Studies on interactions of excited cadmium and mercury atoms with secondary and tertiary alkyl- and silylamines in gas phase

The Cd(³P₁)- and Hg(³P₁)-photosensitized emissions of some secondary and tertiary alkyl- and silylamines have been investigated under conditions of steady illumination at 493 and 298 K, respectively. The emission bands were observed at around 440 nm in the cadmium-photosensitized reactions of these amines. In contrast, no appreciable emission bands were observed in the mercury-photosensitized reactions of these amines. However, upon addition of tert-butyl alcohol to the amine-mercury system, an emission band evolved at around 350 nm in the mercury-photosensitization. The peak-wavelengths for secondary and tertiary alkyl- and silylamines are slightly shorter than the values predicted from the correlations between the peak wavelength and the first ionization energy obtained in the cadmium- and mercury-photosensitized luminescence of ammonia and primary amines. The quenching efficiencies of the cadmium and mercury resonance lines by secondary alkyl- and silylamines are higher than those by tertiary alkyl- and silylamines. These observations suggest that the steric hindrance by the alkyl and silyl groups to the approach of the nitrogen atom in the amines to excited cadmium and mercury atoms seems to be an important factor for the stabilization of the exciplexes and the quenching of the resonance lines. The behavior of silylamines is similar to that of alkylamines in cadmium- and mercury-photosensitized reactions.     

Formation of an exciplex with mixed ligands in the mercury-photosensitized luminescence of alcohol-amine mixtures in the liquid phase

The liquid-phase mercury-photosensitized luminescence of tert-butyl alcohol (TL)-tert-butylamine (TM) mixtures has been investigated by a steady-state illumination method over a wide range of substrate concentrations. The emission bands from exciplexes (HgTL* and HgTM*) between an excited mercury atom and an alcohol or an amine molecule were observed at about 330 nm and 370 nm, respectively, in TL and TM solutions in cyclohexane. Two other bands appeared at 405 nm and 455 nm for TM at high concentrations. These bands were previously assigned to two types of 1:2 exciplexes (HgTM(2)* and HgTM(2)**). In TL-TM mixed solutions, a new band appeared at about 400 nm. The intensity of this band increased with increasing concentrations of TL and TM. This band was attributed to an exciplex with mixed ligands (HgTLTM*). This band was observed for the first time in this study. The energized intermediate, (HgTLTM*)(not equal), formed between HgAL* and AM can be effectively stabilized by collisions with solvent molecules in solution, while it decomposes to HgAM* and AL in the gas phase. The results for TL-TM mixtures can be explained by the proposed reaction mechanism.     

Solvent Effects on the Absorption Spectrum of the Product and the Equilibrium Constant for the Proton Transfer Reaction from 1-Phenacylquinolinium Bromide to Amines

The equilibrium constants, K ₂, have been determined for the proton-transfer reactions of 1-phenacylquinolinium ion, PHQ⁺, with several amines {triethylamine (TEA), N,N,N′,N′-tetramethylethylenediamine (ED), N,N,N′, N′-tetramethylpropanediamine (PD), N,N,N′,N′-tetramethylbutanediamine (BD), and 1,8-bis(dimethylamino-naphthalene (DMAN)} in acetonitrile (AN), AN-tetrahydrofuran (THF) and AN-ethanol (EtOH) mixtures. The reaction was followed spectrophotometrically using a stopped-flow technique. The K ₂ value decreased for DMAN and increased for TEA with increasing vol-% of THF in AN-THF mixtures. The changes in the K ₂ value for ED, PD and BD changed in the order: ED, PD and BD from a pattern similar to TEA to a pattern similar to DMAN. The change in the K ₂ value for DMAN with increasing vol-% of THF in AN-THF mixtures was explained by the effect of polarity on the stability of P⁻Q⁺ (the deprotonated product of PHQ⁺). The effect of THF on the K ₂ value is consistent with that of the peak wavelength of the absorption spectrum of P⁻Q⁺. The change in the K ₂ value for TEA, ED, PD and BD depended on the structures of the protonated bases, one of the products for this reaction. The effect of EtOH on the K ₂ value for DMAN was examined in ternary EtOH-THF-AN mixtures that contain different amounts of EtOH and whose relative permittivities were adjusted to that of EtOH. The K ₂ value increased with increasing vol-% of EtOH because of the stabilization of P⁻Q⁺ upon the formation of the hydrogen-bonded complex with EtOH. The absorption spectrum of P⁻Q⁺ demonstrated a blue shift as the vol-% of EtOH increased.     

A characteristic effect of pressure on inclusion complexation of phenothiazine dyes with p-sulfonatocalix[6]arene in a room-temperature ionic liquid

The inclusion complexation of p-sulfonatocalix[6]arene (Calix-S6) with three kinds of phenothiazine dyes was studied spectrophotometrically in a mixture of a room-temperature ionic liquid [bmim]BF₄ (1-butyl-3-methylimidazolium tetrafluoroborate) and ethanol. We have determined the association constants of Calix-S6 with phenothiazine dyes under external static pressure up to 767 bar in the [bmim]BF₄-ethanol and alcohol-water mixtures. With increasing external pressure, the inclusion equilibrium in the alcohol-water mixtures was shifted to the dissociation side. Conversely, the inclusion equilibrium of methylene blue (MB) and azure A (AA) in the ionic liquid mixture was shifted to the association side. From the analysis of the pressure effects, the reaction volumes ΔV for inclusion complexation were estimated as −7 to 9 cm³ mol⁻¹ in the [bmim]BF₄-ethanol mixture and 20–32 cm³ mol⁻¹ in the alcohol-water mixtures. Based on the results, we have suggested that there is a competing complexation between the included dye and [bmim]BF₄ molecules in the ionic liquid.     

Elucidation of the Role of the Complex in Hydride Transfer Reaction between Methylene Blue and 1-Benzyl-1,4-dihydronictinamide by Effect of γ-Cyclodextrin

The kinetics of the hydride transfer reaction between Methylene Blue (MB⁺) and 1-benzyl-1,4-dihydronicotinamide (BNAH) were studied in 10% ethanol-90% water mixed solvents containing β- and γ-cyclodextrins (β-CD and γ-CD). The pseudo-first order rate constant shows kinetic saturation at high initial concentration of BNAH. This indicates the formation of a complex between MB⁺ and BNAH. The reaction was suppressed by addition of β-CD, but enhanced by addition of γ-CD. MB⁺ and BNAH were separately accommodated within the β-CD cavity and the cavity walls may protect the activity site of the reactants. On the other hand, in the MB⁺-BNAH-γ-CD system, the inclusion of the complex between MB⁺ and BNAH with γ-CD occurred. This effect of γ-CD can distinguish between the productive and non-productive nature of the complex.     

Analysis of the Effects of Protic,Aprotic, and Multi-Component Solvents on the Fluorescence Emission of Naphthalene and its Exciplex with Triethylamine

The emission spectra of naphthalene (NP)–triethylamine (TEA) systems were measured under steady-state illumination conditions in some protic and aprotic solvent-tetrahydrofuran (THF) mixtures. The fluorescence spectrum of the NP–TEA system in THF could be separated into two component bands (band A at 329 nm (fluorescence of NP) and band B at 468 nm (emission from an intermolecular exciplex)). The intensities of bands A and B decreased with increasing solvent polarity. The intensity of band B also decreased owing to the hydrogen-bonding interaction between TEA and protic solvents, but in this case the intensity of band A increased. The decrease in the intensity of band A with increasing solvent polarity is considered to be caused by the enhanced formation of an ion-pair parallel to the formation of an exciplex with increasing solvent polarity. The decrease in the intensity of band B is considered to be caused by the enhanced formation of ion-pair both parallel to and through the formation of the exciplex. The increase in the intensity of band A and the decrease in that of band B upon the addition of protic solvents is caused by the decrease in the concentration of free TEA. Acetonitrile only has a polar effect and trichloroacetic acid only has a hydrogen-bonding (protonation) effect, while alcohols have both the effects.     

电荷转移复合物在反应中作用的研究进展

总结了存在电荷转移复合物反应的反应历程的研究结果,在Ｄｉｅｌｓ－Ａｌｄｅｒ反应和氢负离子转移反应中观测到负的表观活化焓,表明电荷转移复合物是真正的反应中间体。     

Synthesis and oxidative polymerization of dialkyl fluorene-9,9-dicarboxylates

Novel long-chain dialkyl fluorene-9,9-dicarboxylates were synthesized by treating fluorene with lithium diisopropylamide followed by alkyl chloroformates. The fluorene derivatives were readily electro-oxidized to form electroactive films on the surface of a glassy carbon electrode. From the viewpoint of suitable potential window (from −2.5 to 1.5 V vs Ag/Ag⁺), cyclic voltammograms of the films indicated the electroactive properties of the fluorene derivatives that make them good candidates for electrochemical capacitor materials.     

Solid-state polymerization of maleimide by 2,2′-azobisisobutyronitrile

The solid-state polymerization of maleimide by 2,2′-azobisisobutyronitrile was studied over the temperature range 65–85°C. The polymerization was carried out either by heating the solid mixture of maleimide and 2,2′-azobisisobutyronitrile or by heating the two compounds separately in twin ampules. The results of the kinetic study showed that the lifetime of the propagating radicals was short and that the rate of termination was proportional to the mole amount of propagating radicals. The ESR spectrum showed that stable radicals that were not main propagating radicals were in the polymerizing system.     

Conductimetric determination of ion-association constants for calcium,cobalt, zinc,and cadmium sulfates in aqueous solutions at various temperatures between 0°C and 45°C

Thermodynamic ion-association constants for calcium, cobalt, zinc, and cadmium sulfates in aqueous solutions were determined by means of conductivity measurements at various temperatures between 0°C and 45°C. The standard Gibbs energy, enthalpy, and entropy for the reaction M ²⁺ +SO ₄ ^2– M ²⁺ ·SO ₄ ^2– (M=Ca, Co, Zn, and Cd) were calculated from the temperature dependence of the ion-association constants. The values obtained are as follows: G ₂₉₈ ^o =–12.42 kJ-mole ^–1 , H ^o =6.11 kJ-mole ^–1 , and S ₂₉₈ ^o =62.1 J- ^o K ^–1 -mole ^–1 for Ca ²⁺ ·SO ₄ ^2– ; G ₂₉₈ ^o =–12.84 kJ-mole ^–1 , H ^o =5.00 kJ-mole ^–1 , and S ₂₉₈ ^o =59.8 J- ^o K ^–1 -mole^–1 for Co ²⁺ ·SO ₄ ^2– ; G ₂₉₈ ^o =–12.65 kJ-mole ^–1 , H ^o =8.65 kJ-mole ^–1 , and S ₂₉₈ ^o =71.4 J- ^o K ^–1 -mole ^–1 for Zn ²⁺ ·SO ₄ ^2– ; G ₂₉₈ ^o =–13.28 kJ-mole ^–1 , H ^o =8.39 kJ-mole ^–1 , and S ₂₉₈ ^o =72.7 J- ^o K ^–1 -mole ^–1 for Cd ²⁺ ·SO ₄ ^2– .