Radical cation generation from singlet and triplet excited states of all-trans-lycopene in chloroform

On direct photoexcitation, subpicosecond time-resolved absorption spectroscopy revealed that the 1B(u)-type singlet excited state of all-trans-lycopene in chloroform was about seven times more efficient than all-trans-beta-carotene in generating the radical cation. The time constant of radical cation generation from the 1B(u)-type state was found to be approximately 0.14 ps, a value that was comparable for the two carotenoids. On anthracene-sensitized triplet excitation, radical cation generation was found to be much less efficient for lycopene than for beta-carotene. A slow rising phase (20-30 micros) in the bleaching of ground-state absorption was common for both lycopene and beta-carotene in chloroform and was ascribed to an efficient secondary reaction with a solvent radical leading to the formation of carotenoid radical cations. The reverse ordering in the tendency of the excited states of different multiplicities for the two carotenoids to generate radical cations is discussed in relation to the two carotenoids as scavengers of free radicals.     

Unexpected photochemistry and charge-transfer complexes of [CB(11)H(12)](-) carborane

Although the [CB(11)H(12)](-) carborane does not exhibit an absorption band in UV, its triplet excited state can be generated upon 308 nm laser excitation; also unexpectedly carborane acts as electron donor forming a charge transfer complex with methylviologen that upon illumination gives rise to viologen radical cation.     

Excited-state processes in the carotenoid zeaxanthin after excess energy excitation

Aiming for better understanding of the large complexity of excited-state processes in carotenoids, we have studied the excitation wavelength dependence of the relaxation dynamics in the carotenoid zeaxanthin. Excitation into the lowest vibrational band of the S2 state at 485 nm, into the 0-3 vibrational band of the S2 state at 400 nm, and into the 2B(u)+ state at 266 nm resulted in different relaxation patterns. While excitation at 485 nm produces the known four-state scheme (S2 --> hot S1 --> S1 --> S0), excess energy excitation led to additional dynamics occurring with a time constant of 2.8 ps (400 nm excitation) and 4.9 ps (266 nm excitation), respectively. This process is ascribed to a conformational relaxation of conformers generated by the excess energy excitation. The zeaxanthin S state was observed regardless of the excitation wavelength, but its population increased after 400 and 266 nm excitation, suggesting that conformers generated by the excess energy excitation are important for directing the population toward the S state. The S2-S1 internal conversion time was shortened from 135 to 70 fs when going from 485 to 400 nm excitation, as a result of competition between the S2-S1 internal conversion from the vibrationally hot S2 state and S2 vibrational relaxation. The S1 lifetime of zeaxanthin was within experimental error the same for all excitation wavelengths, yielding approximately 9 ps. No long-lived species have been observed after excitation by femtosecond pulses regardless of the excitation wavelength, but excitation by nanosecond pulses at 266 nm generated both zeaxanthin triplet state and cation radical.     

Pulse radiolysis study on the initial processes of radiation-induced cationic polymerization of styrene and α-methylstyrene

Initial processes of radiation-induced cationic polymerization of styrene and α-methylstyrene have been studied by means of microsecond pulse radiolysis. For styrene, absorption bands caused by the monomer cation radical St⁺? appear at 630 and 350 nm in a mixture of isopentane and n-butyl chloride at about ?165°C. In parallel with the decay of St⁺?, three absorption bands appear in the near-infrared (IR) region, and at 600 and 450 nm. The IR and 600 nm bands are assigned to the associated dimer cation radical St₂⁺?, and the 450 nm band to the bonded dimer cation radical St-St⁺?. The kinetic behavior of these species shows that reaction of St⁺? with styrene monomer forms both St₂⁺? and St-St⁺?. With the decay of St-St⁺?, another absorption band appears at 340 nm, and the lifetime of this band is relatively long. The 340 nm band may be due to carbonium ions of the growing polystyrene. For α-methylstyrene, the monomer cation radical (at 690 and 350 nm), the associated dimer cation radical (in the near-IR region and at 620 nm) and the bonded dimer cation radical (at 480 nm) behave in a manner similar to that of the corresponding styrene species. The absorption band caused by carbonium ions of growing poly(α-methylstyrene) appears at 340 nm.     

Resonance CARS study of long-lived species of diphenylhexatriene generated by monophotonic excitation in polar solvent

The transient absorption and resonance CARS (coherent anti-Stokes Raman scattering) spectra of photo-excited all-trans-1,6-diphenyl-1,3, 5-hexatriene (DPH) were studied and a hitherto unknown species was detected from the spectrum observed for an acetone solution. The excited species was generated by monophotonic excitation at 337 nm (ascertained from the dependence of the CARS intensity and that of the transient absorption on the UV power). A lifetime of ≈ 2 μs was obtained by time-resolved CARS. The new species was tentatively ascribed to a radical cation because of its anomalously long lifetime, agreement of the absorption maximum, and disagreement of CARS signals from those of DPH in the S₁ and T₁ states and from those of the radical anion.     

Diffuse-reflectance laser flash photolysis of 16-(1-pyrene)-hexadecanoic acid adsorbed on silica

The absorption and fluorescence of 16-(1-pyrene)-hexadecanoicacid adsorbed on silica have been investigated. Time-resolved transient diffuse reflectance spectra were recorded following pulsed nanosecond laser excitation at 355 nm of pyrene, 1-methylpyrene and 16-(1-pyrene)-hexadecanoicacid adsorbed on silica. In addition to a rapidly decaying transient, absorbing at 420 nm assigned as the triplet state, and of the radical cation, absorbing at 460 nm, another long living transient species absorbing at 420 nm was observed for 16-(1-pyrene)-hexadecanoic acid. The decay is reversible but complete recovery takes several hours. Although no definitive assignment could be made for this transient several possibilities are discussed. The radical cations of the investigated molecules are formed by a biphotonic process. The non-exponential decay of the radical cations could be analyzed in the framework of a Gaussian distribution of free energy barriers.     

RADICAL CATION PRODUCTION IN THE PHOTOLYSIS OF 5-M-ETHOXY-1-M-ETHYLINDOLE

Abstract— The flash photolysis of 5-m-ethoxy-1-m-ethylindole in aqueous media was studied for the purpose of assigning the absorption spectrum of the radical cation. Transients produced in this study were analogous to those formed in the photolysis of 5-m-ethoxyindole. The major transient observed with an absorption maximum of 460 nm was O₂-s_-ensitive and had a lifetime of 20 μs in nitrogen saturated solutions. One radical species is produced with absorption maxima at 445 and 530 nm. Ionic strength effects on the reaction of this species with I⁻ confirms that it is the radical cation of 5-m-ethoxy-l-methylindole. The effect of H⁺ and Br⁻ on the fluorescence, radical cation and triplet yields is discussed in relation to the mechanism of transient formation.     

Identification and reactivity of the triplet excited state of 5-hydroxytryptophan

Both the neurotransmitter serotonin and the unnatural amino acid 5-hydroxytryptophan (5HT), contain the 5-hydroxyindole chromophore. The photochemistry of 5HT is being investigated in relation to the multiphoton excitation of this chromophore to produce a characteristic photoproduct with green fluorescence ('hyperluminescence'). Laser flash photolysis (308 nm) of 5HT in aqueous solution at neutral pH produces both the neutral 5-indoloxyl radical (lambda(max) 400-420 nm) and another transient absorption with lambda(max) 480 nm and lifetime of 2 micros in deaerated solutions. Based on quenching by oxygen and beta-carotene, the species at 480 nm is identified as the triplet excited state of 5HT. In acidic solution a new oxygen-insensitive intermediate with lambda(max) 460 is assigned to the radical cation of 5HT. Time-resolved measurements of luminescence at 1270 nm have shown that the triplet state of 5HT is able to react with oxygen to form singlet excited oxygen (1O2*) with a quantum yield of approximately 0.1. However, 5HT has also been found to be an effective quencher of singlet oxygen with a second order rate constant of 1.3 x 10(8) dm3 mol(-1) s(-1). The results are discussed in the light of recent observations on the multiphoton-excited photochemistry of serotonin.     

Coumarin 314 free radical cation: formation, properties, and reactivity toward phenolic antioxidants

We have explored the photogeneration of the coumarin 314 radical cation by using nanosecond laser excitation at wavelengths longer than 400 nm in benzene, acetonitrile, dichloromethane, and aqueous media. In addition, time-resolved absorption spectroscopy measurements allowed detection of the triplet excited state of coumarin 314 (C(314)) with a maximum absorption at 550 nm in benzene. The triplet excited state has a lifetime of 90 μs in benzene. It is readily quenched by oxygen (k(q) = 5.0 × 10(9) M(-1) s(-1)). From triplet-triplet energy transfer quenching experiments, it is shown that the energy of this triplet excited state is higher than 35 kcal/mol, in accord with the relatively large singlet oxygen quantum yield (Φ(Δ) = 0.25). However, in aqueous media, the coumarin triplet was no longer observed, and instead of that, a long-lived (160 μs in air-equilibrated solutions) free radical cation with a maximum absorbance at 370 nm was detected. The free radical cation generation, which has a quantum yield of 0.2, occurs by electron photoejection. Moreover, density functional theory (DFT) calculations indicate that at least 40% of the electronic density is placed on the nitrogen atom in aqueous media, which explains its lack of reactivity toward oxygen. On the other hand, rate constant values close to the diffusion rate limit in water (>10(9) M(-1) s(-1)) were found for the quenching of the C(314) free radical cation by phenolic antioxidants. The results have been interpreted by an electron-transfer reaction between the phenolic antioxidant and the radical cation where ion pair formation could be involved.     

Triplet excitation dynamics of β-carotene studied in three solvents by ns flash photolysis spectroscopy

Upon anthracene-sensitizing, triplet excitation dynamics of β-carotene(β-Car) were studied in nhexane, in methanol, and in acetonitrile, respectively, by ns flash photolysis spectroscopy. In n-hexane,only the bleaching of the ground state absorption(GSB) and the excitation triplet(~3Car*) absorption were observed, and there were no cationic species detected. In both methanol and acetonitrile, similar excitation dynamics were observed, i.e.,~3Car* having a similar lifetime to that in n-hexane, and the immediate generation of the cation dehydrodimer(~#[Car]2~+) upon excitation following transformation into the radical cation Car*~+, since Car*~+ has much longer lifetime in acetonitrile than in methanol. The results prove that both solvent and carotenoid structure determine the triplet excitation mechanism.     

Photochemistry of the pi-extended 9,10-bis(1,3-dithiol-2-ylidene)-9,10-dihydroanthracene system: generation and characterisation of the radical cation, dication, and derived products

Flash photolysis of bis[4.5-di(methylsulfanyl) 1,3-dithiol-2-ylidene]-9,10(-dihydroanthracene (1) in chloroform leads to formation of the transient radical cation species 1.+ which has a diagnostic broad absorption band at lambdamax approximately 650 nm. This band decays to half its original intensity over a period of about 80 micros. Species 1.+ has also been characterised by resonance Raman spectroscopy. In degassed solution 1.+ disproportionates to give the dication 1(2+), whereas in aerated solutions the photodegradation product is the 10-[4,5-di(methylsulfanyl) 1,3-dithiol-2-ylidene]anthracene-9(10 H)one (2). The dication 1(2+) has been characterised by a spectroelectrochemical study [lambdamax (CH2Cl2) = 377, 392, 419, 479 nm] and by an X-ray crystal structure of the salt 1(2-) (ClO4)2, which was obtained by electrocrystallisation. The planar anthracene and 1,3-dithiolium rings in the dication form a dihedral angle of 77.2 degrees; this conformation is strikingly different from the saddle-shaped structure of neutral 1 reported previously.     

ANTHRALIN-DERIVED TRANSIENTS—II. FORMATION OF THE RADICAL BY SPONTANEOUS FRAGMENTATION OF BOTH SINGLET AND TRIPLET STATES OF THE 10,10''-DEHYDRODIMER: RADICAL PAIR MULTIPLICITY EFFECTS

The singlet and triplet states of the anthralin (1,8-dihydroxy-9-anthrone) dehydrodimer have been produced selectively in benzene via pulsed laser excitation and pulse radiolysis respectively. The lifetime of S1 is less than or equal to 30 ps, that of T1 short but unspecified. Both states fragment spontaneously to yield a pair of anthralin radicals. The singlet radical pair predominantly undergoes geminate recombination within the solvent cage. In contrast, the corresponding triplet radical pair undergoes essentially exclusive cage escape to give the anthralin free radical (lambda max 370, 490 and 720 nm) which recombines under normal diffusive conditions. Both recombination processes lead, at least in part, to one or more species which have been assigned as tautomeric forms of the original dimer. The anthralin free radical in benzene is insensitive to the vitamin E model 6-hydroxy-2,2,5,7,8-pentamethylchroman and reacts only slowly with oxygen.     

A DFT and direct MO dynamics study on the structures and electronic states of phenyl-capped terthiophene

The structures and electronic states of phenyl-capped terthiophene (denoted by P3T) and the ionic species of P3T have been investigated by means of density functional theory (DFT) and direct MO dynamics calculations. P3T is one of the high-performance molecular devices, which has been utilized as a semi-conductor. The calculations indicated that the neutral P3T has a non-planar structure whose the phenyl rings in both ends of thiophene chain are largely deviated from the molecular plane. The cation and anion radicals, dication and dianion were considered as its ionic states. The structure for cation radical of P3T is close to more planar than that of neutral P3T. The structures for anion radical, dication and dianion take a pure planar structure. The first excitation energy of neutral P3T is calculated to be 2.90 eV at the TD-B3LYP/6-31G(d)//B3LYP/6-311+G(d) level, while the P3T cation and anion radicals have lower excitation energies (1.22 and 1.10 eV, respectively). The direct MO dynamics calculation showed that neutral, cation and anion hold near planar structure at 300 K. On the other hand, oligothiophene (n = 5) and its ionic species are strongly deformed from the planar structure, and thiophene rings in both ends of chain rotate rapidly by thermal activation. The mechanism of the electron conductivity in P3T was discussed on the basis of theoretical results.     

TRIPLET YIELD OF MEROCYANINE 540 IN WATER IS WAVELENGTH DEPENDENT

Monomers and aggregates of Merocyanine 540 (MC540) in water are able to photoisomerize. The shape of the photoisomer absorption spectrum is very similar to that of the ground state. Triplet state of MC540 in water has been produced by energy transfer from triplet anthracene and displays a broad absorption spectrum between 600 and 700 nm. The triplet state may also be produced by direct excitation of MC540 with UV light. However, when the dye is excited by visible light, no triplet state absorbance in the red could be detected so that the triplet yield of MC540 in water seems to be excitation wavelength dependent.     

Transient species of fullerenes studied with pulse radiolysis and laser photolysis

The excited triplet of C60 or C70 is generated via either direct excitation by laser light or energy transfer from excited states of solvent to C60 and C70. The cation radical of C60 is produced either via hole transfer from cation radical of CCl4 to C60 or via electron transfer from excited triplet of C60 to CCl4. C60 and C70 could be added to trichloromethyl radical to produce adduct radicals with different mechanisms.     

Redox-switchable squaraines with extended conjugation

[reaction: see text] The redox chemistry of pi-extended squaraines is investigated using cyclic voltammetry, in-situ spectroelectrochemistry and quantum chemical calculations. Squaraine 1 is reversibly oxidized to the radical cation and dication whereas reduction shows limited electrochemical but fully chemical reversibility. The radical cation of 1 reveals absorption bands at 1000 nm and a "two-band feature" at 1600 nm. Their implications on the intramolecular electron transfer are discussed.     

Investigations on the nature of the transient species formed on pulse radiolysis of a aqueous solution of 4-(methylthio)benzoic acid

The transient absorption spectrum (max = 320, 400 and 550 nm) obtained on reaction of OH radicals with 4-(methylthio)benzoic acid is assigned to a solute radical cation with a positive charge on the benzene ring. The reaction with specific one-electron oxidants also produced similar spectrum and the oxidation potential for the formation of solute radical cation is estimated to be between 1.4 and 1.6 V vs NHE. The reaction of e_aq ^- with the solute showed the formation of a transient absorption band at 320 nm and is assigned to solute radical anion with reduction potential more negative than-1.5 V.     

Generation of detectable singlet aryl cations by photodehalogenation of fluoroquinolones

Nanosecond laser flash photolysis (lambdaexc = 355 nm) of neutral aqueous solutions of lomefloxacin (LFX, a 8-fluorinated 7-amino-4-quinolone-3-carboxylic acid derivative) produces a detectable transient species, which shows an absorption maximum at 490 nm and can be assigned to an aryl cation. This intermediate has a lifetime of ca. 200 ns in net water, reacts with Br- and Cl- with rate constants of 3.6 x 10(9) M(-1) s(-1) and 4.1 x 10(8) M(-1) s(-1), respectively, and shows a lack of reactivity toward molecular oxygen. From the photolysis of BAY y3118 (BAY, a 8-chlorinated analogue), an aryl cation is also generated, showing absorption maximum at 480 nm (lifetime of ca. 1 micros in net water) and a reaction rate constant of 9 x 10(9) M(-1) s(-1) with Br(-). The existence of these highly reactive species arising from direct photolysis of LFX and BAY can justify the photogenotoxic properties associated with these antibacterial drugs likely due to direct reaction of their cations with DNA.     

Photoreactivity of biologically active compounds. XVI. Formation and reactivity of free radicals in mefloquine

The formation and reactivity of the triplet state and free radicals of mefloquine hydrochloride (MQ) have been investigated by pulse radiolysis and flash photolysis. The excited triplet, cation radical and anion radical have been produced and their absorption characteristics determined. The triplet-triplet absorption spectrum of MQ showed a maximum at 430 nm, with a molar absorption coefficient of 3600 M(-1) cm(-1) and the quantum yield for intersystem crossing was determined to be close to unity. Deactivation of the triplet, in the absence of oxygen, led to the formation of MQ cation and/or anion radicals. The molar absorption coefficient of the cation radical at 330 nm was determined to be 2300 M(-1) cm(-1), whilst that for the anion radical was 2400 M(-1) cm(-1) at 620 nm and 3600 M(-1) cm(-1) at 350 nm. The molar absorption coefficients of the proposed neutral radical at 320 nm and 520 nm were 4000 M(-1) cm(-1) and 1300 M(-1) cm(-1) respectively. The quantum yield for the formation of singlet oxygen, sensitized by MQ triplet, was determined to be close to unity. Aqueous solutions of MQ were found to photoionize to yield hydrated electron and cation radical of MQ in a biphotonic process. The influences of pH, buffer concentration, oxygen concentration and addition of sodium azide on the formation and reactivity of the transients were evaluated. The reactions between MQ and solvated electrons and superoxide anion were also studied.