Tailoring the Energetic Properties of Pyrazole Hybrids through Functionalization with Dinitromethyl and -Hydroxytetrazole.

The functionalization of pyrazole-based compounds with dinitromethyl and -hydroxytetrazole groups resulted in enhanced energetic properties. Two key compounds, 5-(dinitromethyl)-3,4-dinitro-1-pyrazole () and 5-(3,4-dinitro-1-pyrazol-5-yl)-1-tetrazol-1-ol (), along with their salts, were synthesized and evaluated for their energetic properties. Notably, the bishydroxylammonium salts (: 8778 m·s; : 33.

An Organometallic Erbium Bismuth Cluster Complex Comprising a Bi Zintl Ion.

An organometallic erbium bismuth cluster complex, [K(THF)][Cp*ErBi] (), featuring a heterometallocubane core was isolated. The cube emerges from the rare Bi Zintl ion, bridging two erbium centers for the first time. SQUID magnetometry and calculations uncovered dominant antiferromagnetic coupling enabled through the chair-like hexabismuth anion.

Copper catalyzed benzylic sp C-H alkenylation.

The prenyl group is present in numerous biologically active small molecule drugs and natural products. We introduce benzylic C-H alkenylation of substrates Ar-CH with alkenylboronic esters (CH)OB-CH[double bond, length as m-dash]CMe as a pathway to form prenyl functionalized arenes Ar-CHCH[double bond, length as m-dash]CMe. Mechanistic studies of this radical relay catalytic protocol reveal diverse reactivity pathways exhibited by the copper(ii) alkenyl intermediate [Cu]-CH[double bond, length as m-dash]CMe that involve radical capture, bimolecular C-C bond formation, and hydrogen atom transfer (HAT).

Crystal structure of a tris(2-amino-eth-yl)methane capped carbamoyl-methyl-phosphine oxide compound.

The mol-ecular structure of the tripodal carbamoyl-methyl-phosphine oxide compound diethyl {[(5-[2-(di-eth-oxy-phosphor-yl)acetamido]-3-{2-[2-(di-eth-oxy-phos-phor-yl)acetamido]-eth-yl}pent-yl)carbamo-yl]meth-yl}phospho-nate, CHNOP, features six intra-molecular hydrogen-bonding inter-actions. The phospho-nate groups have key bond lengths ranging from 1.4696 (12) to 1.

Energetic derivatives substituted with trinitrophenyl: improving the sensitivity of explosives.

The incorporation of trinitrophenyl-modified 1,3,4-oxadiazole fragments is commonly observed in high-energy molecules with heat-resistant properties. This study explores the strategy of developing heat-resistant energetic materials by incorporating trinitrophenyl and an azo group into 1,3,4-oxadiazole, which involved the synthesis and characterization of ()-1,2-bis(5-(2,4,6-trinitrophenyl)-1,3,4-oxadiazol-2-yl)diazene (2), -(5-(2,4,6-trinitrophenyl)-1,3,4-oxadiazol-2-yl)nitramide (3), and the energetic salts of 3. Characterization techniques employed included H and C NMR, IR and elemental analysis.

Understanding the Stability of Highly Nitrated Sensitive Pyrazole Isomers.

Two energetic isomers of chemically unstable 3,5-bis(dinitromethyl)-4-nitro-1-pyrazole (), namely, 4-methyl-3,5-dinitro-1-(trinitromethyl)-1-pyrazole () and 5-methyl-3,4-dinitro-1-(trinitromethyl)-1-pyrazole (), each containing five nitro groups and having the same chemical composition, exhibit major differences in their physiochemical properties. These include density, enthalpy of formation, temperature of decomposition, and sensitivity to impact and friction. Notably, both isomer and isomer demonstrate superior thermal stability compared to isomer , making them promising candidates as safer energetic materials.

Open-Cage Copper Complexes Modulate Coordination and Charge Transfer.

This study presents a novel copper-based redox shuttle that employs the PY5 pentadentate polypyridyl ligand in a dye-sensitized solar cell (DSSC). The [Cu(PY5)] complex exhibits a unique five-coordinate square pyramidal geometry, characterized by a strategically labile axial position, to facilitate efficient dye regeneration while minimizing electron recombination, thereby enhancing DSSC performance. Notably, the inclusion of 4--butylpyridine (TBP) as an additive is shown to significantly modulate the electrochemical and photophysical properties of the copper complexes, attributed to its coordination to the vacant axial site.

Porous organic crystals crosslinked by free-radical reactions.

Two hydrogen-bonded crosslinked organic frameworks (HOFs) were synthesized free radical reactions utilizing butadiene and isoprene as crosslinkers. These HOFs exhibit high crystallinity, enabling detailed structural characterization single-crystal X-ray diffraction analysis. Subsequently, one of the olefin-rich HOFs was converted to a hydroxylated framework through hydroboration-oxidation while maintaining the high crystallinity.

Ultradynamic Isoreticularly Expanded Porous Organic Crystals.

Porous organic materials showcasing large framework dynamics present new paths for adsorption and separation with enhanced capacity and selectivity beyond the size-sieving limits, which is attributed to their guest-responsive sorption behaviors. Porous hydrogen-bonded crosslinked organic frameworks (HOFs) are attractive for their remarkable ability to undergo guest-triggered expansion and contraction facilitated by their flexible covalent crosslinkages. However, the voids of HOFs remain limited, which restrains the extent of the framework dynamics.

Azidomethyl-bisoxadiazol-linked-1,2,3-triazole-(ABT)-based potential liquid propellant and energetic plasticizer.

A scalable synthesis of azidomethyl bisoxadiazol linked-1,2,3-triazole-(ABT) based potential liquid propellant and energetic plasticizer is obtained from commercially available diaminomaleonitrile in excellent yield. Newly synthesized compounds were fully characterized by various spectroscopic techniques. These materials exhibit good densities (1.

A Lewis Acid-Controlled Enantiodivergent Epoxidation of Aldehydes.

Two epoxidation catalysts, one of which consists of two VANOL ligands and an aluminum and the other that consists of two VANOL ligands and a boron, were compared. Both catalysts are highly effective in the catalytic asymmetric epoxidation of a variety of aromatic and aliphatic aldehydes with diazoacetamides, giving high yields and excellent asymmetric inductions. The aluminum catalyst is effective at 0 °C and the boron catalyst at -40 °C.

Green Light Promoted Iridium(III)/Copper(I)-Catalyzed Addition of Alkynes to Aziridinoquinoxalines Through the Intermediacy of Azomethine Ylides.

This manuscript describes the development of alkyne addition to the aziridine moiety of aziridinoquinoxalines using dual Ir(III)/Cu(I) catalytic system under green light-emitting diode (LED) photolysis (λ =525 nm). This mild method features high levels of chemo- and regioselectivity and was used to generate 30 highly functionalized substituted dihydroquinoxalines in 36-98 % yield. This transformation was also carried asymmetrically using phthalazinamine-based chiral ligand to provide 9 chiral addition products in 96 : 4 to 86 : 14 e.

Nitroiminotriazole (NIT) based potential solid propellants: synthesis, characterization, and applications.

Nitroimino (R = N-NO) energetic material is a unique class of high energy density materials (HEDM). Synthesis and characterization of insensitive nitroimino compounds are a major challenge. Here triazole-based nitroimino compounds and their high-nitrogen green energetic salts in excellent yields are described.

Manipulating nitration and stabilization to achieve high energy.

Nitro groups have played a central and decisive role in the development of the most powerful known energetic materials. Highly nitrated compounds are potential oxidizing agents, which could replace the environmentally hazardous used materials such as ammonium perchlorate. The scarcity of azole compounds with a large number of nitro groups is likely due to their inherent thermal instability and the limited number of ring sites available for bond formation.

Ortho-Alkoxy-benzamide Directed Formation of a Single Crystalline Hydrogen-bonded Crosslinked Organic Framework and Its Boron Trifluoride Uptake and Catalysis.

Boron trifluoride (BF ) is a highly corrosive gas widely used in industry. Confining BF in porous materials ensures safe and convenient handling and prevents its degradation. Hence, it is highly desired to develop porous materials with high adsorption capacity, high stability, and resistance to BF corrosion.

Tripodal Organic Cages with Unconventional CH···O Interactions for Perchlorate Remediation in Water.

Perchlorate anions used in industry are harmful pollutants in groundwater. Therefore, selectively binding perchlorate provides solutions for environmental remediation. Here, we synthesized a series of tripodal organic cages with highly preorganized C-H bonds that exhibit selectively binding to perchlorate in organic solvents and water.

Crystal structure of a (carb-oxy-meth-yl)tri-ethyl-aza-nium bromide-2-(tri-ethyl-aza-n-ium-yl)acetate (1/1) hydrogen-bonded dimer.

The title compound, CHNO ·Br·CHNO, crystallizes as the bromide salt of a 50:50 mixture of (tri-ethyl-azaniumyl)-carb-oxy-lic acid and the zwitterionic (tri-ethyl-azaniumyl)-carboxyl-ate. The two organic entities are linked by a half-occupied bridging carb-oxy-lic acid hydrogen atom that is hydrogen-bonded to the carboxyl-ate group of the second mol-ecule. The tetra-lkyl-ammonium group adopts a nearly perfect tetra-hedral shape around the nitro-gen atom with bond lengths that agree with known values.

Energetic performance of trinitromethyl nitrotriazole (TNMNT) and its energetic salts.

Little is known about trinitromethyl nitrotriazole (TNMNT) since the crystal structure, density, energetic performance, and thermal properties have not been determined. A detailed characterization of TNMNT and its hydrazinium and potassium salts and their potential as solid propellants and oxidizers has been established. TNMNT exhibits a high density (1.

Trinitromethyl-triazolone (TNMTO): a highly dense oxidizer.

A scalable synthesis of 5-(trinitromethyl)-2,4-dihydro-3-1,2,4-triazol-3-one () is possible from commercially available 2-methylpyrimidine-4,6-diol. It exhibits high density (1.90 g cm) with comparably low thermal stability ( = 80 °C) and positive oxygen balance (OB = 20.

C-H···π interactions disrupt electrostatic interactions between non-aqueous electrolytes to increase solubility.

Grid-scale energy storage applications, such as redox flow batteries, rely on the solubility of redox-active organic molecules. Although redox-active pyridiniums exhibit exceptional persistence in multiple redox states at low potentials (desirable properties for energy storage applications), their solubility in non-aqueous media remains low, and few practical molecular design strategies exist to improve solubility. Here we convey the extent to which discrete, attractive interactions between C-H groups and π electrons of an aromatic ring (C-H···π interactions) can describe the solubility of N-substituted pyridinium salts in a non-aqueous solvent.

A Dihydrazone as a Remarkably Nitrogen-Rich Thermostable and Insensitive Energetic Material.

Hydrogen bonds (H-bonds) in energetic compounds have a very pronounced effect on physicochemical properties such as density, thermal stability, sensitivity, and solubility. Now a strategy to synthesize nitrogen-rich energetic materials with overall good properties, which stem from the synergetic effects of inter- or intramolecular H-bonds, is reported. 1,2-Dihydrazono-1,2-di(1-tetrazol-5-5-yl)ethane (), a new thermostable and insensitive material, is obtained from the reaction of dioxime () with hydrazine hydrate.

Design and Synthesis of High-Performance Planar Explosives and Solid Propellants with Tetrazole Moieties.

A straightforward synthetic strategy for newly designed nitrogen-rich planar explosives and solid propellants is reported. These materials exhibit high densities (1.69-1.

Thiol and HS-Mediated NO Generation from Nitrate at Copper(II).

Reduction of nitrate is an essential, yet challenging chemical task required to manage this relatively inert oxoanion in the environment and biology. We show that thiols, ubiquitous reductants in biology, convert nitrate to nitric oxide at a Cu(II) center under mild conditions. The β-diketiminato complex [ClNN]Cu(κ-ONO) engages in O-atom transfer with various thiols (RSH) to form the corresponding copper(II) nitrite [Cu](κ-ON) and sulfenic acid (RSOH).

Crystal structure of -butyl 3,6-di-iodo-carbazole-9-carboxyl-ate.

The mol-ecular structure of -butyl 3,6-di-iodo-carbazole-9-carboxyl-ate, CHINO, features a nearly planar 13-membered carbazole ring with C-I bond lengths of 2.092 (4) and 2.104 (4) Å.

A mixed phosphine sulfide/selenide structure as an instructional example for how to evaluate the quality of a model.

This paper compares variations on a structure model derived from an X-ray diffraction data set from a solid solution of chalcogenide derivatives of -1,2-bis-(di-phenyl-phosphan-yl)ethyl-ene, namely, 1,2-(ethene-1,2-di-yl)bis-(di-phenyl-phoshpine sulfide/selenide), CHPSSe. A sequence of processes are presented to ascertain the composition of the crystal, along with strategies for which aspects of the model to inspect to ensure a chemically and crystallographically realistic structure. Criteria include mis-matches between and , plots of | | | |, residual electron density, alerts, pitfalls of the OMIT command used to suppress ill-fitting data, comparative size of displacement ellipsoids, and critical inspection of inter-atomic distances.