Syntheses, structures and photophysical properties of heteronuclear Zn-Ln coordination complexes

Four heteronuclear Zn-Ln coordination complexes, [Nd₂Zn₂(p-toluylate)₁₀(phen)₂] (1), [Ln₂Zn₂(p-toluylate)₁₀(phen)₂]·2(HAc)_1/2 (Ln=Tb 2, Ho 3) and [PrZn₂(p-toluylate)₅(Ac)₂(phen)₂] (4) (phen=1, 10-phenanthroline), are synthesized by the hydrothermal method and their structures are measured by single-crystal X-ray diffraction. The IR and UV-vis-NIR absorption spectra and the emission spectra in the visible and near-infrared (NIR) regions of the four complexes are determined at room temperature. In the NIR region (or in the visible region), the complexes show the characteristic emission bands of Ln³⁺ ions, which may be attributed to sensitization from the ligands (the ligand directly-coordinated to Ln³⁺ ions and d-block) to Ln³⁺ ions after forming the Zn-Ln complexes. It is reported for the first time in this paper that the Zn-Pr complex 4 can exhibit the broad emission band in the NIR region. In addition, the shift, split or broadness of the ff emission bands in the NIR region of complexes 1, 3 and 4 are discussed.     

Band intensities in the infrared spectra of metal carbonyl complexes: Chromium,molybdenum and tungsten hexacarbonyls

The absolute integrated intensities for IR absorption bands of M(CO)₆ (M = Cr, Mo, W) were measured. The calculations of dipole moment derivatives of the molecules were performed using a procedure suggested by L. S. Mayants and B. S. Averbukh. The effective atomic charges of M(CO)₆ are estimated and discussed.     

Syntheses,X‐ray crystal structures,and emission properties of protonated tripyridyltriazines and their ruthenium(II) complexes

A series of metal‐free compounds, ie, planar triprotonated triazine, triazineH₃Cl(PF₆)₂ ( 1 ), planar triprotonated triazineH₃Br(PF₆)₂ ( 2 ), and nonplanar monoprotonated triazineHPF₆ ( 3 ), were prepared. Abbreviations used are triazine = tri‐2‐pyridyltriazine. Ruthenium complexes [RuCl(bpy)(L)](PF₆), [RuCl(bpy)(L)](PF₆)₂, and [Ru(L)₂](PF₆)₂ were also prepared, where bpy is 2,2′‐bipyridine and L's are triazine ( 4 ) and monoprotonated triazine ( 5 ), respectively. Ruthenium complexes [Ru(triazine)₂](PF₆)₂ ( 6 ) were also prepared and crystallized. The X‐ray crystal structures of the 3 compounds 1 , 2 , and 3 and the complex 6 were determined. They were also characterized by electrospray ionization mass spectrometry, UV‐vis spectroscopy, and density functional theory calculations.     

Lattice dynamics of molybdenum and tungsten

Summary The lattice dynamics of molybdenum and tungsten has been re-examined within the framework of the transition metal model potential by incorporating the local-field correction to the dynamical matrix for phonon dispersion relation. It is observed that the local-field correction can be represented by an attractive short-range potential which tends to cancel or ?screen? the Born-Mayer repulsion. The numerical calculations for molybdenum and tungsten show that the local-field correction plays a significant role and leads to a better agreement between the theoretically computed phonon dispersion curves and the experimental data.     

Theoretical photoelectronic spectra of molybdenum, tungsten, and rhenium disilicides

Photoelectronic spectra of volume samples of molybdenum, tungsten, and rhenium disilicides are theoretically investigated as functions of the excitation energy (hv = 12–1486 eV) by the method of linearized attached plane waves. The main contribution to the spectrum at low (hv = 12–52 eV) and very high (hv = 1486 eV) excitation energies is given by the metal d-states, while the contribution of the Si p-states is dominant at intermediate excitation energies. An analysis of the calculated results demonstrates that the main peak of the photoelectronic spectra is displaced by 0.2 eV toward the bottom of the valence band when going from MoSi₂ to WSi₂; it is displaced by 0.3 eV when going from WSi₂ to ReSi_1.75. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 75–80, July, 2006.     

Calculation of mechanical strength of crystalline lattices of iron,molybdenum, and tungsten

Semiempirical tensor equations of state were obtained for iron, molybdenum, and tungsten and used to examine the mechanical properties of their crystalline lattices under conditions of a complex system of stresses. The most hazardous systems of stresses were distinguished, and stresses and deformations were calculated. The obtained values of strength are in good agreement with the existing empirical data.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 74–78, 1972.     

Synthesis,structures and near-infrared luminescence properties of Ho and Yb coordination complexes

Four Ln³⁺ coordination complexes with the formulas [Ln(p-toluylate)₂(Ac)(H₂O)]_n (Ln=Ho 1, Yb 2) and {[Ln₂(OOCCH₂CH₂COO)₃(H₂O)₄]·6H₂O}_n (Ln=Ho 3, Yb 4) were synthesized hydrothermally. Their structures were determined by single-crystal X-ray diffraction. Complexes 1 and 2 are isomorphic and form infinite 2D network structures comprising p-toluylate and acetate (Ac^–) moieties. Complexes 3 and 4 are also isomorphic and possess infinite 2D structures in which succinate acts as bridging ligands that are connected to a 3D hydrogen bonding network by O–H…O hydrogen bonds. Solid-state IR and UV-Vis-NIR spectra, excitation and emission spectra were determined for the four complexes at room temperature. Complexes 1 and 2 exhibit characteristic NIR emission bands of Ln³⁺ ions but these are shifted and split relative to the theoretical positions. This is also evident for their UV-Vis-NIR spectra. The influence of ligands on enhancing the NIR luminescence of Ln³⁺ ions in complexes is discussed.     

Syntheses,X‐ray crystal structures,and emission properties of diprotonated tetrapyridylpyrazine and triprotonated terpyridine

A series of metal‐free compounds, that is, planar diprotonated tetraH₂(PF₆)₂ ( 1 ), planar monoprotonated bppzHPF₆ ( 2 ), nonplanar diprotonated bppzH₂(PF₆)₂ ( 3 ), and planar triprotonated terpyH₃Cl(PF₆)₂ ( 4 ), were prepared and characterized by electrospray ionization mass spectrometry, Ultraviolet–visible spectroscopy and cyclic voltammetry. Abbreviations used are tetra = tetra‐2‐pyridylpyrazine, bppz = 2,3‐bis(2‐pyridyl)pyrazine, and terpy = 2,2′:6′,2″‐terpyridine. The X‐ray crystal structures of the four compounds 1 , 2 , 3 , and 4 were determined. Both protonated pyridine rings are hydrogen bonded intramolecularly to the adjacent pyridine ring in compounds 1 and 3 . The π–π* absorption bands in the ultraviolet region for 1 , 2 , 3 , and 4 in acetonitrile were red‐shifted relative to those of the corresponding neutral unprotonated compounds. All the cyclic voltammetry for the protonated species, 1 , 2 , 3 , and 4 , showed the first reduction waves from ?0.37 to ?1.18 V, that were more positive than those of the neutral ones. Density functional theory was applied to interpret the planarity in 1 . The attachment of two protons to the two terminal tetra nitrogens in 1 leads to the remarkable emission (Φ = 0.031). The attachment of three protons to the three terpy nitrogens in 4 also gives the large quantum yield (Φ = 0.48). Copyright © 2015 John Wiley & Sons, Ltd.     

Syntheses, crystal structures, visible and near-IR luminescent properties of ternary lanthanide (Dy, Tm) complexes containing 4,4,4-trifluoro-1-phenyl-1,3-butanedione and 1,10-phenanthroline

The ligands 4,4,4-trifluoro-1-phenyl-1,3-butanedione (Hbfa) and 1,10-phenanthroline (phen) were used to prepare ternary lanthanide (Ln) complexes [Dy(bfa)₃phen and Tm(bfa)₃phen]. Crystal data: Dy(bfa)₃phen C₄₂H₂₆F₉N₂O₆Dy, triclinic, P1¯, a=9.9450(6) Å, b=14.0944(9) Å, c=14.6043(9) Å, α=82.104(1)°, β=87.006(1)°, γ=76.490(1)°, V=1971.1(2) Å³, Z=2; Tm(bfa)₃phen C₄₂H₂₆F₉N₂O₆Tm, triclinic, P1¯, a=9.898(5) Å, b=13.918(5) Å, c=14.753(5) Å, α=83.517(5)°, β=86.899(5)°, γ=76.818(5)°, V=1965.3(14) Å³, Z=2. The coordination number of the central Ln³⁺ (Ln=Dy, Tm) ion is eight, with six oxygen atoms from three Hbfa ligands and two nitrogen atoms from the phen ligand. The photophysical properties of the two complexes were studied by absorption spectra, diffuse reflectance spectra, and emission spectra. They show the characteristic luminescence of the corresponding Ln³⁺ ion in both visible and near-IR (NIR) region. Additionally, the energy transfer mechanisms between the ligands and central Ln³⁺ ions were discussed.     

Three green luminescent cadmium complexes containing 8-aminoquinoline ligands: Syntheses, crystal structures, emission spectra and DFT calculations

Three complexes, Cd(8-aminoql)₂×₂ (8-aminoql=8-aminoquinoline; X⁻=ClO₄⁻, SCN⁻, 1 and 2, respectively) and Cd(8-aminoql)(N₃)₂ (3), were synthesized and structurally characterized. For each complex, the Cd²⁺ ion exhibits distorted octahedral coordination geometry. Two 8-aminoquinoline molecules and two counter-anions are coordinated to the Cd²⁺ center to form a mononuclear species with two trans-ClO₄⁻ anions for 1, while two SCN⁻ anions adopt a cis-configuration for 2. The intermolecular H-bonding interactions between the -NH₂ groups and the O atom (1) and the S atom (2) result in the formation of a 2-D layered structure. In the crystal of 3, the N₃⁻ anions bridging the neighboring Cd(8-aminoql)²⁺ units form a 1-D coordination polymer. The three complexes emit green luminescence. The emission bands possess a broad asymmetric feature, which can be assigned to L′LCT transitions based on DFT and TDDFT calculations.     

Laser photolytic deposition of molybdenum and tungsten thin film microstructures

We have deposited thin metal films of Mo and W with sub-m lateral resolution using the photodissociation of the carbonyls by the frequency doubled radiation of an Arion laser at cw and ps-pulse operation, respectively. In both regimes similar curves are obtained for the intensity dependence of the deposition rate. No difference was observed for the lateral resolution using cw or ps-pulse irradiation. Measurements of the deposition rate as a function of the spot size indicate that the decomposition occurs in the adsorbed phase.     

Field emission studies of selenium adsorption on tungsten and molybdenum

The adsorption of selenium on tungsten and molybdenum field emitters has been studied. Despite the topographical similarity of the two substrates there are marked differences in the migration and localised adsorption of the first two monolayers of selenium. Anomalous behaviour of the emission current and Fowler-Nordheim parameters is found for adsorption on both substrates. Measurements on single crystal planes indicate that this behaviour is not caused by localised growth or clustering effects. It is suggested that the model proposed by Nicolaou and Modinos to explain similar effects during germanium adsorption on tungsten is also applicable in the present case.     

ESCA and IR study of cyclopentadienyl tungsten and molybdenum carbonyl compounds

The ESCA spectra of a selection of cyclopentadienyl tungsten and molybdenum carbonyls are reported. The combination of ESCA and IR provides data of a c     

Highly oriented pyrolitic graphite anomalous structures and fullerenes self-assembly

Scanning tunneling microscopy (STM) was used to look for unusual self-structures on highly oriented pyrolitic graphite (HOPG) that can mimic fullerenes assemblies. HOPG features that may be taken as C₆₀ molecular structures were found on this surface. The HOPG self-structures have been presented earlier as anomalies of the bare HOPG surface in the literature. The experimental results are in agreement with earlier STM reports on bare and modified HOPG.     

Effect of molybdenum doping on the electrochromic properties of tungsten oxide thin films by RF magnetron sputtering

Thin films of pure and molybdenum (Mo)-doped tungsten trioxide (WO₃) were deposited on indium tin oxide (ITO)-coated glass and Corning glass substrates by RF magnetron sputtering technique. The effect of Mo doping on the structural, morphological, optical and electrochromic properties of WO₃ films was studied systematically. The energy dispersive X-ray analysis (EDAX) revealed that the films consist of molybdenum concentrations from 0 to 2 at.%. X-ray diffraction (XRD) studies indicated that with the increase of Mo concentration the structural phase transformation takes place from polycrystalline to amorphous phase. The crystallite size of the films decreased from 24 to 12 nm with increase of doping concentration of Mo in WO₃. Scanning electron microscope (SEM) analysis revealed that Mo dopant led to significant changes in the surface morphology of the films. The electrochemical and electrochromic performance of the pure and Mo-doped WO₃ were studied. The WO₃ films formed with 1.3 at.% Mo dopant concentration exhibited high optical modulation of 44.3 % and coloration efficiency of 42.5 cm²/C.