Synthesis, characterization and photophysical properties of quinolin-8-olato chelated osmium(II) organometallics bearing a pendant imine-phenol motif and electrogeneration of trivalent analogue

The reaction of Os(RL1)(PPh3)2(CO)Br, 1b, with qui-nolin-8-ol (HQ), 2, has furnished complexes of the type [Os(RL2)(PPh3)2(CO)(Q)], 3, in excellent yield (RL1 is C6H2O-2-CHNHC6H4R(p)-3-Me-5, RL2 is C6H2OH-2-CHNC6H4R(p)-3-Me-5 and R is Me, OMe, Cl). In this process, quinolin-8-olato (Q) undergoes five-membered chelation, the iminium-phenolato function tautomerizing to the imine-phenol function. The trans geometry of the Os(PPh3)2 fragment is consistent with the occurrence of a single 31P resonance near –6.0 ppm in 3. In dichloromethane solution, 3 displays a quasireversible 3+/3 couple near 0.40 V vs. SCE (3+ is the osmium (III) analogue of 3). Coulometrically generated solutions of 3+ displays a strong absorption near 340 nm, 415 nm and 500 nm and are one-electron paramagnetic (low-spin d5, S = 1/2) and show rhombic EPR spectra in 1:1 dichloromethanetoluene solution at 77 K with g values near 2.44, 2.20, 1.83. Distortion parameters using the observed g values have been computed. Solutions of 3 absorb near 420 nm and emit near 510 nm at 298 K and 580 nm at 77 K. The fluorescence is believed to originate from the 3MLCT state.

Palladium-catalyzed cross-coupling reaction of phenyl fluoroalkanesulfonates with organometallics

The palladium-catalyzed cross-coupling reaction of phenyl fluoroalkanesulfonates with organozinc,organotin and organoaluminum reagents in the presence of lithium chloride takes place to afford alkylbenzenes in good yields.However,the coupling reaction with organolithium and Grignard reagents proceeds unsatisfactorily with poor regioselectivity.On the basis of the isolation of an oxidative addition product of phenyl fluoroalkanesulfonate to palladium,a catalytic cycle in the reaction is suggested.

Functional Organometallics

1 Results The lecture will address aspects of functional organometallics related to the development of novel organometallic materials.In chromium complexes of fused arenes-regio-and diastereoselectively accessible by chromium-templated benzannulation of arylcarbenes by alkynes[1]-a haptotropic migration of the chromium fragment along the π-face of fused arenes is controlled by both thermodynamics and the substitution pattern of the arene and the metal coligand sphere,and can be applied towards an organo...

High Quality Zinc Sulfide Epitaxial Layers Grown by Metalorganic Chemical Vapour Deposition

ZnS films were successfully grown by metallorganic chemical vapour deposition (MOCVD) at atmospheric pressure on (100) GaAs substrates. The deposition was carried out at a substrate temperature between 280 approximately 550°C with optimisation of reactor design and growth conditions. The gas phase prereaction is effectively restrained. These epilayers exhibit high crystallographic quality and reveal a mirror surface morphology. The peak halfwidths of X-ray diffraction patterns from their (400) faces are within 0.06 approximately 0.09°. The epilayers grown on (111) GaAs, (112¯0) Al2O3 and (100) Si have proven to be single crystalline feature. The optical and electrical characteristics of ZnS epilayers are measured by photoluminescence, cathodeluminescence, and the Van der Pauw method. The results indicate that there are not a large number of deep centers that could be detected both at 77K and at room temperature. A broad CL peak around 2.897eV and 2.672eV was observed only under very strong excitation. Their origin has not been examined. All epilayers present high resistivities up to 1013Ω&middotcm.

Studies on Rare Earth Complexes with Ethylene-1,2-Dioxydiacetic Acid

Some new complexes RE2(EDODA)3&middot3H2O, where RE = La, Nd, Eu, Gd, Tb, Er, Yb, Lu and Y, EDODA = ethylene-1,2-dioxydiacetate, have been synthesized and characterized by elemental analysis, molar conductance, IR spectra, UV spectra, TG-DTA, 1H NMR and 13C NMR spectra. Various analyses indicate that the complexes are of nine-coordinated binuclear structure. The carboxylates are bidentate ligands and the ether oxygen atoms also coordinate to rare earth ions. Three water molecules are crystalline water. In addition, the influence of concentration on the chemical shift has been studied through the 1H NMR spectra of the complex Lu2(EDODA)3&middot3H2O in different concentrations.

Novel organometallic aromatic polyester based on ferrocene

A novel polyester containing ferrocenyl was prepared by low-temperature interface polycondensation of 1,1'-ferrocenedicarboxylic acid chloride with 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one(DHPZ),which is a twisted non-coplanar heterocyclic bisphenol-like monomer.The newly generated polymer was evaluated based on characterization of its solubility,viscosity measurements,elemental analysis,FTIR spectroscopy,differential scanning calorimetric and thermogravimetric studies.

RING OPENING COPOLYMERIZATION OF SUCCINIC ANHYDRIDE-ETHYLENE OXIDE BY Al(Ⅲ) ORGANOMETALLIC CATALYSTS

Ring opening copolymerization of succinic anhydride (SA) with ethylene oxide (EO)was successfully carried out by using a series of aluminum-based catalyst in 1,4-dioxane at62±2℃. The results showed that in-situ AlR_3-H_2O (R=ethyl, iso-butyl) catalysts gavehigher molecular weight (M_w～10~4), while Al(OR)_3 catalysts gave the higher alternatingcopolymer structure with slightly lower molecular weight. The in-situ AlR_3-H_2O systemshave been evaluated in more detail for the reaction which showed the optimum H_2O/Almolar ratio to be 0.5. The copolymers with different composition (F_(SA)/F_(EO)= 36/64to 45/55 mol/mol) were synthesized by using different monomer feed ratio. The melt-ing point (T_m), glass transition temperature (T_g) and enthalpy of fusion (ΔH_f) of thesecopolymers are depended on the copolymer composition and in the range of 87～102℃,-12～-18℃, and 37～66J/g, respectively. The second heating scan of DSC also in-dicated that the higher alternating copolymer was more easily recrystallized. The onsetdecomposition temperature was more than 300℃ under nitrogen and influenced by thecopolymer composition.

Low eradication rate of Helicobacterpyloriwith triple 7-14 days and quadriple therapy in Turkey

AIM:The eradication rate of Helicobacter pylori (H pylori) shows variation among countries and regimens of treatment. We aimed to study the eradication rates of different regimens in our region and some factors affecting the rate of eradication. METHODS:One hundred and sixty-four H pylori positive patients (68 males,96 females;mean age:48±12 years) with duodenal or gastric ulcer without a smoking history were included in the study.The patients were divided into three groups according to the treatment regimens.Omeprazole 20mg,clarithromycin 500mg,amoxicillin 1g were given twice daily for 1 week (Group Ⅰ) and 2 weeks (Group Ⅱ). Patients in Group Ⅲ received bismuth subsitrate 300mg, tetracyline 500mg and metronidazole 500mg four times daily in addition to Omeprazole 20mg twice daily.Two biopsies each before and after treatment were obtained from antrum and corpus,and histopathologically evaluated. Eradication was assumed to be successful if no H pylorus was detected from four biopsy specimens taken after treatment.The effects of factors like age,sex,H pylori density on antrum and corpus before treatment,the total H pylori density,and the inflammation scores on the rate of H pylori eradication were evaluated. RESULTS:The overall eradication rate was 42%.The rates in groups Ⅱ and Ⅲ were statistically higher than that in group Ⅰ (P<0.05).The rates of eradication were 24.5%, 40.7% and 61.5% in groups Ⅰ,Ⅱ and Ⅲ,respectively.The eradication rate was negatively related to either corpus H pylori density or total H pylori density (P<0.05).The median age was older in the group in which the eradication failed in comparison to that with successful eradication (55 yr vs 39 yr,P<0.001).No correlation between sex and H pylori eradication was found. CONCLUSION:Our rates of eradication were significantly lower when compared to those reported in literature.We believe that advanced age and high H pylori density are negative predictive factors for the rate of H pylori eradication.

Global instability index as a crystallographic stability descriptor of halide and chalcogenide perovskites

Crystallographic stability is an important factor that affects the stability of perovskites.The stability dictates the commercial applications of lead-based organometal halide perovskites.The tolerance factor(t)and octahedral factor(μ)form the state-of-the-art criteria used to evaluate the perovskite crystallographic stability.We studied the crystallographic stabilities of halide and chalcogenide perovskites by exploring an effective alternative descriptor,the global instability index(GII)that was used as an indicator of the stability of perovskite oxides.We particularly focused on determining crystallographic reliability by calculating GII.We analyzed the bond valence models of the 243 halide and chalcogenide perovskites that occupied the lowest-energy cubic-phase structures determined by conducting the first-principles-based total energy minimization calculations.The decomposition energy(ΔHD)reflects the thermodynamic stability of the system and is considered as the benchmark that helps assess the effectiveness of GII in evaluating the crystallographic stability of the systems under study.The results indicated that the accuracy of predicting thermodynamic stability was significantly higher when GII(73.6%)was analyzed compared to the cases when t(55%)andμ(39.1%)were analyzed to determine the stability.The results obtained from the machine learning-based data mining method further indicate that GII is an important descriptor of the stability of the perovskite family.

Synthesis, Growth, and Characterization of a New Thiourea and Bismuth Chloride Complex with Excellent Nonlinear Optical Properties

Crystals of a new organometallic nonlinear optical （NLO） compound, di-ta-chloro-bis[chlorotri（thiourea）bismuth（Ⅲ）]- pentachloro（thiourea）bismuth-ate（Ⅲ） （DCBPB）, have been successfully grown from formic acid aqueous solutions of thio-urea and bismuth chloride by a slow evaporation technique. The crystal structure and atomic composition of DCBPB have been confirmed by single crystal X-ray diffraction （SCXRD）, Fourier transform infrared spectra, and elemental analysis. The SCXRD results proved that DCBPB crystallizes in triclinic space group P1 with unit cell dimensions of a = 7.0606（2） A, b = 8.8106（4） A, c = 16.3247（8） A, a = 99.242（4）°, fl = 95.309（3）°, ）/= 105.856（3）°, and Z= 2. DCBPB crystal exhibits excel-lent transmittance from 500 to 2500 nm and green fluorescence with maximum emission at 508 nm. The thermogravimetric-differential scanning calorimetry （TG-DSC） analysis indicates that a solid-phase reaction took place at 170.1 ℃, whereas the decomposition temperature of the crystal material was 189℃. The NLO property obtained by the Kurtz powder test showed that the second harmonic generation efficiency of DCBPB crystal is two-seventh of KDP crystal.

Preparation of CH_3NH_3PbI_3 thin films for solar cells via Vapor Transfer Method

Organometal halide perovskite based solar cells have emerged as one of the most promising candidates for low-cost and high-efficiency solar cell technologies. Here a Vapor Transfer Method （VTM） is used to fabricate high quality perovskite thin films in a balanced vacuum capsule. By adjusting the reaction tem- perature, CH_3NHl_3 saturated vapor which then reacts with Pbl_2 films can be controlled and the formation process of CH_3NH_3Pbl_3 perovskite films can be further influenced. Prepared perovskite films which ex- hibit pure phase, smooth surface and high crystallinity are assembled into planar heterojunction inverted solar cells. The whole fabrication process of solar cell devices is organic solution free. Finally, the cham- pion cell achieved power conversion efficiency （PCE） of 13.08% with negligible current-voltage hysteresis under fully open-air conditions. The photovoltaic performance could be further enhanced by optimizing perovskite composition and the device structure.

A DFT Investigation on Hydrogen Adsorption Based on Alkali-metal Organic Complexes

Using density functional theory calculation based on the B3LYP method,we have studied the interactions of H2 molecules with alkali-metal organic complexes C6H6-nLin（n = 1～3）,C6H5Na and C6H5K.A significant part of the electronic charge of M s orbital（Li 2s,Na 3s,K 4s） is donated to phenyl and is accommodated by H2 bonding orbital.For all the complexes considered,each bonded alkali-metal atom can adsorb up to five H2 in molecular form with the mean binding energy of 0.59,0.55 and 0.56 eV/H2 molecule for C6H6-nLin（n = 1～3）,C6H5Na and C6H5K,respectively.The kinetic stability of these hydrogen-covered organometallic complexes is discussed in terms of energy gap between HOMO and LUMO.It is remarkable that these alkali-metal organic complexes can store up to 23.80 wt% hydrogen.Therefore,the complexes studied may be used as hydrogen storage materials.

ORGANOMETALLIC FERROELECTRIC LIQUID CRYSTALS Ⅰ. LIQUID CRYSTAL PROPERTIES OF ORTHO—PALLADATED BINUCLEAR COMPLEXES OF AZINE, IMINE AND AZO DERIVATIVES

The mesomorphie properties of title complexes are investigated by means of DSC and polarizing microscopy. The mesophase temperature ranges of complexes are wider than that of corresponding organic ligands. The bridging groups of the complexes have profoand effects on the mesomorphic behavior, When the bridging groups are opticallhy active. the compleve show chiral smectic

Recent Advances in Organic-inorganic Hybrid Photoresists

Photoresists are radiation-sensitive materials used for forming patterns to build up IC devices.To date,most photoresists have been based on organic polymers,which have been dominating the semiconductor industries over the past few decades.It is obvious that extreme ultraviolet(EUV)lithography has become the next-generation lithography technology.The development of comprehensive performance EUV resist is one of the most critical issues.However,organic polymeric photoresists are difficult to meet the harsh requirements of EUV lithography.Pure inorganic photoresists such as metal salts,hydrogen silsesquioxane(HSQ)are expected for EUV lithography due to their high resistance and high resolution.But the low sensitivity makes them not suitable for high volume manufacturing(HVM).Organic-inorganic hybrid photoresists,containing both organic and inorganic components,are regarded as one of the most promising EUV resists.They combine both merits of organic and inorganic materials and have significant advantages in machinability,etching resistance,EUV absorption,and chemical/thermal stability.Organic-inorganic hybrid photoresists are considered as ideal materials for realizing industrialgrade patterns below 10 nm.This review mainly focuses on the development of organic-inorganic hybrid photoresists over the past decade.

STUDY ON THE SURFACE OF TITANIUM CARBIDE PARTICLE PACKAGED NICKEL

Two kinds of packaged processes by nickel on the surface of titanium carbide particle are studied in this work. One is the chemical nickel-plating, the other is the organometallic compound decomposition. The composition, structure and morphology of the packaged powder were analyzed with XRD, DAT/TGA, SEM, EPMA etc. It has been shown that nickel was even dispersed on the surface of titanium carbide particle by the. two kinds of processes, deposited nickel exists as spherical particles of about 0.1 μm in diameter. The merits and demerits of the two kinds of processes have been compared, the organometallic copmound decomposition among them is a kind of hopeful method, which is not used by other researchers.

X—RAY STRUCTURE OF A SEMICONDUCTING ORGANOMETALLIC SALT,[FeCp(Tol)]_2[Ni(mnt)_2]

The title compound was prepared and characterized.Its crystal Structure was determined by X—ray diffraction analysis,and consists of segregated cation and an- ion stacks in the perpendicular directions.Crystal data:monoclinic,P2_1/c,Mr=765.21, a=7.882(2)b=15.526(4),c=13.736(2)β=99.87(2)~0,V=1656.0(6)~3,Ac =1.53g/cm^3,Z=2,F(000)=780,R=0.040 and R_w=0.056.

Two-Dimensional Infrared Spectroscopy of the Photoproduct of π-Cyclopentadienyliron Dicarbonyl Dimer

Equilibrium photoproduct of 7r-cyclopentadienyliron dicarbonyl dimer [CpFe（CO）2]2 in non- polar solvent carbon tetrachloride （CC14） is investigated using time-resolved 2D IR spec- troscopy. One of the several possible visible-light-driven photoreaction pathways is confirmed and the product is found to contain a di-carbonyl group that exhibits quantum beating be- tween two equivalent transitions in time-resolved 2D IR spectra, which turns out to be the anti-symmetric and symmetric stretching of the terminal carbonyl stretching modes of CpFe（CO）2C1. This is the main product and its reaction pathway involves radical formation, followed by chloride addition. Quantum-chemistry computations support these experimental results. Our results indicate that 2D IR method can be used to identify in situ structures and dynamics of chemical species involved in condensed-phase chemical reactions.

Surface Organometallic Chemistry——Surface Supported Triruthenium Ketenylidene Clusters and Their Performance in ^(13)CO Isotopic Exchange and Alkylation Reactions

Recently, metal clusters supported on some solids which simultaneously exhibit many excellent properties of both metal clusters and supports have been intensively studled. Such surface organometallic chemistry, which concerns the synthesis, structure, reactivity and catalytic activity of surface-supported organometallfc compounds is a new

Theoretical Investigation on Structures and Second-order Nonlinear Optical Properties of (Thiophene) Manganese Tricarbonyl Cations

The structures of several recently reported organometallic NLO chromophores, (thio-phene) manganese tricarbonyl cations, were fully optimized at the DFT non-local (GGA) level. The calculated results show that the fragments 2-SC4H3CH=CHC6H4-R in these organometallic chromophores are not planar with dihedral angles of 42.2~59.8 between two aromatic rings, which are different from those of uncoordinated counterparts. Based on the DFT geometry opti-mization, the second-order nonlinear optical polarizabilities were calculated by using RPA method. The calculated results indicate that incorporation of +3Mn(CO) unit with thiophene leads to a sub-stantial increase in the second-order polarizability (b).