Structure of the complex UCl<Subscript>4</Subscript>∙2DMF by vibrational infrared spectroscopy and density functional theory

Structural models are designed and spectral characteristics are computed based on DFT calculations for a complex of UCl₄ with two molecules of DMF (UCl₄∙2DMF). The calculations were carried out using a B3LYP hybrid functional in the LANL2DZ effective core potential approximation for the uranium atom and an allelectron basis set, cc-pVDZ, for all other atoms with partial force-field scaling. Two structural variants were found for the complex. The first structure is more stable, has C _i symmetry, and is characterized by trans arrangement of ligands. The energy of the second structure of C₂ symmetry (with cis arrangement of ligands) is greater by 46 kJ/mol. The formation of the complex is shown to be accompanied by significant changes in the structure of UCl₄. The obtained spectral characteristics are analyzed and compared with experimental data. The adequacy of the proposed models and the agreement between calculation and experiment are demonstrated.     

Studies on Pyridylpyrazolone System Iv[1] Spectroscopic Studies of the Tautomeric Structure of 4-Arylazo-L-(Methyl or Phenyl)-3-(3′ -Pyridyl)-Z-Pyrazolin-5-ones

The electronic absorption spectra of a series of 4-aryl-azopyridylpyrazolones were investingated in different organic solvents of different polarities. The ir-spectra analysis suggested the presence of enol-azo and hydrazono-keto tautomeric structures. The ¹H-nmr-spectra of these compounds were analysed and assigned in term of these proposed tautomeric structures. An additional proof of this finding was given by mass spectral fragmentation analyses.     

Molecular Orientation and Aggregation in the Langmuir-Blodgett Films of 4-[4′-(4″-Decyloxy Phenylazo) Naphthloxy] Butyl Trimethylammonium Dextran Sulfate Studied by Ultra-Violet and Infrared Spectroscopy

Infrared transmission, Reflectance-Absorption (RA) and Ultra-Violet (UV) spectra were measured for mono-and multi-layers Langmuir-Blodgett (LB) films of 4-[4′-(4″-decyIoxy phenylazo)naphthloxy] butyl trimethylammonium bromide formed with SDS to study the molecular orientation and aggregation. The results indicate that the compound do not aggregate in the LB films, and the alkyl tail is nearly perpendicular to the substrate surface and the chromorphore part adopts trans-zigzag conformation. These results also suggest that the molecular orientation and aggregation are not depend upon the number of monolayers The comparison of infrared transmission and RA spectra indicates that the hydrocarbon chain is nearly perpendicular to the substrate surface, but the two rings in the chromophore part are tilted considerably from the surface normal.     

Structure and magnetotransport properties of the new quasi-two-dimensional molecular metal β″-(BEDT-TTF)4H3O[Fe(C2O4)3] · C6H4Cl2

The β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G(A^I=NH ₄ ⁺ , H₃O⁺, K⁺, Rb⁺; M^III=Fe, Cr; G = “guest” solvent molecule) family of layered molecular conductors with magnetic metal oxalate anions exhibits a pronounced dependence of the conducting properties on the type of neutral solvent molecules introduced into the complex anion layer. A new organic dichlorobenzene (C₆H₄Cl₂)-containing conductor of this family, namely, β″-(BEDT-TTF)₄H₃O[Fe(C₂O₄)₃] · C₆H₄Cl₂, is synthesized. The structure of the synthesized single crystals studied by X-ray diffraction is characterized by the following parameters: a = 10.421(1) Å, b= 19.991(2) Å, c= 35.441(3) Å, β = 92.87(1)°, V= 7374(1) ų, space groupC2/c, and Z = 4. In the temperature range 0.5&;2-300 K, the conductivity of the crystals is metallic without changing into a superconducting state. The magnetotransport properties of the crystals are examined in magnetic fields up to 17 T at T = 0.5 K. In fields higher than 10 T, Shubnikov-de Haas oscillations are detected, and the Fourier spectrum of these oscillations contains two frequencies with maximum amplitudes of about 80 and 375 T. The experimental results are compared with the related data obtained for other phases of this family. The possible structural mechanisms of the effect of a guest solvent molecule on the transport properties of the β″-(BEDT-TTF)₄A^I[M^III(C₂O₄)₃] · G crystals are analyzed.     

Study on the spin crossover transition and glass transition for Fe(II) complex film, [Fe(II)(H-triazole) 3 ]@Nafion, by means of M?ssbauer spectroscopy

[Fe(II)(H-trz)₃]@Nafion (trz = triazole) is a transparent spin crossover complex film, where the spin crossover transition between the low-spin (S = 0) and the high-spin (S = 2) states takes place between 225?K and 300?K. In this film, two doublets corresponding to the low-spin and high-spin states were observed in the ⁵⁷Fe M?ssbauer spectra, reflecting the spin crossover transition. From the analysis of ⁵⁷Fe M?ssbauer spectra, the Debye temperatures of the low-spin and high-spin sites were estimated at 185?K and 176?K, respectively, in the temperature range between 10?K and 150?K. In this film, the total intensity of the M?ssbauer spectra corresponding to the low-spin and high-spin sites drastically decreases above 200?K, reflecting the glass transition of Nafion, where the lattice vibration of [Fe(H-trz)₃] $_{\rm n}^{\,\,\rm 2n+}$ is softened just as in solution due to micro-Brown motion of the segment of Nafion polymer membrane.     

Coexistence of one-electron- and monoprotonated two-electron-reduced species of the K5[PMo2VW9O40] · 24H2O heteropolyoxometalate identified by EPR

The simulation of the room-temperature experimental electron paramagnetic resonance spectrum of K₅[PMo₂VW₉O₄₀] · 24 H₂O heteropolyoxometalate indicates the presence of equal amounts of a one-electron-reduced species (g _∥ = 1.922,g _⊥ = 1.972,A _∥ = 181 G,A _⊥ = 63 G) and a monoprotonated two-electron-reduced species with mixed-valence V^IV, Mo^V and Mo^VI ions (g _iso = 1.972, ΔB _iso(p-p) = 450 G). Two unprotonated one-electron-reduced isomers are identified in dimethylsulfoxide-H₂O solution of the sample atT = 100 K (g _∥¹ = 1.929,g _⊥¹ = 1.990,A _∥¹ = 179 G,A _⊥¹ = 65 G andg _∥² = 1.918,g _⊥² = 2.000,A _∥² = 187 G,A _⊥² = 80 G, respectively). The values of the in-plane π(V−O) bond π₂² coefficient for the one-electron-reduced species (0.87 at room temperature and 0.83 and 0.74 for the species in frozen solution) suggests the delocalization of the vanadium unpaired electron towards the molybdenum ions via O_b atoms.     

Synthesis,Spectroscopic Characterization and DFT/TD-DFT Calculations of new Fluorescent Derivatives of Imidazo[4′,5′:3,4]Benzo[<Emphasis Type="Italic">c</Emphasis>]Isoxazole

An increasingly wide variety of fluorescent compounds is used in biotechnology, genomics, immunoassays, array technologies, imaging, and drug discovery. Therefore, synthesis of fluorophores with novel structural features can be interesting and useful in various fields. In this paper, four new fluorescent heterocyclic compounds with high quantum yields are introduced. These new fluorophores are synthesized in moderate to high yields via regioselective nitration of 3-alkyl-8-(4-chlorophenyl)-3 H-imidazo[4′,5′:3,4]benzo[c]isoxazoles. The latter compounds are obtained from the reaction of 1-alkyl-5-nitro-1 H-benzoimidazoles with (4-chlorophenyl)acetonitrile in basic MeOH solution. Physical spectral (UV-vis, IR, ¹HNMR, ¹³C NMR, NOESY and fluorescence) and analytical data have established the structures of synthesized compounds. The fluorescence properties of new fluorescent heterocyclic compounds are studied. The fluorescence of all compounds is very intense and fluorescence quantum yields are high (> 0.52). Density functional theory (DFT) calculations are performed to provide the optimized geometries, relevant frontier orbitals and the prediction of ¹H NMR chemical shifts for confirming the exact structure of fluorescent compounds. Calculated electronic absorption spectra were also obtained by time-dependent density functional theory (TD-DFT) method.

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Observed difference between the probabilities of recoilless resonance absorptionf′ and reemissionf″ of gamma-quanta in single crystals of Na2[Fe(CN)5NO]·2 H2O

The recoilless absorption probability factor,f, and recoilless reemission,f, both measured on Na₂[Fe(CN)₅NO]·2 H₂O single crystals using the black filter technique, were found to be different. Unexpectedly, the results found weref>f. In the calculation off, selfabsorption in the scatterer, non-ideality of the black filter and the influence of non-resonant scattering processes have all been taken into account. By varying the scattering geometry for the incoming and outgoing -beam relative to the crystallographic axes only a change in the reemitted valuesf _a, f_b, f_c could be detected because of the long lifetime of the excited nucleus (10^–7 s) relative to the lattice vibration frequencies (10¹² Hz).     

Study on the ferromagnetic state in iron mixed-valence complexes, A[FeIIFeIII(dto)3] (A = (n-CnH2n + 1)4N; dto = C2S2O2) by means of Mössbauer spectroscopy

We have investigated the ferromagnetic states for (n-C_nH_2n?+?1)₄N[Fe^IIFe^III(dto)₃] (n = 3–6; dto = C₂O₂S₂) by means of ⁵⁷Fe Mössbauer spectroscopy. The major component of the spin configuration in the ferromagnetic states for n = 3 and 4 is the low-temperature phase (LTP) with the Fe^III (S = 5/2) and Fe^II (S = 0) states. The high-temperature phase (HTP) of n = 4 remains by more than 20%, which is consistent with two ferromagnetic transitions (T_C = 7 & 13 K). Moreover, it was revealed that the Mössbauer spectra in the ferromagnetic states for n = 5 and 6 correspond to the HTP consisting of the Fe^II (S = 2) and Fe^III (S = 1/2) states.