Theoretical study of the electronic spectrum of binuclear gold(I) complexes

The electronic structure and the spectroscopic properties of [Au₂(CS₃)₂]^?2, [Au₂(pym‐2‐S)₂] (pym = pyrimidethiolate), [Au₂(dpm)₂]⁺² (dpm = bis(diphosphino)methane) were studied using density functional theory (DFT) at the B3LYP level. The absorption spectrum of these binuclear gold(I) complexes was calculated by single excitation time‐dependent (TD) method. All complexes showed a ¹(5dσ* → 6pσ) transition associated with a metal–metal charge transfer, which is strongly interrelated with the gold–gold distance. Furthermore, we have calculated the frequency of the gold–gold vibration (ν_Au2) on the above complexes. The values obtained are theoretically in agreement with experimental range. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Industrial standardization of thermal analysis in Japan

To satisfy the needs for industrial standards for thermal analysis in the Japanese polymer industry, round-robin tests of differential scanning calorimetry (DSC), thermogravimetry (TG), thermomechanical analysis (TMA) and thermodilatometry (TD) have been carried out recently. The results are discussed in this short review. The DSC applications tested were not only for determination of transition temperature but also for measurements of the transition heat and heat capacity. The TG task group did not aim at longterm thermal endurance studies, but relative thermal stability in molding and estimation of filler content, residual solvent content, etc. TMA was found to be a useful tool for measuring softening temperature and heat distortion temperature, especially for high-temperature engineering plastics, instead of the Vicat test which has temperature limitations. For temperature calibration of DSC and TG, ICTA-NIST certified reference materials were used together with other potential temperature standards; some inorganic substances and alloys were not found to be preferable to pure metals. For TMA and TD metal plates were found to be very useful for temperature calibration. Analysis of the round-robin test results also clarified present status of practical applications of thermal analysis, such as reproducibility and causes of errors. Plenary lecture     

Electronic structure and molecular orbital study of the first excited state of the high‐efficiency blue OLED material bis(2‐methyl‐8‐quinolinolato)aluminum(III) hydroxide complex from ab initio and TD‐B3LYP

Bis(2‐methyl‐8‐quinolinolato)aluminum(III) hydroxide complex (AlMq₂OH) is used in organic light‐emitting diodes (OLEDs) as an electron transport material and emitting layer. By means of ab initio Hartree–Fock (HF) and density functional theory (DFT) B3LYP methods, the structure of AlMq₂OH was optimized. The frontier molecular orbital characteristics and energy levels of AlMq₂OH have been analyzed systematically to study the electronic transition mechanism in AlMq₂OH. For comparison and calibration, bis(8‐quinolinolato)aluminum(III) hydroxide complex (Alq₂OH) has also been examined with these methods using the same basis sets. The lowest singlet excited state (S₁) of AlMq₂OH has been studied by the singles configuration interaction (CIS) method and time‐dependent DFT (TD‐DFT) using a hybrid functional, B3‐LYP, and the 6‐31G* basis set. The lowest singlet electronic transition (S₀ → S₁) of AlMq₂OH is π → π* electronic transitions and primarily localized on the different quinolate ligands. The emission of AlMq₂OH is due to the electron transitions from a phenoxide donor to a pyridyl acceptor from another quinolate ligand including C → C and O → N transference. Two possible electron transfer pathways are presented, one by carbon, oxygen, and nitrogen atoms and the other via metal cation Al³⁺. The comparison between the CIS‐optimized excited‐state structure with the HF ground‐state structure indicates that the geometric shift is mainly confined to the one quinolate and these changes can be easily understood in terms of the nodal patterns of the highest occupied and lowest unoccupied molecular orbitals. On the basis of the CIS‐optimized structure of the excited state, TD‐B3‐LYP calculations predict an emission wavelength of 499.78 nm. An absorption wavelength at 380.79 nm on the optimized structure of B3LYP/6‐31G* was predicted. They are comparable to AlMq2OH 485 and 390 nm observed experimentally for photoluminescence and UV‐vis absorption spectra of AlMq₂OH solid thin film on quartz, respectively. Lending theoretical corroboration to recent experimental observations and supposition, the reasons for the blue‐shift of AlMq2OH were revealed. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2004     

Stir bar sorptive extraction with in situ derivatization and thermal desorption-gas chromatography-mass spectrometry for determination of chlorophenols in water and body fluid samples

A new method, stir bar sorptive extraction (SBSE) with in situ derivatization and thermal desorption (TD)-gas chromatography-mass spectrometry (GC-MS), which is used for the determination of trace amounts of chlorophenols, such as 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TrCP), 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP) and pentachlorophenol (PCP), in tap water, river water and human urine samples, is described. The derivatization conditions with acetic acid anhydride and the SBSE conditions such as extraction time are investigated. Then, the stir bar is subjected to TD followed by GC-MS. The detection limits of the chlorophenols in tap water, river water and human urine samples are 1-2, 1-2, and 10-20 pg ml⁻¹ (ppt), respectively. The calibration curves for the chlorophenols are linear and have correlation coefficients higher than 0.99. The average recoveries of the chlorophenols in all the samples are higher than 95% (R.S.D. < 10%) with correction using added surrogate standards, 2,4-dichlorophenol-d₅, 2,4,6-trichlorophenol-¹³C₆, 2,3,4,6-tetrachlorophenol-¹³C₆ and pentachlorophenol-¹³C₆. This simple, accurate, sensitive and selective analytical method may be applicable to the determination of trace amounts of chlorophenols in liquid samples.     

Determination of 4-nonylphenol and 4-tert.-octylphenol in water samples by stir bar sorptive extraction and thermal desorption-gas chromatography-mass spectrometry

A simple and highly sensitive method called thermal desorption (TD)-gas chromatography-mass spectrometry (GC-MS), which is used for the determination of trace amounts of 4-nonylphenol (NP) and 4-tert.-octylphenol (OP) in water samples, is described. NP and OP in samples are extracted from water samples and concentrated by the stir bar sorptive extraction (SBSE) technique. A stir bar coated with polydimethylsiloxane (PDMS) is added to a 2.0 ml water sample and stirring is carried out for 60 min at room temperature (25 °C) in a headspace vial. Then the extract is high sensitively analyzed by TD-GC-MS without any derivatization step. The optimum SBSE conditions are realized at an extraction time of 60 min. The detection limits are 0.02 ng ml⁻¹ for NP and 0.002 ng ml⁻¹ for OP. The method shows good linearity over the concentration range of 0.1-10 ng ml⁻¹ for NP and 0.01-10 ng ml⁻¹ for OP, and the correlation coefficients are higher than 0.999. The average recoveries of NP and OP are higher than 97% (R.S.D.: 3.6-6.2%) with correction using the added surrogate standards, 4-(1-methyl) octylphenol-d₅ and deuterium 4-tert.-octylphenol. This simple, accurate, sensitive and selective analytical method may be used in the determination of trace amounts of NP and OP in tap and river water samples.     

Structural studies and quantum chemical calculations of Cr(III), Fe(III) and Ru(III) bromazepam complexes

The reaction of bromazepam (7‐bromo‐1,3‐dihydro‐5‐(2‐pyridyl)‐2H ‐1,4‐benzodiazepin‐2‐one, BZM) with Cr(III) ( 1 ), Fe(III) ( 2 ) and Ru(III) ( 3 ) salts gives complexes of the type [M(BZM)₃]⋅3X (X = Cl or NO₃). Structural characterization was extensively carried out using various analytical and spectral tools such as infrared, ¹H NMR and UV–visible spectroscopies and magnetic, conductance, elemental and thermal analyses. BZM is a bidentate ligand and interacts with the metal ions via the pyridine and benzodiazepin‐2‐one nitrogen atoms. The magnetic and electronic properties of 2 and 3 are consistent with low‐spin octahedral complexes. The three BZM molecules are non‐isoenergetically coordinated to the metal ions and this is reflected in the values of the second‐order interaction energy. The antibacterial activity was studied using Staphylococcus aureus and Escherichia coli . Coordination of BZM to Cr(III) or Ru(III) ions leads to a marked increase in toxicity with respect to the inactive Fe(III) complex 2 .     

Exploring the electro‐optical properties of conjugated polymers based on oligo‐selenophene and oligo(3,4‐ethylenedioxyselenophene)

For seeking high‐efficiency narrow‐band‐gap donor materials to enhance short‐circuit current density for organic solar cells, a series of oligo‐selenophene (OS) and oligo(3,4‐ethylenedioxyselenophene) (OEDOS) with various chain lengths were designed and characterized using density functional theory (DFT) and time‐dependent DFT calculations. Based on the results, it can be seen that with increasing chain length of the oligomers in both syn‐ and anti‐adding manners, the bond length alternation is decreased which indicates that the π‐electron delocalization is increased. Also, when the chain length is increased the electronic energy gap and the optical energy gap are decreased. It can be concluded that the syn‐(OS)_n=10,14,15, anti‐(OS)_n=14 and anti‐(OEDOS)_n=7–12 oligomers can act as low‐band‐gap polymers. Therefore they can absorb more sunlight based on maximum wavelength (higher than 620 nm). Furthermore, a red shift in the simulated absorption spectra of (OS)_n and (OEDOS)_n donors is observed. It is found that (OS)_n=14,15 with syn configuration of the extended oligomers is the most suitable donor for the design of high‐performance organic solar cells possessing a narrow electronic band gap, high exciton lifetime and broad and intense absorption spectra that cover the solar spectrum leading to complete light‐harvesting efficiency.     

Ultraviolet light absorber with low surface energy: synthesis and characterization

Novel fluorine-containing ultraviolet absorbers (FBPs) with low surface energy were successfully synthesized based on 2,4-dihydroxy benzophenone (BP-1), and their structures were characterized by ¹H NMR, ¹³C NMR, FTIR, and HRMS. UV absorption of FBPs was studied in 10⁻⁴ M dichloromethane (CH₂Cl₂), which demonstrated the superior UV absorption capability of FBPs (ca. ?=1.7×10⁴ to 2.2×10⁴ at λ_max) over the matrix (?=1.7×10⁴ at λ_max). Quantum chemistry calculation was performed to investigate the stable structure and UV electronic absorption bands of FBPs. The surface chemistry information of high-chlorinated polyethylene (HCPE) coating films embedded with ultraviolet absorbers (UVAs) was given by X-ray photoelectron spectroscopy (XPS) and contact angle measurement. The results show that the surface enrichment capability of FBPs is remarkably better than traditional UVAs (including BP-1, BP-3, BP-12) because of the low surface energy properties of FBPs.     

(FD)~2TD计算金属表面场增强

本文首次利用依赖于频率的时域有限差分法(FD)2TD来计算隐失波激励下金属粒子表面的场增强。首先,利用(FD)2TD计算了三维球形银粒子的表面场增强,与国外文献[11]中用不同方法对此问题的计算结果进行了对比,结果较为相符,说明我们自己编写的(FD)2TD程序是可信的。然后,利用此程序计算了在全内反射条件下,处于介质板上纳米尺度边长的正三角形银粒子表面的场增强,给出了该正三角形银粒子三角端点存在场增强的所谓"热点"并给出了该处的场增强值随样品距离的变化曲线。