Humidity-Sensing Properties of an 1D Antiferromagnetic Oxalate-Bridged Coordination Polymer of Iron(III) and Its Temperature-Induced Structural Flexibility

A novel one-dimensional (1D) oxalate-bridged coordination polymer of iron(III), {[NH(CH₃)(C₂H₅)₂][FeCl₂(C₂O₄)]}_n (1), exhibits remarkable humidity-sensing properties and very high proton conductivity at room temperature (2.70 × 10⁻⁴ (Ω·cm)⁻¹ at 298 K under 93% relative humidity), in addition to the independent antiferromagnetic spin chains of iron(III) ions bridged by oxalate groups (J = −7.58(9) cm⁻¹). Moreover, the time-dependent measurements show that 1 could maintain a stable proton conductivity for at least 12 h. Charge transport and magnetic properties were investigated by impedance spectroscopy and magnetization measurements, respectively. Compound 1 consists of infinite anionic zig-zag chains [FeCl₂(C₂O₄)]_nⁿ⁻ and interposed diethylmethylammonium cations (C₂H₅)₂(CH₃)NH⁺, which act as hydrogen bond donors toward carbonyl oxygen atoms. Extraordinarily, the studied coordination polymer exhibits two reversible phase transitions: from the high-temperature phase HT to the mid-temperature phase MT at T ~213 K and from the mid-temperature phase MT to the low-temperature phase LT at T ~120 K, as revealed by in situ powder and single-crystal X-ray diffraction. All three polymorphs show large linear thermal expansion coefficients.     

Thermal Stability and Sublimation Pressures of Some Ruthenocene Compounds

We set out to study the use of a series of ruthenocenes as possible and promising sources for ruthenium and/or ruthenium oxide film formation.The thermal stability of a series of ruthenocenes, including (η⁵-C₅H₄R)(η⁵-C₅H₄R´)Ru (1), R = R´ = H (3), R = H, R´ = CH₂NMe₂ (5), R = H, R´= C(O)Me (6), R = R´ = C(O)Me (7), R = H, R´ = C(O)(CH₂)₃CO₂H (8), R = H, R´ = C(O)(CH₂)₂CO₂H (9), R = H, R´ = C(O)(CH₂)₃CO₂Me (10), R = H, R´= C(O)(CH₂)₂CO₂Me (11), R = R´ = SiMe₃), (η⁵-C₄H₃O-2,4-Me₂)₂Ru (2), and (η⁵-C₅H₅-2,4-Me₂)₂Ru (4) was studied by thermogravimetry. From these studies, it could be concluded that 1–4, 6 and 9–11 are the most thermally stable molecules. The sublimation pressure of these sandwich compounds was measured using a Knudsen cell. Among these, the compound 11 shows the highest vapor pressure.     

Accelerating slow excited state proton transfer

Visible light excitation of the ligand-bridged assembly [(bpy)₂Ru_a^II(L)Ru_b^II(bpy)(OH₂)⁴⁺] (bpy is 2,2′-bipyridine; L is the bridging ligand, 4-phen-tpy) results in emission from the lowest energy, bridge-based metal-to-ligand charge transfer excited state (L^−•)Ru_b^III-OH₂ with an excited-state lifetime of 13 ± 1 ns. Near–diffusion-controlled quenching of the emission occurs with added HPO₄²⁻ and partial quenching by added acetate anion (OAc⁻) in buffered solutions with pH control. A Stern–Volmer analysis of quenching by OAc⁻ gave a quenching rate constant of k_q = 4.1 × 10⁸ M⁻¹⋅s⁻¹ and an estimated pK_a* value of ∼5 ± 1 for the [(bpy)₂Ru_a^II(L^•−)Ru_b^III(bpy)(OH₂)⁴⁺]* excited state. Following proton loss and rapid excited-state decay to give [(bpy)₂Ru_a^II(L)Ru_b^II(bpy)(OH)³⁺] in a H₂PO₄⁻/HPO₄²⁻ buffer, back proton transfer occurs from H₂PO₄⁻ to give [(bpy)₂Ru_a^II(L)Ru_b(bpy)(OH₂)⁴⁺] with k_PT,2 = 4.4 × 10⁸ M⁻¹⋅s⁻¹. From the intercept of a plot of k_obs vs. [H₂PO₄⁻], k = 2.1 × 10⁶ s⁻¹ for reprotonation by water providing a dramatic illustration of kinetically limiting, slow proton transfer for acids and bases with pK_a values intermediate between pK_a(H₃O⁺) = −1.74 and pK_a(H₂O) = 15.7.     

Synthesis,Crystal Structure and Luminescent Property of Mg(II) Complex with N-Benzenesulphonyl-L-Leucine and 1,10-Phenanthroline

A new complex [Mg(L)₂(phen)(H₂O)₂](phen)(H₂O)₂ [L= N-benzenesulphonyl-L-leucine] was synthesized by the reaction of magnesium chloride hexahydrate with N-benzenesulphonyl-L-leucine and 1,10-phenanthroline in the CH₃CH₂OH/H₂O (v:v = 5:1). It was characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. The crystal of the title complex [Mg(L)₂(phen)(H₂O)₂](phen)(H₂O)₂ belongs to triclinic, space group P-1 with a = 0.72772(15) nm, b = 1.4279(3) nm, c = 1.4418(3) nm, α = 63.53(3)°, β = 79.75(3)°, γ = 81.83(3)°, V = 1.3163(5) nm³, Z =1, D_c= 1.258 μg·m⁻³, μ = 0.177 mm⁻¹, F(000) = 526, and final R₁ = 0.0506, ωR₂ = 0.1328. The complex comprises a six-coordinated magnesium(II) center, with a N₂O₄ distorted octahedron coordination environment. The molecules are connected by hydrogen bonds and π-π stacking to form one dimensional chain structure. The luminescent property of the Mg(II) complex has been investigated in solid.     

Attempted hydrogen–deuterium exchange of the protio-trimethyloxonium dication (CH3)3OH2+, study of methylating ability of (CH3)3O+ in superacids and theoretical investigations

Attempted hydrogen–deuterium exchange of trimethyloxonium ion, (CH₃)₃O⁺ with excess of 1:1 ²HF/SbF₅ superacid at −30°C over a period of 30 days showed no exchange. Theoretical calculations at the MP2/6–31G** level are in accord with the lack of hydrogen–deuterium exchange in the methyl group of the (CH₃)₃O⁺ cation as protonation (protosolvation) prefers the oxygen lone pair of electrons, instead of a C—H bond. Methylation of aromatics with the (CH₃)₃O⁺CF₃SO₃⁻ in CF₃SO₃H and 2CF₃SO₃H:B(O₃SCF₃)₃ was also studied. Whereas in triflic acid no alkylation was observed, in triflatoboric acid, a powerful superacid, alkylation takes place, indicating protolytic activation of the trimethyloxonium ion.     

Boost the Crystal Installation and Magnetic Features of Cobalt Ferrite/M-Type Strontium Ferrite Nanocomposites Double Substituted by La3+ and Sm3+ Ions (2CoFe2O4/SrFe12−2xSmxLaxO19)

Spinel cobalt ferrite/hexagonal strontium hexaferrite (2CoFe₂O₄/SrFe_12−2xSm_xLa_xO₁₉; x = 0.2, 0.5, 1.0, 1.5) nanocomposites were fabricated using the tartaric acid precursor pathway, and the effects of La³⁺–Sm³⁺ double substitution on the formation, structure, and magnetic properties of CoFe₂O₄/SrFe_12−2xSm_xLa_xO₁₉ nanocomposite at different annealing temperatures were assayed through X-ray diffraction, scanning electron microscopy, and vibrating sample magnetometry. A pure 2CoFe₂O₄/SrFe₁₂O₁₉ nanocomposite was obtained from the tartrate precursor complex annealed at 1100 °C for 2 h. The substitution of Fe³⁺ ion by Sm³–⁺La³⁺ions promoted the formation of pure 2CoFe₂O₄/SrFe₁₂O₁₉ nanocomposite at 1100 °C. The positions and intensities of the strongest peaks of hexagonal ferrite changed after Sm³⁺–La³⁺ substitution at ≤1100 °C. In addition, samples with an Sm³⁺–La³⁺ ratio of ≥1.0 annealed at 1200 °C for 2 h showed diffraction peaks for lanthanum cobalt oxide (La₃Co₃O₈; dominant phase) and samarium ferrite (SmFeO₃). The crystallite size range at all constituent phases was in the nanocrystalline range, from 39.4 nm to 122.4 nm. The average crystallite size of SrFe₁₂O₁₉ phase increased with the number of Sm³⁺–La³⁺ substitutions, whereas that of CoFe₂O₄ phase decreased with an x of up to 0.5. La–Sm co-doped ion substitution increased the saturation magnetization (Ms) value and the subrogated ratio to 0.2, and the Ms value decreased with the increasing number of double substitutions. A high saturation magnetization value (Ms = 69.6 emu/g) was obtained using a La³⁺–Sm³⁺ co-doped ratio of 0.2 at 1200 for 2 h, and a high coercive force value (Hc = 1192.0 Oe) was acquired using the same ratio at 1000 °C.     

A model for the CO-inhibited form of [NiFe] hydrogenase: synthesis of (CO)3Fe(μ-StBu)3Ni{SC6H3-2,6-(mesityl)2} and reversible CO addition at the Ni site

A [NiFe] hydrogenase model compound having a distorted trigonal-pyramidal nickel center, (CO)₃Fe(μ-S^tBu)₃Ni(SDmp), 1 (Dmp = C₆H₃-2,6-(mesityl)₂), was synthesized from the reaction of the tetranuclear Fe-Ni-Ni-Fe complex [(CO)₃Fe(μ-S^tBu)₃Ni]₂(μ-Br)₂, 2 with NaSDmp at -40 °C. The nickel site of complex 1 was found to add CO or CN^tBu at -40 °C to give (CO)₃Fe(S^tBu)(μ-S^tBu)₂Ni(CO)(SDmp), 3, or (CO)₃Fe(S^tBu)(μ-S^tBu)₂Ni(CN^tBu)(SDmp), 4, respectively. One of the CO bands of 3, appearing at 2055 cm^-1 in the infrared spectrum, was assigned as the Ni-CO band, and this frequency is comparable to those observed for the CO-inhibited forms of [NiFe] hydrogenase. Like the CO-inhibited forms of [NiFe] hydrogenase, the coordination of CO at the nickel site of 1 is reversible, while the CN^tBu adduct 4 is more robust.     

Superionic Solid Electrolyte Li7La3Zr2O12 Synthesis and Thermodynamics for Application in All-Solid-State Lithium-Ion Batteries

Solid-state reaction was used for Li₇La₃Zr₂O₁₂ material synthesis from Li₂CO₃, La₂O₃ and ZrO₂ powders. Phase investigation of Li₇La₃Zr₂O₁₂ was carried out by x-ray diffraction (XRD), scanning electron microscopy (SEM) and energy-dispersive x-ray spectroscopy (EDS) methods. The thermodynamic characteristics were investigated by calorimetry measurements. The molar heat capacity (C_p,m), the standard enthalpy of formation from binary compounds (Δ_oxH_LLZO) and from elements (Δ_fH_LLZO), entropy (S⁰₂₉₈), the Gibbs free energy of the Li₇La₃Zr₂O₁₂ formation (∆_f G⁰₂₉₈) and the Gibbs free energy of the LLZO reaction with metallic Li (∆_rG_LLZO/Li) were determined. The corresponding values are C_p,m = 518.135 + 0.599 × T − 8.339 × T⁻², (temperature range is 298–800 K), Δ_oxH_LLZO = −186.4 kJ·mol⁻¹, Δ_fH_LLZO = −9327.65 ± 7.9 kJ·mol⁻¹, S⁰₂₉₈ = 362.3 J·mol⁻¹·K⁻¹, ∆_f G⁰₂₉₈ = −9435.6 kJ·mol⁻¹, and ∆_rG_LLZO/Li = 8.2 kJ·mol⁻¹, respectively. Thermodynamic performance shows the possibility of Li₇La₃Zr₂O₁₂ usage in lithium-ion batteries.     

Reactive and nonreactive quenching of O(1D) by the potent greenhouse gases SO2F2, NF3, and SF5CF3

A laser flash photolysis–resonance fluorescence technique has been employed to measure rate coefficients and physical vs. reactive quenching branching ratios for O(¹D) deactivation by three potent greenhouse gases, SO₂F₂(k₁), NF₃(k₂), and SF₅CF₃(k₃). In excellent agreement with one published study, we find that k₁(T) = 9.0 × 10^-11 exp(+98/T) cm³ molecule^-1 s^-1 and that the reactive quenching rate coefficient is k_1b = (5.8 ± 2.3) × 10^-11 cm³ molecule^-1 s^-1 independent of temperature. We find that k₂(T) = 2.0 × 10^-11 exp(+52/T) cm³ molecule^-1 s^-1 with reaction proceeding almost entirely (∼99%) by reactive quenching. Reactive quenching of O(¹D) by NF₃ is more than a factor of two faster than reported in one published study, a result that will significantly lower the model-derived atmospheric lifetime and global warming potential of NF₃. Deactivation of O(¹D) by SF₅CF₃ is slow enough (k₃ < 2.0 × 10^-13 cm³ molecule^-1 s^-1 at 298 K) that reaction with O(¹D) is unimportant as an atmospheric removal mechanism for SF₅CF₃. The kinetics of O(¹D) reactions with SO₂ (k₄) and CS₂ (k₅) have also been investigated at 298 K. We find that k₄ = (2.2 ± 0.3) × 10^-10 and k₅ = (4.6 ± 0.6) × 10^-10 cm³ molecule^-1 s^-1; branching ratios for reactive quenching are 0.76 ± 0.12 and 0.94 ± 0.06 for the SO₂ and CS₂ reactions, respectively. All uncertainties reported above are estimates of accuracy (2σ) and rate coefficients k_i(T) (i = 1,2) calculated from the above Arrhenius expressions have estimated accuracies of ± 15% (2σ).     

Comparative Evaluation of Cu(acac)2 and {[Cu(μ-O,O′-NO3) (L-arg) (2,2′-bpy)]·NO3}n as Potential Precursors of Electroless Metallization of Laser-Activated Polymer Materials

This paper presents a comparative assessment of Cu(acac)₂ and {[Cu(μ-O,O′-NO₃) (L-arg)(2,2′-bpy)]·NO₃}_n as potential precursors for the electroless metallization of laser activated polymer materials. Coatings consisting of polyurethane resin, one of the two mentioned precursor compounds, and antimony oxide (Sb₂O₃), as a compound strongly absorbing infrared radiation, were applied on the polycarbonate substrate. The coatings were activated with infrared Nd: YAG laser radiation (λ = 1064 nm) and electroless metallized. It was found that after laser irradiation, a micro-rough surface structure of the coatings was formed, on which copper was present in various oxidation states, as well as in its metallic form. For selected parameters of laser irradiation, it was possible to deposit a copper layer on the coating containing Cu(acac)₂ and Sb₂O₃, which is characterized by high adhesion strength. It was also found that the {[Cu(μ-O,O′-NO₃) (L-arg)(2,2′-bpy)]·NO₃}_n complex was not an effective precursor for the electroless metallization of Nd:YAG laser activated coatings. An attempt was made to determine the influence of the precursor chemical structure on the obtained metallization effects.     

Synthesis,Crystal Structure and Luminescent Property of Cd (II) Complex with N-Benzenesulphonyl-L-leucine

A new trinuclear Cd (II) complex [Cd₃(L)₆(2,2-bipyridine)₃] [L = N-phenylsulfonyl-L-leucinato] has been synthesized and characterized by elemental analysis, IR and X-ray single crystal diffraction analysis. The results show that the complex belongs to the orthorhombic, space group P2₁2₁2₁ with a = 16.877(3) Å, b = 22.875(5) Å, c = 29.495(6) Å, α = β = γ = 90°, V = 11387(4) ų, Z = 4, D_c= 1.416 μg·m⁻³, μ = 0.737 mm⁻¹, F (000) = 4992, and final R₁ = 0.0390, ωR₂ = 0.0989. The complex comprises two seven-coordinated Cd (II) atoms, with a N₂O₅ distorted pengonal bipyramidal coordination environment and a six-coordinated Cd (II) atom, with a N₂O₄ distorted octahedral coordination environment. The molecules form one dimensional chain structure by the interaction of bridged carboxylato groups, hydrogen bonds and π-π interaction of 2,2-bipyridine. The luminescent properties of the Cd (II) complex and N-Benzenesulphonyl-L-leucine in solid and in CH₃OH solution also have been investigated.     

Stereochemical Control of Valence and Its Application to the Reduction of Coordinated NO and N(2)

The electronic structures of transition metal complexes of NO are controlled by the stereochemistry about the metal atom (stereochemical control of valence). The six-coordinate complex, trans-[CoNO(NCS)-(C₆H₄ [As(CH₃)₂]₂)₂]⁺, consists of [Co(III)-(N=O^-)]²⁺ (angle_Co-N-O = 135°), while the pentacoordinate trigonal bipyramidal complex, [CoNO(C₆H₄[As(CH₃)₂]₂)₂] ²⁺, is best formulated as [Co(I)-(NO⁺]²⁺ (angle_Co-N-O = 179°). Evidence indicates that complexes of (NO)⁺ and N₂ are electronically similar. Hence, the principles of stereochemical control of valence may be applied to metal complexes of N₂. In a linearly coordinated Mⁿ˜m(NN) complex, valence electrons can be transferred from the metal to the N₂ ligand producing a bent, protonated, and/or metallated Mⁿ⁺²-(N=N^2-) complex. This reduction of N₂ can be effected by the addition of an appropriate ligand to M or by a change in the coordination geometry about M. Stereo-chemical control of valence leads to the rejection of one of the previously proposed mechanisms for reduction by nitrogenase.     

Surface structural-chemical characterization of a single-site d0 heterogeneous arene hydrogenation catalyst having 100% active sites

Structural characterization of the catalytically significant sites on solid catalyst surfaces is frequently tenuous because their fraction, among all sites, typically is quite low. Here we report the combined application of solid-state ¹³C-cross-polarization magic angle spinning nuclear magnetic resonance (¹³C-CPMAS-NMR) spectroscopy, density functional theory (DFT), and Zr X-ray absorption spectroscopy (XAS) to characterize the adsorption products and surface chemistry of the precatalysts (η⁵-C₅H₅)₂ZrR₂ (R = H, CH₃) and [η⁵-C₅(CH₃)₅]Zr(CH₃)₃ adsorbed on Brønsted superacidic sulfated alumina (AlS). The latter complex is exceptionally active for benzene hydrogenation, with ∼100% of the Zr sites catalytically significant as determined by kinetic poisoning experiments. The ¹³C-CPMAS-NMR, DFT, and XAS data indicate formation of organozirconium cations having a largely electrostatic [η⁵-C₅(CH₃)₅]Zr(CH₃)₂⁺···AlS⁻ interaction with greatly elongated Zr···O_AlS distances of ∼2.35(2) Å. The catalytic benzene hydrogenation cycle is stepwise understandable by DFT, and proceeds via turnover-limiting H₂ delivery to surface [η⁵-C₅(CH₃)₅]ZrH₂(benzene)⁺···AlS⁻ species, observable by solid-state NMR and XAS.     

Coordination of {Mo142} Ring to La3+ Provides Elliptical {Mo134La10} Ring with a Variety of Coordination Modes

A 28-electron reduced C_2h-Mo-blue 34Ǻ outer ring diameter circular ring, [Mo₁₄₂O₄₂₉H₁₀(H₂O)₄₉(CH₃CO₂)₅(C₂H₅CO₂)]^30- (≡{Mo₁₄₂(CH₃CO₂)₅(C₂H₅CO₂)}) comprising eight carboxylate-coordinated (with disorder) {Mo₂} linkers and six defect pockets in two inner rings (four and three for each, respectively), reacts with La³⁺ in aqueous solutions at pH 3.5 to yield a 28-electron reduced elliptical C_i-Mo-blue ring of formula [Mo₁₃₄O₄₁₆H₂₀(H₂O)₄₆{La(H₂O)₅}₄{La(H₂O)₇}₄{LaCl₂(H₂O)₅}₂]^10- (≡{Mo₁₃₄La₁₀}), isolated as the Na₁₀[Mo₁₃₄O₄₁₆H₂₀(H₂O)₄₆{La(H₂O)₅}₄{La(H₂O)₇}₄{LaCl₂(H₂O)₅}₂]·144 H₂O Na⁺ salt. The elliptical structure of {Mo₁₃₄La₁₀} showing 36 and 31 Å long and short axes for the outer ring diameters is attributed to four (A-D) modes of LaO₉/LaO₇Cl₂ tricapped-trigonal-prismatic coordination (TTP) geometries. Two different LaO₂(H₂O)₇ and one LaO₂(H₂O)₂Cl₂ TTP geometries (as A-C modes) for each of two inner rings result from the coordination of all three defect pockets of the inner ring for {Mo₁₄₂(CH₃CO₂)₅(C₂H₅CO₂)}, and two LaO₄(H₂O)₅ TTP geometries (as D mode) result from the displacement of two (acetate/propionate-coordinated) binuclear {Mo₂} linkers with La³⁺ in each inner ring. The isothermal titration calorimetry (ITC) of the ring modification from circle to ellipsoid, showing the endothermic reaction of [La³⁺]/[{Mo₁₄₂(CH₃CO₂)₅(C₂H₅CO₂)}] = 6/1 with ΔH = 22 kJ⋅mol^-1, ΔS = 172 J⋅K^-1⋅mol^-1, ΔG = −28 kJ⋅mol^-1, and K = 9.9 × 10⁴ M^-1 at 293 K, leads to the conclusion that the coordination of the defect pockets to La³⁺ precedes the replacement of the {Mo₂} linkers with La³⁺. ¹³⁹La- NMR spectrometry of the coordination of {Mo₁₄₂(CH₃CO₂)₅(C₂H₅CO₂)} ring to La³⁺ is also discussed.     

The power of the optimal asymptotic tests of composite statistical hypotheses

The easily computable asymptotic power of the locally asymptotically optimal test of a composite hypothesis, known as the optimal C(α) test, is obtained through a “double” passage to the limit: the number n of observations is indefinitely increased while the conventional measure ξ of the error in the hypothesis tested tends to zero so that ξ_nn^½ → τ ≠ 0. Contrary to this, practical problems require information on power, say β(ξ,n), for a fixed ξ and for a fixed n. The present paper gives the upper and the lower bounds for β(ξ,n). These bounds can be used to estimate the rate of convergence of β(ξ,n) to unity as n → ∞. The results obtained can be extended to test criteria other than those labeled C(α). The study revealed a difference between situations in which the C(α) test criterion is used to test a simple or a composite hypothesis. This difference affects the rate of convergence of the actual probability of type I error to the preassigned level α. In the case of a simple hypothesis, the rate is of the order of n^-½. In the case of a composite hypothesis, the best that it was possible to show is that the rate of convergence cannot be slower than that of the order of n^-½ ln n.     

Structure of a Fe4O6-Heteraadamantane-Type Hexacation Stabilized by Chelating Organophosphine Oxide Ligands

Metal-containing heteraadamantanes are compounds of interest due to their spectroscopic and magnetic properties, which make them promising materials for non-linear optics and semiconductors. Herein we report the comprehensive structural characterization of a new coordination compound of the formula [(µ-OH′)₂(µ-OH″)₄(O = P(Ph₂)CH₂CH₂(Ph₂)P = O)₄{Fe(t-BuOH)}₄](PF₆)₄(Cl)₂ with the chelating ligand Ph₂P(O)-CH₂CH₂-P(O)Ph₂. The compound crystallizes as a polynuclear metal complex with the adamantane-like core [Fe₄O₆] in the space group I-43d of a cubic system. The single-crystal XRD analysis showed that the crystal contains one symmetrically independent octahedrally coordinated Fe atom in the oxidation state +3. The adamantine-like scaffold of the Fe complex is formed by hydroxy bridging oxygen atoms only. Hirshfeld surface analysis of the bridging oxygen atoms revealed two types of µ-OH groups, which differ in the degree of exposure and participation in long-range interactions. Additionally, the Hirshfeld surface analysis supported by the enrichment ratio calculations demonstrated the high propensity of the title complex to form C-H^…Cl, C-H^…F and C-H^…O interactions.     

Conformation of cyclo(Gly-L-Pro-L-Pro-Gly-L-Pro-L-Pro)(2)Mg complex crystallized from CH(3)CN solution

The cyclic hexapeptides (Gly-L-Pro-L-Pro-Gly-L-Pro-L-Pro) in the (peptide—Mg—peptide)²⁺ complex have nearly identical asymmetric conformations. Each has two cis Pro-Pro linkages and lacks any intraring hydrogen bonds. The Mg²⁺ ion forms six ligands in a regular octahedral array with the carbonyl oxygen atoms of the two Gly residues and one Pro residue of each peptide. The “sandwich” complex has an approximate 2-fold rotation axis through the Mg²⁺ relating the two peptide moieties. Cyclo(Gly-Pro-Pro-Gly-Pro-Pro)₂Mg(ClO₄)₂· 4C²H₃CN crystallizes in space group P3₁ with a = b = 15.744(4) Å, c = 24.002(6) Å, γ = 120°, and Z = 3. A highlight of the structure determination is the ready location of the Mg self-vector in a Harker section and the development of the entire structure by use of the tangent formula starting with the known position of the Mg atom.     

One-Pot Self-Assembly of Dinuclear,Tetranuclear, and H-Bonding-Directed Polynuclear Cobalt(II), Cobalt(III), and Mixed-Valence Co(II)/Co(III) Complexes of Schiff Base Ligands with Incomplete Double Cubane Core

The reaction of 2,6-diformyl-4-methylphenol (DFMF) with 1-amino-2-propanol (AP) and tris(hydroxymethyl)aminomethane (THMAM) was investigated in the presence of Cobalt(II) salts, (X = ClO₄⁻, CH₃CO₂⁻, Cl⁻, NO₃⁻), sodium azide (NaN₃), and triethylamine (TEA). In one pot, the variation in Cobalt(II) salt results in the self-assembly of dinuclear, tetranuclear, and H-bonding-directed polynuclear coordination complexes of Cobalt(III), Cobalt(II), and mixed-valence Co^IICo^III: [Co₂^III(H₂L⁻¹)₂(AP⁻¹)(N₃)](ClO₄)₂ (1), [Co₄(H₂L⁻¹)₂(µ₃-1,1,1-N₃)₂(µ-1,1-N₃)₂Cl₂(CH₃OH)₂]·4CH₃OH (2), [Co₂^IICo₂^III(HL⁻²)₂(µ-CH₃CO₂)₂(µ₃-OH)₂](NO₃)₂·2CH₃CH₂OH (3), and [Co₂^IICo₂^III (H₂L1²⁻)₂(THMAM⁻¹)₂](NO₃)₄ (4). In 1, two cobalt(III) ions are connected via three single atom bridges; two from deprotonated ethanolic oxygen atoms in the side arms of the ligands and one from the1-amino-2-propanol moiety forming a dinuclear unit with a very short (2.5430(11) Å) Co-Co intermetallic separation with a coordination number of 7, a rare feature for cobalt(III). In 2, two cobalt(II) ions in a dinuclear unit are bridged through phenoxide O and μ₃-1,1,1-N₃ azido bridges, and the two dinuclear units are interconnected by two μ-1,1-N₃ and two μ₃-1,1,1-N₃ azido bridges generating tetranuclear cationic [Co₄(H₂L⁻¹)₂(µ₃-1,1,1-N₃)₂(µ-1,1-N₃)₂Cl₂(CH₃OH)₂]²⁺ units with an incomplete double cubane core, which grow into polynuclear 1D-single chains along the a-axis through H-bonding. In 3, HL²⁻ holds mixed-valent Co(II)/Co(III) ions in a dinuclear unit bridged via phenoxide O, μ-1,3-CH₃CO₂⁻, and μ₃-OH⁻ bridges, and the dinuclear units are interconnected through two deprotonated ethanolic O in the side arms of the ligands and two μ₃-OH⁻ bridges generating cationic tetranuclear [Co₂^IICo₂^III(HL⁻²)₂(µ-CH₃CO₂)₂(µ_3-OH)₂]²⁺ units with an incomplete double cubane core. In 4, H₂L1⁻² holds mixed-valent Co(II)/Co(III) ions in dinuclear units which dimerize through two ethanolic O (μ-RO⁻) in the side arms of the ligands and two ethanolic O (μ₃-RO⁻) of THMAM bridges producing centrosymmetric cationic tetranuclear [Co₂^IICo₂^III (H₂L1⁻²)₂(THMAM⁻¹)₂]⁴⁺ units which grow into 2D-sheets along the bc-axis through a network of H-bonding. Bulk magnetization measurements on 2 demonstrate that the magnetic interactions are completely dominated by an overall ferromagnetic coupling occurring between Co(II) ions.     

Kinetics of the Organic Compounds and Ammonium Nitrogen Electrochemical Oxidation in Landfill Leachates at Boron-Doped Diamond Anodes

Electrochemical oxidation (EO) of organic compounds and ammonium in the complex matrix of landfill leachates (LLs) was investigated using three different boron-doped diamond electrodes produced on silicon substrate (BDD/Si)(levels of boron doping [B]/[C] = 500, 10,000, and 15,000 ppm—0.5 k; 10 k, and 15 k, respectively) during 8-h tests. The LLs were collected from an old landfill in the Pomerania region (Northern Poland) and were characterized by a high concentration of N-NH₄⁺ (2069 ± 103 mg·L⁻¹), chemical oxygen demand (COD) (3608 ± 123 mg·L⁻¹), high salinity (2690 ± 70 mg Cl⁻·L⁻¹, 1353 ± 70 mg SO₄²⁻·L⁻¹), and poor biodegradability. The experiments revealed that electrochemical oxidation of LLs using BDD 0.5 k and current density (j) = 100 mA·cm⁻² was the most effective amongst those tested (C_8h/C₀: COD = 0.09 ± 0.14 mg·L⁻¹, N-NH₄⁺ = 0.39 ± 0.05 mg·L⁻¹). COD removal fits the model of pseudo-first-order reactions and N-NH₄⁺ removal in most cases follows second-order kinetics. The double increase in biodegradability index—to 0.22 ± 0.05 (BDD 0.5 k, j = 50 mA·cm⁻²) shows the potential application of EO prior biological treatment. Despite EO still being an energy consuming process, optimum conditions (COD removal > 70%) might be achieved after 4 h of treatment with an energy consumption of 200 kW·m⁻³ (BDD 0.5 k, j = 100 mA·cm⁻²).     

Tropospheric concentrations of methylchloroform, CH(3)CCl(3), in January 1978 and estimates of the atmospheric residence times for hydrohalocarbons

The ground level tropospheric concentrations of CH₃CCl₃ were measured from 55°N to 53°S during the time period around Jan. 1, 1978. The northern temperate zone concentration of CH₃CCl₃ averaged 94.6 ± 4.0 × 10^-12 by volume. The southern temperate zone concentration averaged 65.2 ± 1.3 × 10^-12, for a worldwide average of 80 × 10^-12 by volume. The ratio of concentrations between the two zones is 1.45 ± 0.07. The observed CH₃CCl₃ concentrations correspond to 0.52 ± 0.05 times the atmospheric release to that date, corresponding to an atmospheric residence time of 6.9 ± 1.2 yr. The atmospheric residence times for 22 other hydrohalocarbon molecules were estimated in comparison to that of CH₃CCl₃ through the relative rates of reaction with OH radicals.