Computational studies on the radiative and nonradiative processes of luminescent N-heteroleptic platinum(II) complexes

Three N-heteroleptic Pt(II) complexes, [Pt(C^C)(O^O)] [O^O = acetylacetonate, C^C = 1-phenyl-1,2,4-triazol-5-ylidene (1), C^C = 4-phenyl-1,2,4-triazol-5-ylidene (2), C^C = 2-phenylpyrazine (3)] have been investigated with density functional theory (DFT) and time-dependent density functional theory (TDDFT). The radiative decay rate constants of complexes 1–3 have been discussed with the oscillator strength (f_n), the strength of spin–orbit coupling (SOC) interaction between the lowest energy triplet excited state (T₁) and singlet excited states (S_n), and the energy gaps between E(T₁) and E(S_n). To illustrate the nonradiative decay processes, the transition states between triplet metal-centered (³MC) and T₁ states have been optimized and were verified with the calculations of vibrational frequencies and intrinsic reaction coordinate (IRC). In addition, the minimum energy crossing points (MECPs) between ³MC and ground states (S₀) were optimized. At last, the potential energy curves relevant to the nonradiative decay pathways are simulated. The results show that complex 3 has the biggest photoluminescence quantum yield because the complex 3 has the biggest radiative decay rate constant and the smallest nonradiative decay rate constant in complexes 1–3.     

Synthesis of heterocyclic metal complexes and their evaluation as marine antifoulants

4-Amino-3-thio-1,24-triazolidine (L₁) and 4-amino-5-thio-1,3,4-thiadiazole (L_II) as well as their metal complexes of the general formulae ML_I·2H₂O and ML_IICl (M; Pb(II), Cd(II) and Zn(II)) were prepared. With Sn(II), we obtained Sn(L_I)₂·2H₂O and SnL_IICl, respectively. The structures of the compounds were identified through elemental analysis, and IR and UV spectra measurements, in addition to thermal analysis in case of the metal complexes. The antifouling properties of the compounds were tested by their incorporation into paint formulations which were applied to PVC substrates and tested in water from Alexandria western harbour. When the compounds were added at 17·5% by volume, the coated panels were fouled after 3 months of immersion. The addition of 6·7% by volume of tributyltin oxide to 15·8% of the prepared compounds in one formulation elevated the paint efficiency and prevented fouling for 11 months. Paint containing solely tributyltin oxide at the same concentration was inactive against algae.     

Synthesis and characterization of poly(ethylene aspartate)-metal complexes

Poly(ethylene aspartate) [PEA] was synthesized by the melt condensation of D,L-aspartic acid and ethylene glycol. PEA containing pendent amino and carbonyl groups in its repeating chain was used as the polymeric ligand for complexation with transition metal ions, viz. Co(II), Ni(II), Cu(II), Mn(II), Zn(II), Cd(II), Ca(II), Mg(II), Pb(II) and Hg(II). Complexation was found to be most effective in DMSO. The resulting polyester-metal complexes were solid coloured materials which have been characterized by IR spectroscopy, elemental analysis and magnetic susceptibility measurements. The thermal stability of the polyester-metal complexes was investigated by thermogravimetric analysis (TGA). On the basis of the physico-chemical studies, an oxygen and nitrogen coordinated structure for the polyester-metal complexes is proposed.     

Study on Adsorption Behavior of Rare Earth Complexes on Nanometer-Size Titanium Dioxide with ICP-AES

Inrecentyears ,rareearthelements (REEs)havebeenwidelyusedinfunctionalmaterials ,cata lystsandotherproductsinindustry ,diagnosisreagentsofmagneticresonanceimaging (MRI)inmedicineandsomefertilizersinagricultureespeciallyinChina .However,asaresultoftheirusage ,moreandmoreREEsaregettingintotheenvironment,andalsointohumanbodyviafoodchain[1,2 ] .Itisnotclearwhetherrareearthelementsareessentialforman ,soitisveryurgenttostudythebiologicaleffectofrareearthelementsinhumanhealthandenvironment .Inthes…     

硫酸铵-氯化亚锡-孔雀绿体系浮选分离铂

研究了在盐酸介质中硫酸铵存在下氯化亚锡—孔雀绿—水体系浮选分离铂的方法。在最佳实验条件下，铂的浮选率可达100．0％，并与常见贱金属完全分离。     

Electrical conductivity in iodine-doped ethyl cellulose

The electrical conductivity of solution-grown ethyl cellulose (EC) films, 5–30 μm thick, has been studied in the sandwich configuration (metal–EC–metal) as a function of iodine concentration from 0.5 to 5.0 wt% ratio. The studies were conducted in the temperature range 333–383 K, while the field was varied over the range (3.0–5.5) × 10⁴V/cm. Aluminium was used as the lower electrode, while the upper electrode was of Al, Ag, Cu, Au or Sn. Certain transient effects such as a large burst of current immediately after the application of field were observed. An attempt was made to identify the nature of the current by comparing the observed dependence on electric field, electrode material and temperature with the respective characteristic features of the existing theories of electrical conduction. The results show that the electrical conduction follows Ohm's law at lower fields, while at higher fields, space-charge limited current (SCLC) was observed. It was also found that Richardson–Schottky emission was responsible, to some extent, for the transport of charge carriers in the polymer. The conductivity of the films increased on doping with iodine. The dopant molecules are considered to act as additional trapping centes and provide links between the polymer molecules in the amorphous region, thus resulting in the formation of charge transfer complexes.     

Near‐Infrared Light‐Emitting Diodes (LEDs) Based on Poly(phenylene)/Yb‐tris(β‐Diketonate) Complexes

Near‐infrared‐emitting electroluminescent (EL) devices using blue‐light‐emitting polymers blended with the Yb complexes Yb(DBM)₃phen (DBM = dibenzoylmethane), Yb(DNM)₃phen (DNM = dinaphthoylmethane), and Yb(TPP)L(OEt) (L(OEt) = [(C₅H₅)Co{P(O)Et₂}₃]^–) have been studied. EL devices composed of Yb(DNM)₃phen blended with PPP‐OR11 showed enhanced near‐IR output at 977 nm when compared to those fabricated with Yb(DBM)₃phen/PPP‐OR11 blends. The maximum near‐IR external efficiencies of the devices with Yb(DBM)₃phen and Yb(DNM)₃phen are, respectively, 7 × 10^–5 (at 6 V and at 0.81 mA mm^–2) and 4 × 10^–4 (at 7 V, and 0.74 mA mm^–2). The optimal blend composition for EL device performance consisted of PPP‐OR11 blended with 10–20 mol‐% Yb(DNM)₃phen. A device fabricated using Yb‐(TPP)L(OEt)/PPP‐OR11 showed significantly enhanced near‐IR output efficiency, and future efforts will focus on devices fabricated using porphyrin‐based materials.     

Mixtures of tertiary amine functionalized azo-containing mesogens with acid-functionalized polymers

A tertiary amine functionalized 4-nitro-4′-alkoxy azobenzene mesogen with a 10 or 12 carbon spacer (azo-nN) was synthesized and complexed in equimolar proportions with poly(acrylic acid) (PA-H) and poly(sulfonic acid) (PSS-H), and investigated by thermogravimetric analysis, differential scanning calorimetry, polarizing optical microscopy, Fourier transform infrared spectroscopy and X-ray diffraction. The neat azo-nN is characterized by a partial bilayer S_A mesophase at higher temperatures, and a highly ordered phase, in which the molecules are stacked orthogonally in bilayers, at lower temperatures. As supported by infrared analysis, for the azo-nN/PA-H mixture, the complexation is partial while for the same azo-nN/PSS-H mixture, complete proton transfer occurs. When the azo-nN is blended with the PA-H, regarded as a weak acid, a biphasic system is generated and the thermotropic behavior of neat mesogen is not significantly affected. In contrast, by mixing the same mesogen with a PSS-H (regarded as a strong acid), the thermotropic behavior is significantly influenced: the complexation generated a partial or interdigitated smectic A or tilted smectic C lamellar phase.