RESUMEN

Preparation of a redox-frustrated high-energy-density energetic material is achieved by gentle protolysis of Mn[N(SiMe3)2]2 with the perchlorate salt of the tetrazolamide [H2NtBuMeTz]ClO4 (Tz = tetrazole), yielding the Mn6N6 hexagonal prismatic cluster, Mn6(µ3-NTztBuMe)6(ClO4)6. Quantum mechanics-based molecular dynamics simulations of the decomposition of this molecule predict that magnetic ordering of the d5 Mn2+ ions influences the pathway and rates of decomposition, suggesting that the initiation of decomposition of the bulk material might be significantly retarded by an applied magnetic field. We report here experimental tests of the prediction showing that the presence of a 0.5 T magnetic field modulates the ignition onset temperature by +10.4 ± 3.9 °C (from 414 ± 4 °C), demonstrating the first example of a magnetically modulated explosive.

RESUMEN

The energetic content of the compounds MgTp2, FeTp2, MnTp2, and TiTp2 is measured by bomb calorimetry and compared to theoretical calculations (Tp = trispyrazoylborate). TiTp2 had the largest heat of combustion of the four compounds. Comparison of the heat of combustion of the Ti complex to those of Mg and Mn complexes suggests an effective combustion energy of TiII of between 1400 and 3000 kJ/mol, affirming the role of TiII as a strong fuel atom.

RESUMEN

The metal-organic framework Zr6O4(OH)4(bpydc)6 (bpydc2- = 2,2'-bipyridine-5,5'-dicarboxylate) is used to template the growth of a cluster fragment of the two-dimensional solid MnBr2, which was predicted to exhibit spin frustration. Single-crystal and powder X-ray diffraction analyses reveal a cluster with 19 metal ions arranged in a triangular lattice motif. Static magnetic susceptibility measurements indicate antiferromagnetic coupling between the high-spin (S = 5/2) MnII centers, and dynamic magnetic susceptibility data suggest population of low-lying excited states, consistent with magnetic frustration. Density functional theory calculations are used to determine the energies for a subset of thousands of magnetic configurations available to the cluster. The Yamaguchi generalized spin-projection method is then employed to construct a model for magnetic coupling interactions within the cluster, enabling facile determination of the energy for all possible magnetic configurations. The confined cluster is predicted to possess a doubly degenerate, highly geometrically frustrated ground state with a total spin of STotal = 5/2.

RESUMEN

A significant number of challenges are encountered when developing biocidal agents with high throwing capacity for biosafety applications. Now a three-dimensional metal-organic framework (3D MOF) {MOF (2), [Cu(atrz)(IO3)2]n (atrz = 4,4'-azo-1,2,4-triazole)} was obtained using a postsynthetic method from MOF (1) {[Cu(atrz)3(NO3)2]n}. Benefitting from the oxygen-rich and small volume of the iodate (IO3) ligands (2.73 Å) in MOF (2) compared to the atrz ligand (7.70 Å) in MOF (1), the density of MOF (2) is 3.168 g cm-3, nearly twice that of its precursor. Its detonation velocity of 7271 ms-1 exceeds that of TNT (trinitrotoluene) and its detonation pressure of 40.6 GPa is superior to that of HMX (cyclotetramethylenetetranitramine) (1,3,5,7-tetranitro-1,3,5,7-tetrazoctane, 39.2 Gpa), which are the highest detonation properties for a biocidal agent. Its superior detonation performance results in its main product, I2, being distributed over a wide area, markedly reducing the diffusion of harmful microorganisms. This study offers novel insight not only for high-energy-density materials but also for huge potential applications as biocidal agents.

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We present an NMR crystallographic investigation of two as-made forms of the recently characterized gallophosphate GaPO-34A, which has an unusual framework composition with a Ga:P ratio of 7:6 and contains both hydroxide and fluoride anions and either 1-methylimidazolium or pyridinium as the structure-directing agent. We combine previously reported X-ray crystallographic data with solid-state NMR spectroscopy and periodic density functional theory (DFT) calculations to show that the structure contains at least three distinct types of disorder (occupational, compositional, and dynamic). The occupational disorder arises from the presence of six anion sites per unit cell, but a total occupancy of five of these, leading to full occupancy of four sites and partial occupancy of the fifth and sixth (which are related by symmetry). The mixture of OH and F present leads to compositional disorder on the occupied anion sites, although the occupancy of some sites by F is calculated to be energetically unfavorable and signals relating to F on these sites are not observed by NMR spectroscopy, confirming that the compositional disorder is not random. Finally, a combination of high-field 71Ga NMR spectroscopy and variable-temperature 13C and 31P NMR experiments shows that the structure directing agents are dynamic on the microsecond time scale, which can be supported by averaging the 31P chemical shifts calculated with the SDA in different orientations. This demonstrates the value of an NMR crystallographic approach, particularly in the case of highly disordered crystalline materials, where the growth of large single crystals for conventional structure determination may not be possible owing to the extent of disorder present.

RESUMEN

The synthesis of a new solid solution of the oxyhydroxide Ga5-xAlxO7(OH) is investigated via solvothermal reaction between gallium acetylacetonate and aluminum isopropoxide in 1,4-butanediol at 240 °C. A limited compositional range of 0 ≤ x ≤ 1.5 is produced, with the hexagonal unit cell parameters refined from powder X-ray diffraction (XRD) showing a linear contraction in unit cell volume with an increase in Al content. Solid-state 27Al and 71Ga nuclear magnetic resonance (NMR) spectroscopies show a strong preference for Ga to occupy the tetrahedral sites and Al to occupy the octahedral sites. Using isopropanol as the solvent, γ-Ga2-xAlxO3 defect spinel solid solutions with x ≤ 1.8 can be prepared at 240 °C in 24 h. These materials are nanocrystalline, as evidenced by their broad diffraction profiles; however, the refined cubic lattice parameter shows a linear relationship with the Ga:Al content, and solid-state NMR spectroscopy again shows a preference for Al to occupy the octahedral sites. Thermal decomposition of Ga5-xAlxO7(OH) occurs via poorly ordered materials that resemble ε-Ga2-xAlxO3 and κ-Ga2-xAlxO3, but γ-Ga2-xAlxO3 transforms above 750 °C to monoclinic ß-Ga2-xAlxO3 for 0 ≤ x ≤ 1.3 and to hexagonal α-Ga2-xAlxO3 for x = 1.8, with intermediate compositions of 1.3 < x < 1.8 giving mixtures of the α- and ß-polymorphs. Solid-state NMR spectroscopy shows only the expected octahedral Al for α-Ga2-xAlxO3, and for ß-Ga2-xAlxO3, the ∼1:2 tetrahedral:octahedral Al ratio is in good agreement with the results of Rietveld analysis of the average structures against powder XRD data. Relative energies calculated by periodic density functional theory confirm that there is an ∼5.2 kJ mol-1 penalty for tetrahedral rather than octahedral Al in Ga5-xAlxO7(OH), whereas this penalty is much smaller (∼2.0 kJ mol-1) for ß-Ga2-xAlxO3, in good qualitative agreement with the experimental NMR spectra.

RESUMEN

Reaction of 1,3-diazidopropane with an electron-rich Mn(II) precursor results in oxidation of the metal center to a Mn complex with concomitant assembly of the macrocyclic ligand into the 1,2,3,4,8,9,10,11-octaazacyclotetradeca-2,9-diene-1,4,8,11-tetraido (OIM) ligand. Although describable as a Werner Mn(V) complex, analysis by X-ray diffraction, magnetic measurements, X-ray photoelectron spectroscopy, cyclic voltammetry, and density functional theory calculations suggest an electronic structure consisting of a Mn(III) metal center with a noninnocent OIM diradical ligand. The resulting complex, (OIM)Mn(NH tBu), reacts via proton-coupled electron transfer (PCET) with phenols to form phenoxyl radicals, with dihydroanthracene to form anthracene, and with (2,4-di tert-butyltetrazolium-5-yl)amide to extrude a tetrazyl radical. PCET from the latter generates the isolable corresponding one-electron reduced compound with a neutral, zwitterionic axial 2,4-di tert-butyltetrazolium-5-yl)amido ligand. Electron paramagnetic resonance and density functional theoretical analyses suggest an electronic structure wherein the manganese atom remains Mn(III) and the OIM ligand has been reduced by one electron to a monoradical noninnocent ligand. The result indicates PCET processes whereby the proton is transferred to the axial ligand to extrude tBuNH2, the electron is transferred to the equatorial ligand, and the central metal remains relatively unperturbed.

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The combustion mechanism of [AlCp*]4 (Cp* = pentamethylcyclopentadienyl), a ligated aluminum(I) cluster, was studied by a combination of experimental and theoretical methods. Two complementary experimental methods, temperature-programmed reaction and T-jump time-of-flight mass spectrometry, were used to investigate the decomposition behaviors of [AlCp*]4 in both anaerobic and oxidative environments, revealing AlCp* and Al2OCp* to be the major decomposition products. The observed product distribution and reaction pathways are consistent with the prediction from molecular dynamics simulations and static density functional theory calculations. These studies demonstrated that experiment and theory can indeed serve as complementary and predictive means to study the combustion behaviors of ligated aluminum clusters and may help in engineering stable compounds as candidates for rocket propellants.

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Biohazards and chemical hazards as well as radioactive hazards have always been a threat to human health. The search for solutions to these problems is an ongoing worldwide effort. In order to control biohazards by chemical methods, a synthetically useful fused tricyclic iodine-rich compound, 2,6-diiodo-3,5-dinitro-4,9-dihydrodipyrazolo [1,5- a:5',1'- d][1,3,5]triazine (5), with good detonation performance was synthesized, characterized, and its properties determined. This compound which acts as an agent defeat weapon has been shown to destroy certain microorganisms effectively by releasing iodine after undergoing decomposition or combustion. The small iodine residues remaining will not be deleterious to human life after 1 month.

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The templated zeolite-analogue GaPO-34 (CHA structure type) crystallises from a gel precursor Ga2O3 : 2H3PO4 : 1HF : 1.7SDA : 70H2O (where SDA = structure directing agent), treated hydrothermally for 24 hours at 170 °C using either pyridine or 1-methylimizadole as SDA and one of either poorly crystalline ε-Ga2O3 or γ-Ga2O3 as gallium precursor. If the same gels are stirred for periods shorter than 2 hours but treated under identical hydrothermal conditions, then a second phase crystallises, free of GaPO-34. If ß-Ga2O3 is used as a reagent only the second phase is found to crystallise, irrespective of gel aging time. The competing phase, which we denote GaPO-34A, has been structurally characterised using synchrotron powder X-ray diffraction for the pyridine material, GaPO-34A(pyr), and using single-crystal X-ray diffraction for the 1-methylimiazole material, GaPO-34A(mim). The structure of GaPO-34A(pyr), P1[combining macron], a = 10.22682(6) Å, b = 12.09585(7) Å, c = 13.86713(8) Å, α = 104.6531(4)°, ß = 100.8111(6)°, γ = 102.5228(6)°, contains 7 unique gallium sites and 6 phosphorus sites, with empirical formula [Ga7P6O24(OH)2F3(H2O)2]·2(C5NH6). GaPO-34A(mim) is isostructural but is modelled as a half volume unit cell, P1[combining macron], a = 5.0991(2) Å, b = 12.0631(6) Å, c = 13.8405(9) Å, α = 104.626(5)°, ß = 100.346(5)°, γ = 101.936(4)°, with a gallium and a bridging fluoride partially occupied and two partially occupied SDA sites. Solid-state 31P and 71Ga NMR spectroscopy confirms the structural complexity of GaPO-34A with signals resulting from overlapping lineshapes from multiple Ga and P sites, while 1H and 13C solid-state NMR spectra confirm the presence of the protonated SDA and provide evidence for disorder in the SDA. The protonated SDA is located in 14-ring one-dimensional channels with hydrogen bonding deduced from the SDA nitrogens to framework oxygen distances. Upon thermal treatment to investigate SDA removal, structure collapse occurs, which may be due the large number of bridging hydroxides and fluorides in the as-made material, and the unequal amounts of gallium and phosphorus present.

RESUMEN

Sodium salts of iodine-rich pyrazole and imidazole with 1-(2-bromoethyl)-5-aminotetrazole are useful precursors for energetic N,N'-ethylene-bridged polyiodoazoles. Compounds 1-3 were characterized with IR, and 1 H and 13 C NMR spectroscopy as well as elemental analyses. The molecular structures of 1 and 2 were confirmed by using single crystal X-ray diffraction. Heats of formation were calculated using Gaussian 03 and detonation properties and biocidal efficiency were calculated with CHEETAH 7. The decomposition products of 1-3 destroy microbes more effectively than some previously reported biocides since the thermal decomposition occurs at below 400 °C without addition of oxidizer or combustion adjuvant.

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Energetic bridged triiodopyrazoles and triiodoimidazoles were designed and synthsized by reacting potassium triiodopyrazolate or triiodoimidazolate with corresponding dichloro compounds. All compounds were fully characterized by 1H and 13C NMR spectroscopy, IR spectroscopy, and elemental analyses. The structure of compound 1 was further confirmed by single-crystal X-ray diffraction. All of the compounds exhibit good thermal stability with decomposition temperatures between 199 and 270 °C and high densities ranging from 2.804 to 3.358 g/cm3. The detonation performances and the detonation products were calculated by CHEETAH 7. Compound 3 (Dv = 4765 m s-1; P = 17.9 GPa) and compound 7 (Dv = 4841 m s-1; P = 18.5 GPa) show comparable detonation pressure to TNT, and high iodine content makes them promising as energy and biocides storage compounds.

RESUMEN

The tetrameric Al(I) cyclopentadienyl compound Al4Cp*4 (Cp* = C5Me5) is a prototypical low-valence Al compound, with delocalized bonding between four Al(I) atoms and η5 ligands bound to the cluster exterior. The synthesis of new [AlR]4 (R = C5Me4Pr, C5Me4iPr) tetramers is presented. Though these systems failed to crystallize, comparison of variable-temperature 27Al NMR data with density functional theory (DFT) calculations indicate that these are Al4R4 tetramers analogous to Al4Cp*4 but with increased ligand steric bulk. NMR, DFT, and Atoms in Molecules analyses show that these clusters are enthalpically more stable as tetramers than the Cp* variant, due in part to noncovalent interactions across the bulkier ligand groups. Thermochemistry calculations for the low-valence metal interactions were found to be extremely sensitive to the DFT methodology used; the M06-2X functional with a cc-pVTZ basis set is shown to provide very accurate values for the enthalpy of tetramerization and 27Al NMR shifts. This computational method is then used to predict geometrical structures, noncovalent ligand interactions, and monomer/tetramer equilibrium in solution for a series of Al(I) cyclopentadienyl compounds of varying steric bulk.

RESUMEN

Two classes of iodine-rich salts that consist of iodine-rich cations and iodate (IO3-) or periodate (IO4-) anions were synthesized. The synthesis of analogous I3O8- salts was more difficult because of poor solubility and hydrolytic instability. All iodine-rich salts were fully characterized by infrared, 1H nuclear magnetic resonance, and 13C nuclear magnetic resonance spectroscopy as well as elemental analyses. The molecular structures of compounds 15 and 24 were elucidated by X-ray single-crystal diffraction. Additionally, the heats of formation were calculated with Gaussian 03. The detonation properties and biocidal efficiency were calculated and evaluated using CHEETAH 7.

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A class of tunable visible and near-infrared donor-acceptor Stenhouse adduct (DASA) photoswitches were efficiently synthesized in two to four steps from commercially available starting materials with minimal purification. Using either Meldrum's or barbituric acid "acceptors" in combination with aniline-based "donors", an absorption range spanning from 450 to 750 nm is obtained. Additionally, photoisomerization results in complete decoloration for all adducts, yielding fully transparent, colorless solutions and films. Detailed investigations using density functional theory, nuclear magnetic resonance, and visible absorption spectroscopies provide valuable insight into the unique structure-property relationships for this novel class of photoswitches. As a final demonstration, selective photochromism is accomplished in a variety of solvents and polymer matrices, a significant advantage for applications of this new generation of DASAs.

RESUMEN

The first synthetic manganese tetrazene complexes are described as a redox pair comprising anionic [Mn(N4 Ad2 )2 ](-) (1) and neutral Mn(N4 Ad2 )2 (2) complexes (N4 Ad2 =[Ad-N-N=N-N-Ad](2-) ). Compound 1 is obtained in two forms as lithium salts, one as a cationic Li2 Mn cluster, and one as a Mn-Li 1D ionic polymer. Compound 1 is electronically described as a Mn(III) center with two [N4 Ad2 ](2-) ligands. The one-electron oxidized 2 is crystalized in two morphologies, one as pure 2 and one as an acetonitrile adduct. Despite similar composition, the behavior of 2 differs in the two morphologies. Compound 2-MeCN is relatively air and temperature stable. Crystalline 2, on the other hand, exhibits a compositional, dynamic disorder wherein the tetrazene metallacycle ring-opens into a metal imide/azide complex detectable by X-ray crystallography and FTIR spectroscopy. Electronic structure of 2 was examined by EPR and XPS spectroscopies and DFT calculations, which indicate 2 is best described as a Mn(III) ion with an anion radical delocalized across the two ligands through spin-polarization effects.

RESUMEN

4-Iodo-1H-1,2,3-triazole (2) and 4,5-diiodo-1H-1,2,3-triazole (3) were synthesized using an efficient and viable synthetic route. The N-alkylation of 3 resulted in the formation of two tautomers. The N-alkyl-diiodo-triazoles were nitrated with 100% nitric acid to form monoiodo-mononitro-triazoles. The structures of 2-methyl-4,5-diiodo-1,2,3-triazole (5), 1-ethyl-4,5-diiodo-1,2,3-triazole (6), 1-methyl-4-nitro-5-iodo-1,2,3-triazole (8) and 1-ethyl-4-nitro-5-iodo-1,2,3-triazole (10) were confirmed by X-ray crystal analysis. All of the new triazoles were fully characterized via NMR, and infrared spectra, and elemental analyses as well as by their thermal and sensitivity properties. Decomposition products calculated using Cheetah 7 software show that these iodo-nitro triazoles liberate iodine.

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The neutral homoleptic tris-bpy aluminum complexes Al((R)bpy)3, where R = tBu (1) or Me (2), have been synthesized from reactions between AlX precursors (X = Cl, Br) and neutral (R)bpy ligands through an aluminum disproportion process. The crystalline compounds have been characterized by single-crystal X-ray diffraction, electrochemical experiments, EPR, magnetic susceptibility, and density functional theory (DFT) studies. The collective data show that 1 and 2 contain Al(3+) metal centers coordinated by three bipyridine (bpy(•))(1-) monoanion radicals. Electrochemical studies show that six redox states are accessible from the neutral complexes, three oxidative and three reductive, that involve oxidation or reduction of the coordinated bpy ligands to give neutral (R)bpy or (R)bpy(2-) dianions, respectively. Magnetic susceptibility measurements (4-300 K) coupled with DFT studies show strong antiferromagnetic coupling of the three unpaired electrons located on the (R)bpy ligands to give S = (1)/2 ground states with low lying S = (3)/2 excited states that are populated above 110 K (1) and 80 K (2) in the solid-state. Complex 2 shows weak 3D magnetic interactions at 19 K, which is not observed in 1 or the related [Al(bpy)3] complex.

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Synthetic, structural, spectroscopic and aging studies conclusively show that the main colorant of historical iron gall ink (IGI) is an amorphous form of Fe(III) gallate·xH2O (x = ∼1.5-3.2). Comparisons between experimental samples and historical documents, including an 18th century hand-written manuscript by George Washington, by IR and Raman spectroscopy, XRD, X-ray photoelectron spectroscopy, and Mössbauer spectroscopy confirm the relationship between the model and authentic samples. These studies settle controversy in the cultural heritage field, where an alternative structure for Fe(III) gallate has been commonly cited.

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Ab initio simulations are used to show that graphene vacancy sites may offer a means of templated growth of metalloid aluminum clusters from their monohalide precursors. We present density functional theory and ab initio molecular dynamics simulations of the aluminum halide AlCl interacting with a graphene surface. Unlike a bare Al adatom, AlCl physisorbs weakly on vacancy-free graphene with little charge transfer and no hybridization with carbon orbitals. The barrier for diffusion of AlCl along the surface is negligible. Covalent bonding is seen only with vacancies and results in strong chemisorption and considerable distortion of the nearby lattice. Car-Parrinello molecular dynamics simulations of AlCl liquid around a graphene single vacancy show spontaneous metalloid cluster growth via a process of repeated insertion reactions. This suggests a means of templated cluster nucleation and growth on a carbon substrate and provides some confirmation for the role of a trivalent aluminum species in nucleating a ligated metalloid cluster from AlCl and AlBr solutions.