Solute-solvent exciplexes as the source of anomalous fluorescence from 4-N,N-dimethylamino-ethylbenzoate in 1,4-dioxane and in polar solvents

The behaviour of 4-N,N-dimethylamino-ethylbenzoate in its lowest electronically excited singlet and triplet states in solutions in apolar and polar solvents has been investigated by measuring the lifetime and quantum yield of the fluorescence, quantum yield of the triplet state and transient dielectric loss induced by laser pulse excitation. The major conclusion is that the anomalous fluorescence of the compound in 1,4-dioxane and in polar solvents is emitted by solute-solvent exciplexes. The previously reported anomalous fluorescence of the compound in alkanes has not been observed.     

The role of water in the dual luminescence of 4-N,N-dimethylaminobenzonitrile

The observation of the dual luminescence of the title compound in very concentrated solutions in specially dried acetonitrile rules out water impurities as being at the origin of the anomalous emission. Water produces a quenching of the anomalous emission as well as a red-shift of the emission spectrum.     

4-N,N-dimethylaminobenzonitrile: the absence of a1 fluorescence under jet-cooled conditions

Excitation and dispersed fluorescence spectra and fluorescence lifetimes of jet-cooled 4-N,N-dimethylaminobenzonitrile (DMABN) and its van der Waals complex with methanol are reported. Neither the bare molecule nor the monosolvated complex exhibits the anomalous a fluorescence seen in polar solution. Multiple solvation of DMABN with methanol resulted in a dramatic reduction in fluorescence quantum yield which can be interpreted in terms of formation of an a state which is non-emissive under jet-cooled conditions.     

Free radical formation in the hydroperoxide oxidation of carbonyl compounds

The inhibitor method using tetranitromethane was used to demonstrate a radical pathway in the oxidation of carbonyl compounds by organic hydroperoxides or hydrogen peroxide in water at 25°C. The initial radical formation rate was studied relative to the concentration and nature of the components and pH of the medium.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2857–2859, December, 1989.     

Dipole moments of exciplexes of heteroaromatic compounds with N,N-dimethylaniline

The influence of the polarity of a solvent on the position of the maximum of the fluorescence band of exciplexes of N, N-dimethylaniline (DMA) with exctied molecules of phenazine, acridine, and their benzo-, dibenzo- and tetrabenzo derivatives was studied. From the regularities found, the ²/³h values were evaluated, giving an estimate of the dipole moments of the exciplexes under consideration. An attempt was made to find a correlation between ²/³h values and the value of the enthalpy of formation H of the corresponding excited complexes. It was concluded that for the first members of the azine series, the ²/³h value does not reflect the degree of charge transfer in the exciplex, and cannot be correlated with AH. Explanations are presented which give as the main reason for this lack of correlation the possible conformational changes undergone by the excited molecules of azines during the formation of the exciplexes.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 4, pp. 484–488, July–August, 1985.     

Competitive decay pathways of the radical ions formed by photoinduced electron transfer between quinones and 4,4'-dimethoxydiphenylmethane in acetonitrile

The reactivity of the cation radical of (4-MeOC6H4)2CH2 photosensitized by 1,4-benzoquinone (BQ), 2,5-dichloro-1,4-benzoquinone (Cl2BQ), and tetrachloro-1,4-benzoquinone (chloranil, CA) was investigated in acetonitrile. The main photoreaction products obtained by steady-state irradiation were identified to be: (4-MeOC6H4)2-CHOC6H4OH, sensitized by BQ; (4-MeOC6H4)2CHCl, sensitized by Cl2BQ; (4-MeOC6H4)2CHOH, sensitized by CA. The mechanism of their formation was investigated by nanosecond laser flash photolysis that allowed transient species (radical ions, neutral radicals, and ions) to be detected and characterized in terms of absorption spectra, formation quantum yields, and decay rate constants. For all systems, the interaction between the triplet quinone (Q) and (4-MeOC6H4)2CH2 produced the corresponding radical ions (quantum yield phi > or = 0.72) which mainly decay by back electron transfer processes. Less efficient reaction routes for the radical ions Q*- and (4-MeOC6H4)2CH2*+ were also: i) the proton-transfer process with the formation of the radical (4-MeOC6H4)2CH* by use of Cl2BQ; ii) the hydrogen-transfer process with the formation of the cation (4-MeOC6H4)2CH+ in the case of CA. Instead. BQ sensitized a much higher yield of BOH* and (4-MeOC6H4)2CH*, mainly by the direct interaction of triplet BQ with (4-MeOC6H4)2CH2. It was also shown that the presence of salts decreases significantly the rate of the back electron transfer process and enhances the quantum yields of formation of the neutral radicals and ions when Cl2BQ and CA are used, respectively. The behavior of BQ*-, Cl2BQ*-, and CA*- appears to be mainly determined by the Mulliken charges on the oxygen atom obtained from quantum mechanical calculations with the model B3LYP/6-311G(d,p). Spin densities seem to be much less important.     

Excited-state electronic coupling and photoinduced multiple electron transfer in two related ligand-bridged hexanuclear mixed-valence compounds

The synthesis, characterization, electrochemical, photophysical, and photochemical properties of two hexanuclear mixed-valence compounds are reported. Each supramolecular species consists of two cyano-bridged [(NC)(5)Fe(II)-CN-Pt(IV)(NH(3))(3)L-NC-Fe(II)(CN)(5)] triads that are linked to each other through a Pt(IV)-L-Pt(IV) bridge, where L = 4,4'-dipyridyl (bpy) or 3,3'-dimethyl-4,4'-dipyridyl (dmb). The major difference between the two compounds is the electronic nature of the bridging ligand between the two Pt atoms. Both species exhibit a broad Fe(II) --> Pt(IV) intervalent (IT) absorption band at 421 nm with an oscillator strength that is approximately four times that for [(NC)(5)Fe(II)-CN-Pt(IV)(NH(3))(5)] and twice that for [(NC)(5)Fe(II)-CN-Pt(IV)(NH(3))(4)-NC-Fe(II)(CN)(5)].(4-) When L = bpy, the resonance Raman spectrum obtained by irradiating the IT band at 488 nm exhibits several dipyridyl ring modes at 1604, 1291, and 1234 cm(-1) which are not present in the spectrum when L = dmb. In addition, femtosecond pump-probe spectroscopy performed at 400 nm yields a transient bleach of the IT absorption band with a single exponential decay of 3.5 ps for L = bpy, compared with only 1.8 ps for L = dmb and 2.1 ps for [(NC)(5)Fe(II)-CN-Pt(IV)(NH(3))(4)-NC-Fe(II)(CN)(5)].(4-) Last, prolonged irradiation of the complexes at 488 nm leads to the formation of 4 equiv of ferricyanide with a quantum efficiency of 0.0014 for L = bpy and 0.0011 for L = dmb. The transient absorption, resonance Raman, and photochemical data suggest that the degree of excited electronic coupling in these compounds is tunable by changing the electronic nature of the Pt-L-Pt bridging ligand.     

Synthesis of heterocyclic compounds using radical reactions and evidence for the formation of spiro radical intermediates

Synthesis of novel heterocycles using radical reactions have been described. Reaction mechanism of their formation is also presented.     

Inhibition of the formation and decay of stilbene core radical cations by the dendron during the photoinduced electron transfer

Formation and decay processes of stilbene core radical cation (ST*+) during the photoinduced electron transfer have been studied for a series of stilbene bearing benzyl ether-type dendrons (D). ST*+ and the radical cation of peripheral dendron (D*+) were generated by intermolecular hole transfer from biphenyl radical cation, which was generated from photoinduced electron transfer from biphenyl to the singlet-excited 9,10-dicyanoanthracene in a mixture of acetonitrile and 1,2-dichloroethane (3:1). An intramolecular dimer radical cation of benzyl groups at the terminal of stilbene dendrimer was indicated as a hole trapping site. Subsequent hole transfer from the trapping site to the core ST generated ST*+. The shielding effects of D depending on the dendrimer generation on the growth and decay of ST*+ were observed. It was revealed for the first time that D acts as the hole trapping site and the hole conductor on the way of the exothermic hole transfer from the terminal of D to the central core ST. We also found that D inhibits the charge recombination with 9,10-dicyanoanthracene radical anion because of the steric hindrance.     

Dodecacarbonyltriosmium catalysed formation of bis(4-N,N-dimethylaminophenyl)methane from N,N-dimethylaniline

Os₃(CO)₁₂ catalyses the conversion of NMe₂Ph to (4-NMe₂C₆H₄)₂CH₂ and NHMePh in refluxing N,N-dimethylaniline. This reaction is similarly catalysed by H₄Os₄(CO)₁₂, while (4-NHMeC₆H₄)₂CH₂ may be obtained from NHMePh. In this case, however, NMe₂Ph and NH₂Ph are also formed, and after longer reaction times mixed products of type (4-NRR′C₆H₄)₂CH₂ (R or R′ = H or Me) are obtained. The formation of H₃Os₃(CH)(CO)₉ indicates methyl transfer from nitrogen to osmium which may be a key step in the catalysis, but it does not appear that clusters are essential since Fe(CO)₅ and Cr(CO)₆ are also weakly active.     

The formation and structure of phenylcamphoric acid and related compounds

The complete structure and stereochemistry of (+)-phenylcamphoric acid has been determined. The acid obtained from the Friedel-Crafts reaction of benzene with isolauronolic acid is identified as (±)-phenylcamphoric acid, α-Campholytic acid is shown to be a likely precursor of phenylcamphoric acid in these reactions. The Friedel-Crafts reaction of 3-cyano-1,2,2-trimethylcyclopentanecarbonyl chloride or 3-cyano-2,2-dimethyl-1-methylenecyclopentane with benzene provides a mixture of phenylcamphornitrile and an isomer. Isofenchocamphoric anhydride similarly provides a mixture of the epimeric 4-phenyl-2,2,4-trimethylcyclopentanecarboxylic acids.     

Photoinitiation mechanism of free radical photopolymerization in the presence of cyclic acetals and related compounds

The behavior of six cyclic acetals and related compounds in the photoinitiation step of a radical photopolymerization was investigated. As shown by the photopolymerization kinetic data obtained from FTIR spectroscopy, most of them are efficient coinitiators in the presence of benzophenone (BP) with efficiencies close to a reference amine coinitiator (ethyl dimethylaminobenzoate, EDB). Laser flash photolysis and ESR spin trapping technique were used to study the photochemical mechanisms of the production of initiating radicals and explain the differences in reactivity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

The nature and fragmentation pathways of the molecular ions of some arylureas,arylthioureas, acetanilides,thioacetanilides and related compounds

Evidence as to the nature of the molecular ions of the title compounds near the ionization thresholds and of their fragmentation processes is presented and discussed. The mode of formation of 5-membered rings, involving the loss of an ortho substituent, is compared and contrasted with the formally similar process reported for the N-dimethyl N'-(o-X-phenyl) formamidines.     

Complex formation of uranium(VI) with 4-hydroxy-3-methoxybenzoic acid and related compounds

Summary The complex formation of uranium(VI) with 4-hydroxy-3-methoxybenzoic acid as well as with benzoic acid and 4-hydroxybenzoic acid was studied. In aqueous solution weak carboxylic 1 : 1 complexes, are formed in which the carboxyl group is bidentately coordinated to the metal atom. The logarithmic stability constants of these complexes regarding the reaction of the uranyl ion with the single charged anion of the respective ligands are 2.78±0.02, 2.68±0.04, and 2.71±0.04 at an ionic strength of 0.1 mol/l (NaClO₄) and at 25 °C. Bis(4-hydroxy-3-methoxybenzoato)dioxouranium(VI) was obtained as a crystalline compound if the concentrations of the starting components for the synthesis are increased. The monoclinic compound has a reflections-rich X-ray powder diffraction pattern. The lattice constants are a = 13.662(9) ?, b = 21.293(7) ?, c = 11.213(3) ?, b = 107.49(4), and V = 3111(2) ?.³