed by replacing N–H with N–NO2 and N–OH groups. Two H3tta derivatives (B and F) were selected for the design of 1:1 (cation:anion) energetic salts. Their heats of formation (HOF) and densities were predicted and combined to estimate the velocities of detonation (VOD) and detonation pressures (DP). Impact sensitivity of H3tta compounds containing nitramine functionality was assessed using h50, free space in a crystal lattice, and heats of detonation (Q). The calculated explosive power index about picric acid showed that most of the H3tta compounds and salts can be used as potential energetic materials. Those compounds and salts were found to exhibit superior detonation performance when compared with RDX and HMX. According to our results, newly designed H3tta derivatives may be used to develop high-performance energetic materials with lower sensitivity.

Five new poly-fluorine containing molecules were synthesized from economical and commercially available materials for high energy material applications by straightforward routes. All the synthesized molecules were characterized using IR, NMR spectroscopy, elemental analysis, single crystal X-ray diffraction and thermal (TG-DTA), impact, and friction stability measurements. In addition, the crystal structures of 4, 7 and 8 are presented. The synthesized poly-fluorine compounds were found to have reasonable detonation properties based on calculations (EXPLO5 v6.01), which are in the range of TNT and RDX. These compounds are thermally stable (Tdec > 150 °C) and are insensitive toward impact and friction.

A library of some novel 1,4-disubstituted-1,2,3-triazole-thiosemicarbazone hybrid molecules were designed and synthesized from (4-Prop-2-ynyloxy-benzylidene)-thiosemicarbazone and aryl azides under Cu(I)-catalyzed cycloaddition reaction. All newly synthesized [4-(1-Benzyl-1H-[1,2,3]triazol-4-ylmethoxy)-benzylidene] -thiosemicarbazone hybrid molecules were efficiently characterized by IR, 1H NMR, 13C NMR, HRMS and structure of alkynes 3 & 12 were finally supported by X-ray crystallographic data. Compounds 5c, 5d, 9c, 9d 13c and 13d demonstrated excellent potency results for B. Subtilis and P. Aeruginosa bacterial strains with MIC values 0.0141, 0.0152, 0.0562, 0.0608, 0.0141, 0.0608, 0.0141, 0.0304, 0.0281, 0.0304, 0.0281, 0.0304, respectively as compared to reference drug Ciprofloxacin. Antibacterial activity results were supported by molecular docking and DFT studies.

By understanding the rampant infections of Mycobacterium tuberculosis (Mtb) and inflammations caused due to the generation of radical species during the Mtb infection, a series of (E)-2-(2-allylidenehydrazinyl)thiazole derivatives, with dual-action properties, was designed. The molecules were designed with a considerable variation in LogP, one of the critical parameters in physicochemical properties, and analyzed for their drug-likeness. For the synthesis, a simple, green, and multicomponent one-pot synthesis method was developed. The in vitro inhibition potentials were evaluated against Mtb H37 Rv by the microplate Alamar Blue assay. The results reveal that compound 6 was potent, with a MIC value of 6.5 µg/ml, and showed better interactions with the KasA protein with binding free energy (ΔG) of -9.4 kcal/mol. Also, the radical scavenging properties were studied to establish the dual-action properties of the molecules. Compound 9 exhibited promising antioxidant and nitric oxide radical scavenging activities, with 81.7% and 81.0%, respectively, at 1,000-μg/ml concentration.

The undesired research results of triazole synthesis were successfully utilized as a simpler, sensitive and selective turn-on fluorescent probe 2 namely chloro-acetic acid 2-benzothiazol-2-yl-phenyl ester (HBT-AcCl) which was synthesized by simple chloroacylation of 2-hydroxyphenyl benzothiazole (HBT). Only one simple chloroacetate, a trigger unit as the reaction site of probe 2 makes it more simple, sensitive and selective for Cys and Hcy over other Amino Acids. The presented probe HBT-AcCl conserves simple structure, reduces the use of extra chloroacetate and improves %atom economy as compare to similar reported probes. Paper strip tests were carried out to explore the potential application for naked-eye detection of Cys under UV lamp. The selectivity of the HBT-AcCl probe for Cys and Hcy is supported by the results of absorbance and emission spectroscopy experiments and theoretical DFT calculations.

Two urea-linked 1,2,3-triazole based sensors (5a and 5b) have been synthesized by 1,3-dipolar cycloaddition between 1-(4-fluorophenyl)-3-(prop-2-yn-1-yl)urea (2) and phenyl azides (4a-4b) via copper(I)-catalyzed click reaction. The synthesized sensors 5a and 5b have been evaluated for their sensing ability towards anions (F−, Br−, Cl−, I−, H2PO4− and AcO−) and cations (Cu2+, Zn2+, Ca2+, Co2+, Cd2+, Hg2+, Pb2+ and Ni2+) through UV–Visible, fluorescence and NMR spectral techniques. It was observed that sensor 5a exhibited selective sensing for F− ion with a bathochromic shift in absorption spectrum and showed fluorescence “turn-on” behaviour in the emission spectroscopy. The UV–Visible experiments exhibited that 5a interact with F− ion with a stability constant (K) of 2.058 × 104 M−1 and detection limit of 5a for F− ions was found to be 65.76 ± 0.45 μM. Furthermore, these results were also supported by density functional theory (DFT) calculations.

Developing novel energetic materials of high detonation performance and low sensitivity is one of the primary objectives related to explosive research. By employing ab initio calculations, a series of energetic ionic salts based on 5,5′-bitetrazole-1,1′-diolate (BTO) were thoroughly investigated to understand the structure–property–performance interrelationship. The physicochemical and detonation characteristics of these energetic ionic salts including structural, electronic, vibrational and performance parameters (heats of formation, detonation pressures, and detonation velocities) were discussed in detail. The strong intermolecular hydrogen bonding environment between the BTO2− anion and various cations is mainly responsible for prominent detonation performance and enhanced molecular stability. Such strong intermolecular hydrogen bonds are observed in hydrazine and hydroxylammonium cations compared to other cations. To predict an accurate band gap, electronic band structures of the studied energetic ionic salts (EIS) were calculated using the HSE06 hybrid functional and they are found to be wide band gap insulators with a bandwidth ranging from 4.33–5.05 eV. Careful inspection of various EIS revealed that the hydroxylammonium and hydrazine cations produce the highest density relative to other cations when combined with the BTO anion. The detonation characteristics of BTO2− are computed using EXPLO5 code. In particular, HA-BTO and TKX-50 exhibit high detonation pressure (38.85 and 40.23 GPa) and detonation velocities (9.94 and 9.91 km s−1), superior to those of traditional nitrogen-rich energetic materials with moderate sensitivities. These results highlight the importance of hydrogen bonding interactions in designing energetic salts for next-generation explosives, propellants, and pyrotechnics.

Gas-phase heats of formation of 48 commonly used nitrogen-rich cations in energetic salts composed of H, C, N, and O atoms have been calculated at the Gaussian-3 (G3), Gaussian-4 (G4), and G4 (MP2) theories using the atomization reaction. The discrepancies between the predicted and the reported HOFs vary in the range of 0.28–470.78 kJ/mol. The reported HOFs for twenty cations were observed within 5 kJ/mol deviation, ten cations within 6–10 kJ/mol deviation, eleven cations within 11–50 kJ/mol, five cations within 51–100 kJ/mol, while two cations differed by more than 420 kJ/mol with respect to G4 data. The calculated HOFs with the G4 composite method at 298.15 K were recommended for selected cations as being more reliable than the reported data.

The computational design of energetic salts based on 3,6,7-triamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazol-2-ium (cation A) and 3,7-diamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazol-2-ium (cation B) is described. Selective energetic anions have been combined with these cations to tune the performance parameters. All the designed salts (A1–11 and B1–11) exhibited reasonable densities ranging from 1.54 to 1.85 g/cm $$^{3}$$ , and positive heats of formation between 301 kJ/mol and 854 kJ/mol. The detonation properties for the A1–11 and B1–11 salts were computed using Kamlet–Jacobs method, and the corresponding values were found in the ranges of 6.12 km/s to 8.79 km/s and 15.12 GPa to 34.84 GPa. Admirable energetic performance and reasonable sensitivity indicate A4 and B4 as promising energetic salts. SYNOPSIS The computational design of energetic salts based on 3,6,7-triamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazol-2-ium and 3,7-diamino-7H-[1,2,4]triazolo[4,3-b][1,2,4]triazol-2-ium is described. All the salts possess positive HOF range from 301 to 854 kJ/mol. Among the designed salts, two salts (A4 and B4) exhibit superior performance, and efforts can be made for their development as potential high energy materials (HEMs).

We compared the effectiveness of different molecular surface electrostatic potential (MESP)-based methods for calculating the density of CHNO explosives. Densities computed for 221 CHNO explosives of different chemical nature and functional groups and compared with the experimental values. The CHNO explosives in this work are divided into seven groups as group I nitrate-esters, group II nitramines, group III azides, group IV energetic materials containing benzene ring, group V energetic materials containing caged and strained rings, group VI energetic materials containing heterocyclic backbone, and group VII are the energetic materials containing fused ring. The computed densities using molecular volume method, Lee method, Kim method, Politzer method, and Rice method judged with experimental data indicates that Politzer and Rice method can be applied for the prediction of density. This study will be useful in selecting an MESP-based approach for the density estimation and directing research efforts towards the development of new CHNO explosives. Graphical Abstract The effectiveness of different molecular surface electrostatic potential (MESP)-based methods such as Lee method, Kim method, Politzer method, and Rice method for calculating the density of 221 CHNO explosives is assessed. The CHNO explosives are divided into seven groups as nitrate-esters, nitramines, azides, energetic materials containing- benzene ring, -caged and strained rings, -heterocyclic backbone, and -fused ring.

The application of average atomic volumes to predict the crystal densities of benzene-derived energetic compounds of general formula C a H b N c O d is presented, along with the reliability of this method. The densities of 119 neutral nitrobenzenes, energetic salts, and cocrystals with diverse compositions were estimated and compared with experimental data. Of the 74 nitrobenzenes for which direct comparisons could be made, the % error in the estimated density was within 0–3% for 54 compounds, 3–5% for 12 compounds, and 5–8% for the remaining 8 compounds. Among 45 energetic salts and cocrystals, the % error in the estimated density was within 0–3% for 25 compounds, 3–5% for 13 compounds, and 5–7.4% for 7 compounds. The absolute error surpassed 0.05 g/cm3 for 27 of the 119 compounds (22%). The largest errors occurred for compounds containing fused rings and for compounds with three –NH2 or –OH groups. Overall, the present approach for estimating the densities of benzene-derived explosives with different functional groups was found to be reliable.

Density-function-theory calculations were performed to find the performance of a series of 2,2’-(1,2,4,5-tetrazine-3,6diyl) dihydrazinecarboxamide-based nitrogen-rich macrocyclic compounds as an energetic plasticizer. Reliable methods have been used to predict energetic properties such as gas-phase and solid-phase heat of formation (HOF), density, detonation velocity, detonation pressure, explosive power, heat of combustion, heat of detonation, specific impulse, flame temperature, brisance, and sensitivity. All the designed macrocycles possess a nitrogen content of over 48%. The designed compounds show positive HOFs and high predicted densities ranging from 1.81[Formula: see text]g/cm3 to 1.86[Formula: see text]g/cm3. The predicted properties were compared with GAP, polyGLYN and their monomers which establish the designed macrocycles of interest for further investigations concerning their suitability as plasticizers in energetic formulations.

Ammonium DiNitramide (ADN) is one of the most promising green energetic oxidizers for future rocket propellant formulations. In the present work, we report a detailed theoretical study on structural, elastic, and vibrational properties of the emerging oxidizer under hydrostatic compression using various dispersion correction methods to capture weak intermolecular (van der Waals and hydrogen bonding) interactions. The calculated ground state lattice parameters, axial compressibilities, and equation of state are in good accord with the available experimental results. Strength of intermolecular interactions has been correlated using the calculated compressibility curves and elastic moduli. Apart from this, we also observe discontinuities in the structural parameters and elastic constants as a function of pressure. Pictorial representation and quantification of intermolecular interactions are described by the 3D Hirshfeld surfaces and 2D finger print maps. In addition, the computed infra-red (IR) spectra at ambient pressure reveal that ADN is found to have more hygroscopic nature over Ammonium Perchlorate (AP) due to the presence of strong hydrogen bonding. Pressure dependent IR spectra show blue- and red-shift of bending and stretching frequencies which leads to weakening and strengthening of the hydrogen bonding below and above 5 GPa, respectively. The abrupt changes in the calculated structural, mechanical, and IR spectra suggest that ADN might undergo a first order structural transformation to a high pressure phase around 5-6 GPa. From the predicted detonation properties, ADN is found to have high and low performance characteristics when compared with ammonium based energetic oxidizers and well-known secondary explosives, respectively., Comment: 28 pages, 11 figures