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.     

Synthesis,Molecular Structure and Cytotoxicity of Molecular Materials Based on Water Soluble Half-Sandwich Rh(III) and Ir(III) Tetranuclear Metalla-Cycles

The neutral dinuclear complexes [(η⁵-C₅Me₅)₂Rh₂(μ-dhnq)Cl₂] (1) and [(η⁵-C₅Me₅)₂Ir₂(μ-dhnq)Cl₂] (2) (dhnqH₂ = 5,8-dihydroxy-1,4-naphthoquinone) were obtained from the reaction of [(η⁵-C₅Me₅)M(μ-Cl)Cl]₂ (M = Rh, Ir) with dhnqH₂ in the presence of CH₃COONa. Treatment of 1 or 2 in methanol with linear ditopic ligands L (L = pyrazine, 4,4′-bipyridine or 1,2-bis(4-pyridyl)ethylene), in the presence of AgCF₃SO₃, affords the corresponding tetranuclear metalla-rectangles [(η⁵-C₅Me₅)₄M₄(μ-dhnq)₂(μ-L)₂]⁴⁺ (L = pyrazine, M = Rh, 3; M = Ir, 4; L = 4,4′-bipyridine, M = Rh, 5; M = Ir, 6; L = 1,2-bis(4-pyridyl)ethylene, M = Rh, 7; M = Ir, 8). All complexes were isolated as their triflate salts and were fully characterized by infrared, ¹H and ¹³C NMR spectroscopy, and some representative complexes by single-crystal X-ray structure analysis. The X-ray structures of 3, 5 and 6 confirm the formation of the tetranuclear metalla-cycles, and suggest that complexes 5 and 6 possess a cavity of sufficient size to encapsulate small guest molecules. In addition, the antiproliferative activity of the metalla-cycles 3–8 was evaluated against the human ovarian A2780 (cisplatin sensitive) and A2780cisR (cisplatin resistant) cancer cell lines and on non-tumorigenic human embryonic kidney HEK293 cells. All cationic tetranuclear metalla-rectangles were found to be highly cytotoxic, with IC₅₀ values in the low micromolar range.     

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.     

Magnetic and Electrical Behaviors of the Homo- and Heterometallic 1D and 3D Coordination Polymers Based on the Partial Decomposition of the [Cr(C2O4)3]3− Building Block

One-dimensional (1D) oxalate-bridged homometallic {[Mn(bpy)(C₂O₄)]·1.5H₂O}_n (1) (bpy = 2,2’-bipyridine) and heterodimetallic {[CrCu₃(bpy)₃(CH₃OH)(H₂O)(C₂O₄)₄][Cu(bpy)Cr(C₂O₄)₃]·CH₂Cl₂·CH₃OH·H₂O}_n (2) coordination polymers, as well as the three-dimensional (3D) heterotrimetallic {[CaCr₂Cu₂(phen)₄(C₂O₄)₆]·4CH₃CN·2H₂O}_n (3) (1,10-phenanthroline) network, have been synthesized by a building block approach using a layering technique, and characterized by single-crystal X-ray diffraction, infrared (IR) and impedance spectroscopies and magnetization measurements. During the crystallization process partial decomposition of the tris(oxalato)chromate(III) happened and 1D polymers 1 and 2 were formed. The antiferromagnetic interactions between the manganese(II) ions were mediated by oxalate ligands in the chain [Mn(bpy)(C₂O₄)]_n of 1, with intra-chain super-exchange interaction 𝐽 = (−3.134 ± 0.004) K; magnetic interaction between neighbouring chains is negligible making this system closer than other known Mn-chains to the ideal 1D Heisenberg antiferromagnet. Compound 2 comprises a 1D coordination anion [Cu(bpy)Cr(C₂O₄)₃]_nⁿ⁻ (Cr2–Cu4) with alternating [Cr(C₂O₄)₃]³⁻ and [Cu(bpy)]²⁺ units mutually bridged through the oxalate group. Another chain (Cr1–Cu3) is similar, but involves a homodinuclear unit [Cu(bpy)(H₂O)(µ-C₂O₄)Cu(bpy)(CH₃OH)]²⁺ (Cu1–Cu2) coordinated as a pendant group to a terminal oxalate oxygen. Magnetic measurements showed that the Cu1−Cu2 cationic unit is a strongly coupled antiferromagnetic dimer, independent from the other magnetic ions within ferromagnetic chains Cr1–Cu3 and Cr2–Cu4. A 3D polymer {[CaCr₂Cu₂(phen)₄(C₂O₄)₆]·4CH₃CN·2H₂O}_n (3) comprising three different metal centers (Ca²⁺, Cr³⁺ and Cu²⁺) oxalate-bridged, contains Ca²⁺ atoms as nodes connected with four Cr³⁺ atoms through oxalate ligands. The network thus formed can be reduced to an underlying graph of diamondoid (dia) or (6⁶) topology. Magnetization of 3 shows the ferromagnetic oxalate-bridged dimers [Cu^IICr^III], whose mutual interaction could possibly originate through the spin polarization of Ca²⁺ orbitals. Compounds 1 and 3 exhibit lower electrical conductivity at room temperature (RT) in comparison to compound 2.     

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.     

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.     

Physicochemical Study of the Self-Disintegration of Calcium Orthosilicate (β→γ) in the Presence of the C12A7 Aluminate Phase

The β-γ polymorphic transition of calcium orthosilicate (C₂S) is a key phenomenon in cement chemistry. During this transition, the compound expands due to structural changes and a significant reduction in its density is observed, leading to its disintegration into a powder with a very high specific surface area. Owing to this tendency of the C₂S material to “self-disintegrate”, its production is energy-efficient and thus environmentally friendly. A physicochemical study of the self-disintegration process was conducted with the aim of determining how the amount of dodecacalcium hepta-aluminate (C₁₂A₇) in calcium orthosilicate (C₂S) affects the temperature at which the polymorphic transi-tions from α’L-C₂S to β-C₂S and from β-C₂S to γ-C₂S undergo stabilization. The applied techniques included differential thermal analysis (DTA), calorimetry and X-ray diffraction (XRD), and they made it possible to determine what C₂S/C₁₂A₇ phase ratio in the samples and what cooling rate constitute the optimal conditions of the self-disintegration process. The optimal cooling rate for C₂S materials with a C₁₂A₇ content of up to 60 wt% was determined to be 5 K·min⁻¹. The optimal mass ratio of C₂S/C₁₂A₇ was found to be 70/30, which ensures both efficient self-disintegration and desirable grain size distribution.     

Crystal Structure,Spectroscopic Characterization,Antioxidant and Cytotoxic Activity of New Mg(II) and Mn(II)/Na(I) Complexes of Isoferulic Acid

The Mg(II) and heterometallic Mn(II)/Na(I) complexes of isoferulic acid (3-hydroxy-4-methoxycinnamic acid, IFA) were synthesized and characterized by infrared spectroscopy FT-IR, FT-Raman, electronic absorption spectroscopy UV/VIS, and single-crystal X-ray diffraction. The reaction of MgCl₂ with isoferulic acid in the aqueous solutions of NaOH resulted in synthesis of the complex salt of the general formula of [Mg(H₂O)₆]⋅(C₁₀H₉O₄)₂⋅6H₂O. The crystal structure of this compound consists of discrete octahedral [Mg(H₂O)₆]²⁺ cations, isoferulic acid anions and solvent water molecules. The hydrated metal cations are arranged among the organic layers. The multiple hydrogen-bonding interactions established between the coordinated and lattice water molecules and the functional groups of the ligand stabilize the 3D architecture of the crystal. The use of MnCl₂ instead of MgCl₂ led to the formation of the Mn(II)/Na(I) complex of the general formula [Mn₃Na₂(C₁₀H₇O₄)₈(H₂O)₈]. The compound is a 3D coordination polymer composed of centrosymmetric pentanuclear subunits. The antioxidant activity of these compounds was evaluated by assays based on different antioxidant mechanisms of action, i.e., with ^•OH, DPPH^• and ABTS^•+ radicals as well as CUPRAC (cupric ions reducing power) and lipid peroxidation inhibition assays. The pro-oxidant property of compounds was measured as the rate of oxidation of Trolox. The Mg(II) and Mn(II)/Na(I) complexes with isoferulic acid showed higher antioxidant activity than ligand alone in DPPH (IFA, IC₅₀ = 365.27 μM, Mg(II) IFA IC₅₀ = 153.50 μM, Mn(II)/Na(I) IFA IC₅₀ = 149.00 μM) and CUPRAC assays (IFA 40.92 μM of Trolox, Mg(II) IFA 87.93 μM and Mn(II)/Na(I) IFA 105.85 μM of Trolox; for compounds’ concentration 10 μM). Mg(II) IFA is a better scavenger of ^•OH than IFA and Mn(II)/Na(I) IFA complex. There was no distinct difference in ABTS^•+ and lipid peroxidation assays between isoferulic acid and its Mg(II) complex, while Mn(II)/Na(I) complex showed lower activity than these compounds. The tested complexes displayed only slight antiproliferative activity tested in HaCaT human immortalized keratinocyte cell line within the solubility range. The Mn(II)/Na(I) IFA (16 μM in medium) caused an 87% (±5%) decrease in cell viability, the Mg salt caused a comparable, i.e., 87% (±4%) viability decrease in a concentration of 45 μM, while IFA caused this level of cell activity attenuation (87% ± 5%) at the concentration of 1582 μM (significant at α = 0.05).     

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).     

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.     

A synthetic precedent for the [FeIV2(mu-O)2] diamond core proposed for methane monooxygenase intermediate Q

Intermediate Q, the methane-oxidizing species of soluble methane monooxygenase, is proposed to have an [Fe^IV₂(μ-O)₂] diamond core. In an effort to obtain a synthetic precedent for such a core, bulk electrolysis at 900 mV (versus Fc^+/0) has been performed in MeCN at −40°C on a valence-delocalized [Fe^IIIFe^IV(μ-O)₂(L^b)₂]³⁺ complex (1b) (E_1/2 = 760 mV versus Fc^+/0). Oxidation of 1b results in the near-quantitative formation of a deep red complex, designated 2b, that exhibits a visible spectrum with λ_max at 485 nm (9,800 M⁻¹·cm⁻¹) and 875 nm (2,200 M⁻¹·cm⁻¹). The 4.2 K Mössbauer spectrum of 2b exhibits a quadrupole doublet with δ = −0.04(1) mm·s⁻¹ and ΔE_Q = 2.09(2) mm·s⁻¹, parameters typical of an iron(IV) center. The Mössbauer patterns observed in strong applied fields show that 2b is an antiferromagnetically coupled diiron(IV) center. Resonance Raman studies reveal the diagnostic vibration mode of the [Fe₂(μ-O)₂] core at 674 cm⁻¹, downshifting 30 cm⁻¹ upon ¹⁸O labeling. Extended x-ray absorption fine structure (EXAFS) analysis shows two O/N scatterers at 1.78 Å and an Fe scatterer at 2.73 Å. Based on the accumulated spectroscopic evidence, 2b thus can be formulated as [Fe^IV₂(μ-O)₂(L^b)₂]⁴⁺, the first synthetic complex with an [Fe^IV₂(μ-O)₂] core. A comparison of 2b and its mononuclear analog [Fe^IV(O)(L^b)(NCMe)]²⁺ (4b) reveals that 4b is 100-fold more reactive than 2b in oxidizing weak CH bonds. This surprising observation may shed further light on how intermediate Q carries out the hydroxylation of methane.     

New Volatile Perfluorinated Amidine–Carboxylate Copper(II) Complexes as Promising Precursors in CVD and FEBID Methods

In the present study, we have synthesised and characterised newly copper(II) complexes with the general formula [Cu₂(NH₂(NH=)CC₂F₅)₂(µ–O₂CR_F)₄], where R_F = CF₃, C₂F₅, C₃F₇, C₄F₉. Infrared spectroscopy, mass spectrometry with electron ionisation (EI MS), and density-functional theory (DFT) calculations were used to confirm compounds’ composition and structure. The volatility of the compounds was studied using thermal analysis (TGA), EI MS mass spectrometry, variable temperature infrared spectroscopy (VT IR), and sublimation experiments. Research has revealed that these compounds are the source of metal carriers in the gas phase. The thermal decomposition mechanism over reduced pressure was proposed. TGA studies demonstrated that copper transfer to the gaseous phase occurs even at atmospheric pressure. Two selected complexes [Cu₂(NH₂(NH=)CC₂F₅)₂(µ–O₂CC₂F₅)₄] and [Cu₂(NH₂(NH=)CC₂F₅)₂(µ–O₂CC₃F₇)₄] were successful used as chemical vapour deposition precursors. Copper films were deposited with an evaporation temperature of 393 K and 453 K, respectively, and a decomposition temperature in the range of 573–633 K without the use of hydrogen. The microscopic observations made to investigate the interaction of the [Cu₂(NH₂(NH=)CC₂F₅)₂(µ–O₂CC₂F₅)₄] with the electron beam showed that the ligands are completely lost under transmission electron microscopy analysis conditions (200 keV), and the final product is copper(II) fluoride. In contrast, the beam energy in scanning electron microscopy (20 keV) was insufficient to break all coordination bonds. It was shown that the Cu-O bond is more sensitive to the electron beam than the Cu-N bond.     

An atomic kinetic energy functional with full Weizsacker correction

A functional is proposed for representing the electronic kinetic energy of the ground state of an N-electron atom or ion in terms of its electron density, [Formula: see text] Here T_w is the Weizsacker quantity (⅛)∫(ρ·ρ/ρ)dτ and T₀ is the Thomas-Fermi quantity C_F ∫ ρ^{5 / 3}dτ. From Hartree-Fock data on 55 neutral atoms, C = 1.412 ± 0.033; for 1200 atoms and ions, C = 1.332 ± 0.053. The proposed functional gives the derivative δT/δρ its most important correct properties. The term T_w is shown to give the kinetic energy of the K shell, whereas the term (C/N^⅓)T₀ gives an incorrect statistical estimate of that energy. An alternative correction -(C/N^⅓)T gives even better results.     

Nonlinear Optical Properties of Porphyrin,Fullerene and Ferrocene Hybrid Materials

In this research, we investigated the second-order nonlinear optical (NLO) properties of multicomponent hybrid materials formed by meso-tetraphenylporphyrin P (both as free base and Zn^II complex), carrying in 2 or 2,12 β-pyrrolic position an electron donor ferrocene (Fc), and/or an electron acceptor fullerene (C60) moiety, connected to the porphyrin core via an ethynyl or an ethynylphenyl spacer. We measured the NLO response by the electric-field-induced second-harmonic generation (EFISH) technique in CH₂Cl₂ solution with a 1907 nm incident wavelength, recording for all the investigated compounds unexpected negative values of μβ₁₉₀₇. Since density functional theory (DFT) calculations evidenced for P-Fc dyads almost null ground state dipole moments and very low values for P-C60 dyads and Fc-P-C60 triads, our EFISH results suggested a significant contribution to γ_EFISH of the purely electronic cubic term γ(−2ω; ω, ω, 0), which prevails on the quadratic dipolar orientational one μβ(−2ω; ω, ω)/5kT, as confirmed by computational evidence.     

Effects of non-steroidal anti-inflammatory drugs and prostaglandins on alkali secretion by rabbit gastric fundus in vitro

The effects of non-steroidal anti-inflammatory drugs and prostaglandins E₂ and F_2α on the secretory and electrical activity of isolated rabbit fundic mucosa have been studied. Spontaneous acid secretion was inhibited by serosal side application of sodium thiocyanate (6×10⁻²M) and the resulting alkali secretion measured by pH stat tiration. Serosal side application of indomethacin (10⁻⁵M) or aspirin (3×10⁻³M) inhibited alkali secretion (0·55±0·06 to 0·12±0·06 μmol/cm²/h, n=6, p<0·01 and 0·28±0·06 to 0·11±0·03 μmol/cm²/h, n=7, p<0·02 respectively). Mucosal or serosal side prostaglandin E₂ (10⁻⁵ to 10⁻¹⁰M) and F_2α (10⁻⁴ to 10⁻¹⁰M) failed to alter the rate of alkalinisation but secretion was significantly increased by serosal side 16,16-dimethyl-prostaglandin E₂ (10⁻⁶M) (0·90±0·20 to 1·50±0·30 μmol/cm²/h, n=6, p<0·01). Serosal side application of 10⁻⁶M prostaglandin E₂ to fundic mucosae pretreated with either aspirin (5×10⁻³M) or indomethacin (10⁻⁵M), to reduce endogenous E₂ formation, also failed to alter alkali secretion. Pretreatment of the mucosa with 16,16-dimethyl-E₂ (10⁻⁶M) abolished the inhibitory effect of indomethacin (10⁻⁵M) on alkali secretion (n=6) but did not modify the secretory response to aspirin (3×10⁻³M) (fall in alkali secretion with aspirin = 81±11% and with aspirin plus 16,16-dimethyl-E₂ = 72±10%, n=7). In the doses used, none of the prostaglandins or non-steroidal anti-inflammatory drugs altered transmucosal potential difference or electrical resistance. These results show that the damaging agents, aspirin and indomethacin, both inhibit gastric alkali secretion but that modes of action may differ. The observation that prostaglandins, E₂ and F_2α failed to increase alkali production suggests that their protective activity against a variety of damaging agents as shown by others, may be mediated by another mechanism.     

Molecular and Polymer Ln2M2 (Ln = Eu,Gd, Tb,Dy; M = Zn,Cd) Complexes with Pentafluorobenzoate Anions: The Role of Temperature and Stacking Effects in the Structure; Magnetic and Luminescent Properties

Varying the temperature of the reaction of [{Cd(pfb)(H₂O)₄}⁺_n·n(pfb)⁻], [Ln₂(pfb)₆(H₂O)₈]·H₂O (Hpfb = pentafluorobenzoic acid), and 1,10-phenanthroline (phen) in MeCN followed by crystallization resulted in the isolation of two type of products: 1D-polymers [LnCd(pfb)₅(phen)]_n·1.5nMeCN (Ln = Eu (I), Gd (II), Tb (III), Dy (IV)) which were isolated at 25 °C, and molecular compounds [Tb₂Cd₂(pfb)₁₀(phen)₂] (V) formed at 75 °C. The transition from a molecular to a polymer structure becomes possible because of intra- and intermolecular interactions between the aromatic cycles of phen and pfb from neighboring tetranuclear Ln₂Cd₂ fragments. Replacement of cadmium with zinc in the reaction resulted in molecular compounds Ln₂Zn₂ [Ln₂Zn₂(pfb)₁₀(phen)₂]·4MeCN (Ln = Eu (VI), Tb (VIII), Dy (IX)) and [Gd₂Zn₂(pfb)₁₀(H₂O)₂(phen)₂]·4MeCN (VII). A new molecular EuCd complex [Eu₂Cd₂(pfb)₁₀(phen)₄]·4MeCN (X)] was isolated from a mixture of cadmium, zinc, and europium pentafluorobenzoates (Cd:Zn:Ln = 1:1:2). Complexes II-IV, VII and IX exhibit magnetic relaxation at liquid helium temperatures in nonzero magnetic fields. Luminescent studies revealed a bright luminescence of complexes with europium(III) and terbium(III) ions.     

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.     

Improved Electrical Characteristics of Gallium Oxide/P-Epi Silicon Carbide Static Induction Transistors with UV/Ozone Treatment Fabricated by RF Sputter

In this study, static induction transistors (SITs) with beta gallium oxide (β-Ga₂O₃) channels are grown on a p-epi silicon carbide (SiC) layer via radio frequency sputtering. The Ga₂O₃ films are subjected to UV/ozone treatment, which results in reduced oxygen vacancies in the X-ray photoelectron spectroscopy data, lower surface roughness (3.51 nm) and resistivity (319 Ω·cm), and higher mobility (4.01 cm²V⁻¹s⁻¹). The gate leakage current is as low as 1.0 × 10⁻¹¹ A at V_GS = 10 V by the depletion layer formed between n-Ga₂O₃ and p-epi SiC at the gate region with a PN heterojunction. The UV/O₃-treated SITs exhibit higher (approximately 1.64 × 10² times) drain current (V_DS = 12 V) and on/off ratio (4.32 × 10⁵) than non-treated control devices.     

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.     

Structural and kinetic modeling of an activating helix switch in the rhodopsin-transducin interface

Extracellular signals prompt G protein-coupled receptors (GPCRs) to adopt an active conformation (R*) and catalyze GDP/GTP exchange in the α-subunit of intracellular G proteins (Gαβγ). Kinetic analysis of transducin (G_tαβγ) activation shows that an intermediary R*·G_tαβγ·GDP complex is formed that precedes GDP release and formation of the nucleotide-free R*·G protein complex. Based on this reaction sequence, we explore the dynamic interface between the proteins during formation of these complexes. We start from the R* conformation stabilized by a G_tα C-terminal peptide (GαCT) obtained from crystal structures of the GPCR opsin. Molecular modeling allows reconstruction of the fully elongated C-terminal α-helix of G_tα (α5) and shows how α5 can be docked to the open binding site of R*. Two modes of interaction are found. One of them – termed stable or S-interaction – matches the position of the GαCT peptide in the crystal structure and reproduces the hydrogen-bonding networks between the C-terminal reverse turn of GαCT and conserved E(D)RY and NPxxY(x)_5,6F regions of the GPCR. The alternative fit – termed intermediary or I-interaction – is distinguished by a tilt (42°) and rotation (90°) of α5 relative to the S-interaction and shows different α5 contacts with the NPxxY(x)_5,6F region and the second cytoplasmic loop of R*. From the 2 α5 interactions, we derive a “helix switch” mechanism for the transition of R*·G_tαβγ·GDP to the nucleotide-free R*·G protein complex that illustrates how α5 might act as a transmission rod to propagate the conformational change from the receptor-G protein interface to the nucleotide binding site.