On the emitters of sulfuric acid sonoluminescence

A comparative study of the sonoluminescence spectra of water and argon-saturated aqueous H₂SO₄ solutions was carried out. At an H₂SO₄ concentration of 18 mol L⁻¹, the sulfuric acid sonoluminescence is fifty times more intense than water sonoluminescence. The sulfuric acid luminescence spectrum differs from the water sonoluminescence spectrum caused by the emission of excited water molecules and OH radicals from the gas phase of cavitation bubbles. The sulfuric acid sonoluminescence spectrum exhibits maxima at 330, 420, 500, and 630 nm. Emitters of sonoluminescence of sulfuric acid are the singlet (330–340 nm) and triplet (∼420 nm) excited SO₂ molecules formed by sonolysis of H₂SO₄ molecules. Another product of sonolysis of H₂SO₄, atomic oxygen, is assumed to be responsible for the luminescence at λ = 630 nm. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1742–1745, August, 2005.     

Photoactivation mechanism of orthovanadate-like (V=O)O3 species

The photoluminescence spectrum and action spectrum for the photooxidation of orthovanadate-like (V=O)O₃ species exhibiting photoluminescence at 520 nm indicate that the triplet excited state T₁ of the orthovanadate-like species, which is formed from the singlet excited states S₁ and S₂ by intersystem crossing, is directly involved in the photooxidation of cyclohexane into cyclohexanone in the presence of molecular oxygen.     

Kinetics and Mechanism of the Photoinduced Addition of Water and Methanol to the Double Bond of 2,2,4-Trimethyl-8-Methoxy-1,2-Dihydroquinoline

The mechanism of the photoinduced Markovnikov addition of water and methanol to the double bond of 2,2,4-trimethyl-8-methoxy-1,2-dihydroquinoline was studied by flash photolysis over a wide range of acid and alkali concentrations. In neutral MeOH solutions, the successive formation of two active intermediates was observed. These intermediates have absorption bands at _max = 420 and 500 nm, respectively, and lifetimes of a few milliseconds. The rate constants of decay for these species (k ₁ and k ₂) were measured over the temperature range from 10 to 45°C, and the activation energies E ₁ (3.7 ± 0.4) and E ₂ (6.9 ± 0.7) kcal/mol were determined in MeOH. The addition of an acid accelerates the conversion of the former intermediate into the latter. The rate constant for the reaction of the former intermediate with the acid is (2.0 ± 0.4) × 10⁸ l mol^–1 s^–1. The latter intermediate was proposed to be a corresponding carbocation. In H₂O at pH < 9, the formation of the carbocation (_max = 500 nm) was observed on a millisecond timescale, with the lifetime being an order of magnitude higher than that in MeOH. In alkaline media, only the former intermediate (_max = 420 nm) was observed with a lifetime of 150 or 400 ms in MeOH or H₂O, respectively, at [NaOH] > 2 × 10^–3 mol/l. The quantum yields of the product and the quantum yields of fluorescence were measured as functions of acidity. Possible mechanisms of the reaction are discussed.     

Ultrafast fluorescence resonance energy transfer in a bile salt aggregate: Excitation wavelength dependence

Fluorescence resonance energy transfer (FRET) from Coumarin 153 (C153) to Rhodamine 6G (R6G) in a secondary aggregate of a bile salt (sodium deoxycholate, NaDC) is studied by femtosecond up-conversion. The emission spectrum of C153 in NaDC is analysed in terms of two spectra-one with emission maximum at 480 nm which corresponds to a non-polar and hydrophobic site and another with maximum at ∼530 nm which arises from a polar hydrophilic site. The time constants of FRET were obtained from the rise time of the emission of the acceptor (R6G). In the NaDC aggregate, FRET occurs in multiple time scales — 4 ps and 3700 ps. The 4 ps component is assigned to FRET from a donor (D) to an acceptor (A) held at a close distance (R _DA ∼ 17 ?) inside the bile salt aggregate. The 3700 ps component corresponds to a donor-acceptor distance ∼48 ?. The long (3700 ps) component may involve diffusion of the donor. With increase in the excitation wavelength (λ _ex) from 375 to 435 nm, the relative contribution of the ultrafast component of FRET (∼4 ps) increases from 3 to 40% with a concomitant decrease in the contribution of the ultraslow component (∼3700 ps) from 97 to 60%. The λ _ex dependence is attributed to the presence of donors at different locations. At a long λ _ex (435 nm) donors in the highly polar peripheral region are excited. A short λ _ex (375 nm) ‘selects’ donor at a hydrophobic location.     

Theoretical studies on Ru(fppz)2(CO)L (L = N -heterocyclic ligand): Electronic structure, absorption, phosphorescence, and solvatochromism

A series of ruthenium(II) complexes Ru(fppz)₂(CO)L [fppz = 3-trifluoromethyl-5(2-pyridyl)pyrazole; L = pyridine (1), 4-dimethylaminopyridine (2), 4-cyanopyridine (3)] were designed and investigated theoretically to explore their electronic structures, absorption, and emissions as well as the solvatochromism. The singlet ground state and triplet excited state geometries were fully optimized at the B3LYP/LANL2DZ and CIS/LANL2DZ level, respectively. The HOMO of 1–3 is composed of d_yz(Ru) atom and π(fppz). The LUMO of 1 and 2 is dominantly contributed by π*(fppz) orbital, but that of 3 is contribute by π*(L). Absorption and phosphorescence in vacuo, C₆H₁₂, and CH₃CN media were calculated using the TD-DFT level of theory with the PCM model based on the optimized ground and excited state geometries, respectively. The lowest-lying absorption of 1 and 2 at 387 and 391 nm is attributed to {[d_yz(Ru) + π(fppz)] → [π*(fppz)]} transition, but that of 3 at 479 nm is assigned to {[d_yz(Ru) + π(fppz)] → [π*(L)]} transition. The phosphorescence of 1 and 2 at 436 and 438 nm originates from ³{[d_yz(Ru) + π(fppz)] [π*(fppz)]} excited state, while that of 3 at 606 nm is from ³{[d_yz(Ru) + π(fppz)] [π*(L)]} excited state. The calculation results showed that the absorption and emission transition character can be changed from MLCT/ILCT to MLCT/LLCT transition by altering the substituent on the L ligand. The phosphorescence of 1 and 2 does not have solvatochromism, but that of 3 at 606 nm (vacuo), 584 nm (C₆H₁₂), and 541 nm (CH₃CN) is strongly dependent on the solvent polarity, so introducing electron-withdrawing group on ligand L will induce remarkable solvatochromism. Supported by the National Natural Science Foundation of China (Grant Nos. 20573042, 20703015, and 20333050)     

A TD‐DFT Study on the Effect of Intermolecular Hydrogen Bonding on the Photophysical Properties of N‐Methyl‐1,8‐naphthalimide

The effect of intermolecular hydrogen bonding on the photophysical properties of N‐methyl‐1,8‐naphthalimide ( 2 ) has been investigated by time‐dependent density functional theory (TD‐DFT) method. The UV and IR spectra of 2 monomer and its hydrogen‐bonded complexes formed with 2,2,2‐trifluoroethanol (TFE) 2 +TFE and 2 +2TFE have been calculated, which confirm the presence of intermolecular hydrogen bonding interactions between the carbonyl groups of the aromatic imide and the hydroxyl group of the polyfluorinated alcohol. The absorption and fluorescence intensities going from 2 monomer via hydrogen‐bonded complex 2 +TFE to 2 +2TFE were found to be gradually enhanced with the wavelength gradually red‐shifted. The enhancements of the fluorescence intensities from 2 monomer to hydrogen‐bonded complexes 2 +TFE and 2 +2TFE were attributed to the decrease of the intersystem crossing (ISC) efficiency from the first excited singlet state S₁ ¹(ππ*) to the second excited triplet state T₂ ³(nπ*), whose energy was increased relative to its ground state due to the intermolecular hydrogen bonding interactions.     

Role of steric hindrance in photoinduced proton transfer from solvent to excited molecules of 1,2-dihydroquinolines

It was shown that the photolysis of 1,2,6-trimethyl-1,2-dihydroquinoline (126TMDHQ) in water, methanol, ethanol, and isopropanol affords the corresponding adducts of water and the alcohols, unlike the case of 2,2,4-trimethyl-1,2-dihydroquinolines bearing the methyl, alkoxyl, and hydroxyl substituents in the 1-, 6-, and 8-positions, which were previously found to form adducts only in the presence of water and MeOH. The quantum yield of the 126TMDQ photolysis (Φ) in this solvent series changes as Φ_MeOH:Φ_EtOH:Φ_PrOH = 10:3:1. The results were rationalized in terms of the effect of steric hindrance caused by substituents on the heterocycle and increasing size of the alcohol alkyl group on proton transfer from the solvent to the 1,2-dihydroquinoline molecule in the excited singlet state. The existence of two adduct isomers was revealed. The preferential formation of one of the isomers was considered from the standpoint of carbocation accessibility to the solvent by nucleophilic attack.     

Photostimulated changes in WO3 nanosized films

During the irradiation of WO₃ films d = 7–160 nm thick by light at λ = 320 nm (I = (1.5–7) × 10¹⁵ quantum cm⁻² s⁻¹), absorption band at λ = 850 nm appeared along with absorption band edge shift to shorter waves. The subsequent irradiation of samples at λ = 850 nm caused the disappearance of the longwave absorption band. The intrinsic absorption edge of WO₃ films was determined (λ = 320 nm). The degree of transformations of WO₃ films increased under atmospheric conditions as the intensity of incident light and the time of irradiation (1–140 min) grew and as film thickness decreased. A mechanism of photochemical transformations of WO₃ films was suggested. This mechanism included the generation of electron-hole pairs, the recombination of part of nonequilibrium charge carriers, the formation of [eV_a²⁺e] centers, and the isolation of photolysis products.     

Determination of energizers in energy drinks

The method of UV/VIS derivative spectrophotometry for the determination of caffeine and B vitamins in energy drinks after solid phase extraction has been developed. Caffeine has been determined in the mixture with B₂ vitamin with zero-crossing technique from the I derivative spectra (λ = 266.8 nm), and B₃ in mixture with B₆ vitamin from the II derivative spectra (λ = 280.1 nm). B₁₂ vitamin has also been determined in a three-component mixture with vitamins B₃ and B₆. Taurine in drinks has been determined from the basic spectra after derivatization with ninhydrin (λ = 570 nm).     

Photolysis of 6-ethoxy-2,2,4-trimethyl-8-nitro-1,2-dihydroquinoline. Unusual dependence on the irradiation wavelength

The spectral and kinetic parameters of transient species generated in the irradiation of 6-ethoxy-2,2,4-trimethyl-8-nitro-1,2-dihydroquinoline were examined by stationary and pulse photolysis in the solvents: heptane, acetonitrile, methanol, and ethanol. Upon excitation of the long-wavelength absorption band (λ_ex > 450 nm), a reversible photochemical reaction was revealed, and the spectral and kinetic parameters of three transient species observed in the photolysis were characterized (λ_max = 390, 400, and 420 nm (acetonitrile), k = 97, 500, and 2000 s⁻¹, respectively). The absorption spectra and the rate constants of the decay of transient species are almost independent of the medium polarity and the presence of oxygen in the system. The excited state generated during irradiation to the short-wavelength absorption band (290 < λ_ex < 350 nm) is inactive in the photochemical reaction and deactivates without the formation of transient species. The mechanism of the reversible photochemical reaction is suggested, which involves the opening of the heterocycle N-C bond upon photoexcitation of the long-wavelength absorption band and the thermal back reaction.     

Solution ozonolysis of C<Subscript>70</Subscript>: stable products and chemiluminescence

For the first time the total and relative contents of the stable ozonolysis products of fullerene C₇₀ solutions were identified by IR spectroscopy and elemental and chemical analyses. At the 100% conversion of C₇₀ a mixture of products corresponding to the empirical formula C₇₀O_14.3H_0.21 (epoxides: polyketones: polyesters: secondary fullerene ozonides (SFOZ): acids = 1.07: 6: 6: 0.21: 1.02) is formed. The content of polyketones, polyesters, acids, and SFOZ increases during the whole ozonolysis time (1 h). The number of oxygen atoms in epoxides C₇₀O _n (n = 1–4) is lower than that in epoxides C₆₀O _n (n = 1–6) formed by the ozonolysis of fullerene C₆₀. The kinetic curve of accumulation of epoxides C₇₀O _n (n = 1–4) passes through a maximum, which is observed 0.5 min after the beginning of ozonolysis. No epoxides were identified among the products 3.5 min after the ozonolysis. The photoluminescence (PL) (λ_max = 645 and 685 nm) of fullerene polyketones in glassy EtO₂/EtOH solutions frozen at 77 K was observed. This PL is much brighter, than that of polyketones formed upon the ozonolysis of fullerenes C₆₀. For the first time the chemiluminescence (CL) was detected and studied upon the ozonolysis of C₇₀ solutions at 300 K. The CL emitters are excited states of fullerene polyketones. The CL spectrum is partially overlapped with the known CL spectrum appeared upon the ozonolysis of C₆₀ (λ_max = 685 nm) but contains the greater number of maxima (λ_max = 645 and 685 nm), which is related to a lower symmetry of the C₇₀ oxidation products.     

The photochemical addition of 2,2,2-trifluoroethanol to methoxy-substituted stilbenes

The excited-state lifetime of the trans-stilbene chromophore in acetonitrile is prolonged by methoxy substituents in the meta positions. The long-lived singlet excited state of trans-3,5-dimethoxystilbene (trans-2d) is quenched upon the addition of 2,2,2-trifluoroethanol (TFE), and the Markovnikov ether is observed as the major product from steady-state irradiations. The results indicate that the reaction pathway proceeds through a carbocation intermediate.     

Solvent-dependent C-OH homolysis and heterolysis in electronically excited 9-fluorenol: the life and solvation time of the 9-fluorenyl cation in water

The primary pathways of the photodecomposition of 9-fluorenol (FOH) were studied in polar and nonpolar solvents by use of laser flash-photolysis with a resolution time of 10 ps. In solvents of high polarity, that is, in 1,1.1,3,3,3-hexafluoroisopropanol (HFIP), 2,2,2-trifluoroethanol (TFE), formamide or water, the fluorenyl cation, F+, forms by heterolytic C-O bond cleavage. In H2O, the initial (10 ps) spectrum of F+ has lambdamax at <460 nm. This absorption red-shifts with T = 25 ps to the "classical" spectrum with lambdamax = 510-515 nm. This process is assigned to the solvation of the initial "naked" cation, or rather, the contact ion pair. The lifetime of the solvated fluorenyl cation in H2O (or D2O) and TFE was measured to be tau 20 ps and 1 ns, respectively. In solvents of lower polarity such as alkanes, ethers and alcohols, the long-lived (tau 1/2 1 micros) fluorenyl radical, F., (lambdamax = 500 nm) forms through homolytic C-O cleavage. In addition to the radical and the cation, the vibrationally relaxed excited singlet state of FOH is seen with its absorption at approximately 640 nm; its lifetime is strongly dependent on the solvent, from 10 ps for formamide to 1.7 ns for cyclohexane. The rate constant for singlet decay increases exponentially with the polarity of the solvent (as expressed by the Dimroth-Reichardt ET value) or with the Gutmann solvent acceptor number. The relaxation of S1 to S0 is accompanied by homolytic C9-O bond cleavage (except in HFIP, TFE, and water, where S1 is not seen).     

Radiation chemical investigations on aqueous solutions of C60(OH)18

The ultraviolet-visible absorption spectrum of C₆₀(OH)₁₈ in water showed an absorption band with λ_max = 215 nm and other characteristic absorption bands of C₆₀ are not observed. The singlet-singlet and triplet-triplet absorption bands are not observed in the 400–900 nm region. It has low reactivity with e_aq⁻ and formed an absorption band with λ_max = 580 nm. The hydroxyl radicals react with a bimolecular rate constant of 2.4×10⁹ dm³ mol⁻¹ s⁻¹ and showed an absorption band at 540 nm.     

Crystal structure of solvate [Cd2L2Cl4]·CH2Cl2 (L = pyrazolylquinoline, the derivative of monoterpenoid (+)-3-carene) and photoluminescence of chiral complex CdLCl2

Using the single crystal X-ray diffraction data (150 K, Bruker X8 Apex CCD autodiffractometer, MoK α radiation), the crystal structure of the [Cd₂L₂Cl₄]·CH₂Cl₂ (L = pyrazolylquinoline, the derivative of monoterpenoid (+)-3-carene) compound is determined. Crystals are monoclinic, unit cell parameters are: a = 10.7005(4) ?, b = 16.8491(4) ?, c = 11.9658(4) ?, β = 93.308(1)°, P2₁ space group. The structure is formed from discrete acentric molecules of a binuclear [Cd₂L₂Cl₄] complex and uncoordinated CH₂Cl₂ molecules. The Cd²⁺ ions coordinate N atoms of bidentate chelating ligands L, which leads to the closure of two five-membered chelate CdN₃C rings. The coordination sphere of Cd atoms also includes three Cl atoms (two bridging and one terminal), consequently, two CdCl₃N₂ coordination sites and a Cd₂Cl₂ metal ring are formed. The Cl₃N₂ polyhedra have the form of distorted tetragonal pyramids. The CH₂Cl₂ molecules located in the channels formed by the complexes are linked with them by weak H-bonds. The excitation spectra of L and the CdLCl₂ compound contain bands with λ_max of 352 nm and 360 nm respectively. At 300 K and λ_excit 350 nm, in the photoluminescence spectrum of L a rather intense broad split band with λ_max 372 nm and 386 nm is observed. The photoluminescence spectrum of the CdLCl₂ compound contains a broad band with λ_max 418 nm. The photoluminescence intensity of this compound is significantly lower than that of L.     

Structure and properties of Li<Subscript>2</Subscript>Zn<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript> crystals activated with copper and chromium ions

Based on the corrected phase diagrams proper growth conditions for Li2Zn2(MoO₄)₃ crystals are selected. Large crystals (up to 100 mm), both impurity-free and activated by transition metal ions (Cu, Cr), are grown by the low-gradient Czochralski method. By the EPR method the charge state and structural position of copper and chromium ions are determined. The performed studies of luminescent properties show that for impurity-free crystals luminescence with λ = 388 nm with a two-exponential luminescence decay with τ₁ = 2 ns and τ₂ = 6 ns is observed at room temperature. At 77 K for both impurity-free crystals and those activated with transition metal ions luminescence with λ = 560 nm and the luminescence lifetime τ = 100 ns is observed, the intensity of luminescence with λ = 560 nm depending on the nature and concentration of transition metal ions. Cation vacancies responsible for the charge compensation of impurity transition metal ions are assumed to be also responsible for low-temperature luminescence.     

C-Br Bond Dissociation Mechanisms of 2-Bromothiophene and 3-Bromothiophene at 267 nm

C-Br bond dissociation mechanisms of 2-bromothiophene and 3-bromothiophene at 267 nm were investigated using ion velocity imaging technique. Translational energy distributions and angular distributions of the photoproducts, Br(²P_3/2) and Br^*(²P_½), were obtained and the possible dissociation channels were analyzed. For these two bromothiophenes, the Br fragments were produced via three channels: (i) the fast predissociation following the intersystem crossing from the excited singlet state to repulsive triplet state; (ii) the hot dissociation on highly vibrational ground state following the internal conversion of the excited singlet state; and (iii) the dissociation following the multiphoton ionization of the parent molecules. Similar channels are involved for photoproduct Br^* of the 2-bromothiophene dissociation at 267 nm; whereas for the photoproduct Br^* of 3-bromothiophene, the dissociation channel via internal conversion from the excited singlet state to highly vibrational ground state became dominating and the fast predissociation channel via the excited triplet state almost disappeared. Informations about the relative contribution, energy disposal, and the anisotropy of each channel were quantitatively given. It was found that with the position of Br atom in thienyl being far from S atom, the relative ratios of products from channels (i) and (ii) decreased obviously and the anisotropies corresponding to each channel became weaker.     

Pulse radiolysis study of 2-Mercapto-benzothiazole-a corrosion inhibitor

Pulse radiolysis of 2-Mercaptobenzothiazole (2-MBT) has been undertaken in aqueous solution. The semi-oxidized species formed at pH 4.5 due to the reaction of OH^•, Br₂ ^•− and N₃ ^• and at pH 10.5 with OH^• yielded a spectrum with λ_max = 348 and 595 nm. These semi-oxidized species were able to oxidize phenothiazine drugs (E^o⋟0.8 V). Reducing species such as e_aq ⁻, CO₂ ^•− and H^• atoms react with 2-MBT resulting in the formation of a transient having λ_max = 350 nm and reducing in nature. Kinetic and spectroscopic data of interest are reported.     

Effect of the nature of inert solvent on the decay kinetics of the carbocation generated in the photolysis of 1,2-dihydroquinolines in methanol

The dependence of the quantum yield and the decay rate constant for the carbocation generated in the photolysis of 6-ethoxy-1,2,2,4-tetramethyl-1,2-dihydroquinoline (6-EtO-DHQ) in methanol on the solvent composition was studied in the mixtures of methanol with isopropanol, acetonitrile, and pentane by pulse photolysis. The addition of these solvents decreases the yield of the carbocation and differently affects the kinetic parameters of its decay. The carbocation decay in the mixtures MeOH-i-PrOH and MeOH-C₅H₁₂ is described by the pseudo-first order equation (k ₁), with the dependence of k ₁ having a maximum at 50 vol % of MeOH in the MeOH-i-PrOH mixtures, and k ₁ increasing with a decrease in the MeOH concentration in the MeOH-C₅H₁₂ mixtures. In the MeOH-MeCN mixtures, the value of k ₁ decreases with a decrease in the MeOH concentration, and, at the concentration of MeOH lower than 50 vol %, the contribution of the second-order reaction (k ₂) is observed. The activation energies and preexponential factors were determined in the MeOH-C₅H₁₂ mixtures of different compositions, and it was shown that E _act practically did not depend on the solvent composition and were close to E _act for other carbocations obtained in MeOH. The increase in k ₁ with a decrease in the MeOH concentration is caused by an increase in the preexponential factor. The results were discussed on the basis of the reaction mechanism involving the competing reactions of the carbocation combination with two nucleophilic particles, the MeOH molecule and the MeO⁻ anion. The composition of the mixture and the nature of the inert solvent affect strongly the course of these reactions. Published in Russian in Kinetika i Kataliz, 2009, Vol. 50, No. 3, pp. 411–416. The article was translated by the authors.     

Excited state character of Cibalackrot-type compounds interpreted in terms of Hückel-aromaticity: a rationale for singlet fission chromophore design

The exact energies of the lowest singlet and triplet excited states in organic chromophores are crucial to their performance in optoelectronic devices. The possibility of utilizing singlet fission to enhance the performance of photovoltaic devices has resulted in a wide demand for tuneable, stable organic chromophores with wide S₁–T₁ energy gaps (>1 eV). Cibalackrot-type compounds were recently considered to have favorably positioned excited state energies for singlet fission, and they were found to have a degree of aromaticity in the lowest triplet excited state (T₁). This work reports on a revised and deepened theoretical analysis taking into account the excited state Hückel-aromatic (instead of Baird-aromatic) as well as diradical characters, with the aim to design new organic chromophores based on this scaffold in a rational way starting from qualitative theory. We demonstrate that the substituent strategy can effectively adjust the spin distribution on the chromophore and thereby manipulate the excited state energy levels. Additionally, the improved understanding of the aromatic characters enables us to demonstrate a feasible design strategy to vary the excited state energy levels by tuning the number and nature of Hückel-aromatic units in the excited state. Finally, our study elucidates the complications and pitfalls of the excited state aromaticity and antiaromaticity concepts, highlighting that quantitative results from quantum chemical calculations of various aromaticity indices must be linked with qualitative theoretical analysis of the character of the excited states.

Cibalackrot-type compounds are Hückel instead of Baird aromatic in their first triplet states (T₁). By choice of substituents and additional benzannelation we adjust the T₁ energies, providing a new strategy for singlet fission chromophore design.