Spectral and photophysical studies on cruciform oligothiophenes in solution and the solid state

The photophysical and spectroscopic properties of a new class of oligothiophene derivatives, designated as cruciform oligomers, have been investigated in solution (room and low temperature) and in the solid state (as thin films in Zeonex matrixes). The study comprises absorption, emission, and triplet-triplet absorption spectra, together with quantitative measurements of quantum yields (fluorescence, intersystem crossing, internal conversion, and singlet oxygen formation) and lifetimes. The overall data allow the determination of the rate constants for all decay processes. From these, several conclusions are drawn. First, in solution, the main deactivation channels for the compounds are the radiationless processes: S(1) --> S(0) internal conversion and S(1) --> T(1) intersystem crossing. Second, in general, in the solid state, the fluorescence quantum yields decrease relative to solution. A comparison is made with the analogous linear alpha-oligothiophenes, revealing a lower fluorescence quantum efficiency and, in contrast to the normal oligothiophenes, that internal conversion is an important channel for the deactivation of the singlet excited state. Replacement of thiophene by 1,4-phenylene units in the longer-sized cruciform oligomer increases the fluorescence efficiency. The highly efficient generation of singlet oxygen through energy transfer from the triplet state (S(Delta) approximately 1) provides support for the measured intersystem crossing quantum yields and suggests that reaction with this may be an important pathway to consider for degradation of devices produced with these compounds.     

PHOTOCHEMISTRY OF FLAVINS. II. PHOTOPHYSICAL PROPERTIES OF ALLOXAZINES AND ISOALLOXAZINES

Abstract. Pulsed laser photolysis at 347nm has been used to study the transient spectroscopy of alloxazine, lumichrome, lumiflavin, and riboflavin in acidic (pH 2.2) aqueous solution and in ethanol. Intersystem crossing quantum yields (φ_ISC) were determined by a modification of the comparative laser excitation method which utilizes the variation of the triplet yield with intensity in conjunction with a kinetic model for the various photophysical and photochemical processes occurring during the pulse. Fluorescence quantum yields and lifetimes are also reported. Correction for quenching of the excited singlet state by H⁺ ions shows that, in neutral aqueous solution, intersystem crossing for flavins is an efficient process (φ_ISC˜ 0.7) which, in conjunction with fluorescence, accounts for the fate of all absorbed photons. For alloxazine (φ_ISC˜ 0.45) and lumichrome (φ_ISC˜ 0.7) the results are more difficult to interpret owing to interconversion between alloxazine and isoalloxazine structures in the singlet excited state. For all four compounds, the quantum yield of products derived from the singlet excited state is estimated as ˜0.04. There is evidence of biphotonic product formation at high laser energies. In ethanol, where φ_ISC for lumichrome is about twice that of lumiflavin, internal conversion between the excited singlet and ground states appears to be a significant process. Complete triplet-triplet absorption spectra in the region 260–750nm are reported. For lumichrome at pH 2.2 there is spectral evidence for isomeric triplet states which appear to be in equilibrium.     

COMPARISON OF THE SOLID-MATRIX LUMINESCENCE PROPERTIES AND PHOTOPHYSICAL PARAMETERS OF TWO PRODUCTS FROM BENZO(a)PYRENE-DNA ADDUCTS

Abstract: The solid-matrix luminescence properties and several calculated photophysical parameters of two important products from the benzo(a)pyrene-DNA adducts were compared. The products were benzo(a)pyrene-r-7,t-8,9,c-10-tetrahydrotetrol (I-1) and 7R,8S,9S-trihydroxy-10-( N ²-deoxyguanosyl-3'-phosphate)-7,8,9,10-tetrahydroben-zo(a)pyrene (BPDE-dG). The solid-matrix luminescence data were obtained for I-1 and BPDE-dG adsorbed on two different solid matrices, namely, 1%α-cyclodextrin (CD)/NaCl and 25% trehalose/NaCl and at two different temperatures (93 K and 296 K). The 25% trehalose/NaCl gave higher fluorescence and phosphorescence quantum yields from both I-1 and BPDE-dG in contrast to the 1%α-CD/NaCl matrix. The BPDE-dG showed lower fluorescence quantum yields on the solid matrices compared to I-1. The lower fluorescence quantum yields for BPDE-dG were attributed to a photoinduced electron transfer mechanism. In contrast to the room-temperature solution fluorescence of BPDE-dG, BPDE-dG gave rather high fluorescence quantum yields at room temperature when adsorbed on the two solid matrices. From solid-matrix luminescence quantum yields and solid-matrix luminescence lifetimes, many photophysical parameters were calculated and compared. Several differences among the rate constants were noted with the two solid matrices for BPDE-dG and I-1. For example, BPDE-dG showed internal conversion at 296 K with 25% trehalose/NaCl, but no internal conversion was observed at 93 K with this solid matrix. Also, for BPDE-dG the phosphorescence rate constants at 296 K and 93 K were very small with 25% trehalose/NaCl, but the intersystem crossing rate constants from the triplet state to the ground state were very large. The results from this work show how solid-matrix luminescence can be employed to obtain unique luminescence information from the I-1 and BPDE-dG systems.     

THE PHOTOPHYSICS OF MEROCYANINE 540. A COMPARATIVE STUDY IN ETHANOL AND IN LIPOSOMES

Abstract— Absorption and fluorescence emission spectra, fluorescence lifetimes, fluorescence quantum yields, photoisomerization quantum yields and triplet quantum yields were measured for Merocyanine 540 (MC540) in ethanol and in large unilamellar dimyristoyl phosphatidylcholine vesicles. The major differences in the photophysics between the two media are the increase of the fluorescence quantum yield from 0.15 in ethanol to 0.6 in vesicles at 25° C, and the appearance of a second fluorescence decay with a lifetime of 1.87 ns in the latter medium. Upper and lower limits for the photoisomerization quantum yields were determined by combining the data from laser flash photolysis and optoacoustic spectroscopy. The decrease in photoisomerization quantum yield upon incorporation of the dye into the lipid bilayer by a factor 2 suggests that this process competes directly with fluorescence. The temperature dependence of the fluorescence and photoisomerization quantum yields in solution supports this model. In both media MC540 has a very low triplet quantum yield with values 0.002 > (> ø_T > 0.02 in ethanol and 0.01 > ø_T- > 0.09 in liposomes Our data are consistent with the model whereby the dye is incorporated into the lipid bilayer as a monomer with two different orientations and this model is adopted on the basis of the biexponential behaviour of the fluorescence and photoisomer decay.     

QUENCHING OF THE TRIPLET STATE OF CHLOROPHYLL a BY ASCORBIC ACID AND ASCORBATE IN ETHANOLIC SOLUTION

Abstract— Ascorbic acid and ascorbate in chlorophyll ethanol solution were found to be fairly efficient quenchers of the chlorophyll triplet state; comparable to the efficiency of ascorbic acid as a quencher in aqueous pyridine solution.
It has been well established that ascorbic acid quenches the triplet state of chlorophyll in aqueous pyridine solution.^(1,2) The bimolecular quenching constant, kQ , is very much less than that for O₂ or quinine.^(3,4)
Information regarding the quenching of the triplet state of chlorophyll by ascorbic acid in ethanolic solution is lacking. There has been some question as to whether ascorbic acid reduces photoexcited chloro-phyll-ethanolic solution because of its high oxidation potential, or because like the ascorbate ion, it acts only as a quencher; both ascorbic acid and ascorbate in high concentrations gave low quantum yields.⁽⁵⁾ The quenching of the triplet state by ascorbic acid and ascorbate was determined by the flash-photolytic method.     

DEPENDENCE OF THE TRIPLET YIELD ON EXCITATION ENERGY IN ALL-TRANS AND 11-CIS RETINAL*

Abstract. The triplet-triplet absorption of all-trans and 11- cis retinal was measured as a function of the exciting radiation from 423 nm to 365 nm in a glass of 3-methylpentane at 77 K. This experiment was also accomplished with all-trans retinal in hexane at ambient temperature. The relative triplet formation quantum yields of all-trans and 11-cis retinal at 77 K were found to be independent (±10%) of the frequency of the exciting radiation. At room temperature we measured an increase in this relative quantum yield for all- trans retinal from 1.0 at 365 nm to 1.82 at 423 nm [Bensasson et al. (1975) measured an absolute quantum yield of 0.45 at 353 nm]. These results are used to evaluate previous interpretations for photophysical decay processes in all-trans retinal, and previous suggestions for wavelength dependent radiationless transitions are shown to be unacceptable. High energy excitation of 300 K solutions of all- trans retinal produce excited states that result in less efficient intersystem crossing. These states appear to be inaccessible in the 77 K matrices. We suggest that steric restrictions introduced by the retinal matrix interaction at 77 K are able to block this new internal conversion pathway back to the ground state.     

KINETIC PHOTOCHEMICAL AND PHOTOVOLTAIC ENERGY CONVERSION MODELS

Abstract— An energy conversion model descending from, and generalising, models due to BjoUrn, Calvin, Knox. Ross and others has been developed. It uses three sets of levels between which radiative, non-radiative and storage transitions are possible. Maximisation of the rate of power storage with respect to the absorption threshold yields wavelengths of the order of 680 nm is in good agreement with the absorption peak of chlorophyll a. Departure from the experimental spectra, for example by the substitution of equivalent black-body spectra, and passage to two sets of levels only, tends to destroy this agreement, which presents chlorophyll a as a materia! optimised through evolution for a maximum rate of power storage in day light. Various meteorological conditions are considered. The results found are not very sensitive to cloud cover. The simplified model for two sets of levels yields an interpretation in terms of transition probabilities of the parameters which occur in the simple solar cell theory. Both types of conversion are thus covered by the same theory. The model is also general enough to deal with photochemical or photovoltaic conversion in undersea conditions.     

PHOTOSTATIONARY FLUORESCENCE EMISSION AND TIME RESOLVED SPECTROSCOPY OF SYMMETRICALLY DISUBSTITUTED ANTHRACENES ON THE meso AND SIDE RINGS: THE UNUSUAL BEHAVIOR OF THE 1,4 DERIVATIVE*

Abstract— Steady state and time resolved fluorescence emission properties of symmetrical dialkoxy-anthracenes (especially substituted on the side rings) 1-X, Y were studied in methylcylohexane. At room temperature, the fluorescence spectra of 1-X, Y show bands in the region of 380–550 nm and quantum yields (φ_F) in the range of 0.2–1. The fluorescence emission decays were found to be single exponential. The determination of the intersystem crossing quantum yields (φ_isc) for the weakly fluorescent compounds (1–1,5, 1–1,8 and 1–2,3) demonstrates that internal conversion is negligible compared with fluorescence emission and intersystem crossing, as previously observed for other anthracene derivatives. The fluorescence emission efficiency of compounds 1-X,Y is controlled by the relative mutual positions of the second triplet T₂ (whose energy varies significantly with substitution) and the first excited singlet S₁ states, respectively. An unusual solvatochromism was found for compound 1–1,4 which has a very weak permanent dipole moment in the ground state. This behavior was assigned to strong changes in the electronic densities between the excited singlet state and the ground state.     

How To Make Nitroaromatic Compounds Glow: Next-Generation Large X-Shaped,Centrosymmetric Diketopyrrolopyrroles

Red-emissive π-expanded diketopyrrolopyrroles (DPPs) with fluorescence reaching λ=750 nm can be easily synthesized by a three-step strategy involving the preparation of diketopyrrolopyrrole followed by N-arylation and subsequent intramolecular palladium-catalyzed direct arylation. Comprehensive spectroscopic assays combined with first-principles calculations corroborated that both N-arylated and fused DPPs reach a locally excited (S₁) state after excitation, followed by internal conversion to states with solvent and structural relaxation, before eventually undergoing intersystem crossing. Only the structurally relaxed state is fluorescent, with lifetimes in the range of several nanoseconds and tens of picoseconds in nonpolar and polar solvents, respectively. The lifetimes correlate with the fluorescence quantum yields, which range from 6 % to 88 % in nonpolar solvents and from 0.4 % and 3.2 % in polar solvents. A very inefficient (T₁) population is responsible for fluorescence quantum yields as high as 88 % for the fully fused DPP in polar solvents.     

CURCUMIN-DERIVED TRANSIENTS: A PULSED LASER AND PULSE RADIOLYSIS STUDY

Abstract In this paper we report a time-resolved investigation of transients derived from curcumin, which may be intimately involved in the processes leading to its biological activity. Fluorescence and triplet quantum yields are respectively 0.06 and 0.11. The high percentage of internal conversion is proposed to proceed via H-transfer within the thermodynamically favored enol structure of what is formally a 1,3-diketone. The triplet energy (191 ± 2 kJ mol⁻¹), natural lifetime (1.5 μs) and self-quenching rate constant (5.0 × 10⁸ L mol⁻¹ s⁻¹) have been determined. Oxygen quenching of the triplet leads to the production of singlet oxygen with unit efficiency. Curcumin quenches the latter species very inefficiently (2.5 × 10⁵ L mob⁻¹ s⁻¹). The curcumin radical has been produced via three mechanistically distinct methods. This species is unreactive toward oxygen but is repaired by vitamins C and E and anthralin.     

Direct photolysis of phenols

Conclusions The photodissociation quantum yields were determined for a series of phenols in nonpolar media and the increase in quantum yield with increasing excitation energy was shown to be a function of competition of internal intercombinational conversion process.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 438–441, February, 1987.     

Photophysical Characterization of the Naturally Occurring Dioxobacteriochlorin Tolyporphin A and Synthetic Oxobacteriochlorin Analogues

Tolyporphins are tetrapyrrole macrocycles produced by a cyanobacterium‐containing culture known as HT‐58‐2. Tolyporphins A–J are free base dioxobacteriochlorins, whereas tolyporphin K is an oxochlorin. Here, the photophysical characterization is reported of tolyporphin A and two synthetic analogues, an oxobacteriochlorin and a dioxobacteriochlorin. The characterization (in toluene, diethyl ether, ethyl acetate, dichloromethane, 1‐pentanol, 2‐butanone, ethanol, methanol, N,N‐dimethylformamide and dimethylsulfoxide) includes static absorption and fluorescence spectra, fluorescence quantum yields and time‐resolved data. The data afford the lifetime of the lowest singlet excited state and the yields of the nonradiative decay pathways (intersystem crossing and internal conversion). The three macrocycles exhibit only modest variation in spectroscopic and excited‐state photophysical parameters across the solvents. The long‐wavelength (Q_y) absorption band of tolyporphin A appears at ~680 nm and is remarkably narrow (full‐width‐at‐half‐maximum ~7 nm). The position of the long‐wavelength (Q_y) absorption band of tolyporphin A (~680 nm) more closely resembles that of chlorophyll a (662 nm) than bacteriochlorophyll a (772 nm). The absorption spectra of tolyporphins B–I, K (which were available in minute quantities) are also reported in methanol; the spectra of B–I closely resemble that of tolyporphin A. Taken together, tolyporphin A generally exhibits spectral and photophysical features resembling those of chlorophyll a.     

PHOTOPHYSICAL BEHAVIOUR OF 5-METHOXYPSORALEN IN DIOXANE-WATER MIXTURES

Abstract— Triplet-triplet absorption spectra, intersystem crossing quantum yields, fluorescence lifetimes, and fluorescence quantum yields of 5-methoxypsoralen (5MOP) in dioxane-water mixtures are reported. The fluorescence and triplet formation quantum yields depend strongly on the water content in the mixtures, increasing up to maximum values which are, respectively, twentyfold and fivefold larger than in dioxane and then decreasing. This behaviour is essentially due to the variation of the internal conversion rate constant. With these solvent mixtures it is possible to emulate the dielectric response of 5MOP photophysical parameters in other media, such as in biological model systems and in human blood lipoproteins. The biological importance of these results is discussed.     

How To Make Nitroaromatic Compounds Glow: Next‐Generation Large X‐Shaped,Centrosymmetric Diketopyrrolopyrroles

Red‐emissive π‐expanded diketopyrrolopyrroles (DPPs) with fluorescence reaching λ=750 nm can be easily synthesized by a three‐step strategy involving the preparation of diketopyrrolopyrrole followed by N‐arylation and subsequent intramolecular palladium‐catalyzed direct arylation. Comprehensive spectroscopic assays combined with first‐principles calculations corroborated that both N‐arylated and fused DPPs reach a locally excited (S₁) state after excitation, followed by internal conversion to states with solvent and structural relaxation, before eventually undergoing intersystem crossing. Only the structurally relaxed state is fluorescent, with lifetimes in the range of several nanoseconds and tens of picoseconds in nonpolar and polar solvents, respectively. The lifetimes correlate with the fluorescence quantum yields, which range from 6 % to 88 % in nonpolar solvents and from 0.4 % and 3.2 % in polar solvents. A very inefficient (T₁) population is responsible for fluorescence quantum yields as high as 88 % for the fully fused DPP in polar solvents.     

Absolute fluorescence quantum yields for vapour-phase benzene and naphthalene,and comments on the non-radiative processes

Optic—acoustic measurements have been employed in the determination of absolute quantum yields for benzene and naphthalene. Heat yields are measured by a method using oxygen quenching of both triplet and singlet states. For vibrationally relaxed excited singlet states the fluorescence quantum yields, φ^B_f, are 0.16 ± 0.02 and 0.79 ± 0.02 for benzene and naphthalene respectively. For 0.07 torr naphthalene at room temperature with 248 nm excitation, φ_f = 0.35 ± 0.03 and the quantum yield of internal conversion is less than 0.05. The decay of the highly vibrationally excited triplet state is dominated by vibrational relaxation for 0.07 torr naphthalene, but for benzene, even at high pressures, strong competition comes from an indirect coupling process to the ground state.     

Some aspects of photochemical systems for direct light-induced hydrogen production

Various possible pathways for photochemical conversion of light energy, including light-induced electron transfer and hydride transfer, are described. Several problems diminishing the photoconversion efficiency as well as side reactions affecting the stability of these systems are discussed. Oxidation of photosensitizers by singlet oxygen as well as attack by OH radicals is supposed to be the main degradation pathway for dyes and for the photoinduced reactions. The stability of viologens (acting as electron transfer agents) is mainly affected by hydrogenation, for which a reaction mechanism is presented. The dependence of rate constants on the free enthalpy of reaction is discussed with respect to quantum yields for light energy conversion. Following this, quantum yields of cyclic water splitting based on diffusion-controlled reactions are very low. Selective catalysis or vectorial processes (with a spatial charge separation) could enhance the quantum yields.     

Viscosity dependence of the fluorescence lifetimes of cryptocyanine,pinacyanol and DDI

Viscosity dependence of the fluorescence lifetimes of cryptocyanine, pinacyanol and I, I'-diethyl-2,2'-dicarbocyanine iodide (DDI) has been studied by making relative quantum yield measurements in five solvents. It has also been established. by means of flash kinetic spectroscopy, that, in rigid solvents, φ^o_F+φ^o_IC ≈ 1 for all three dyes, where φ^o_F and φ^o_IC stand for the intrinsic quantum yields of fluorescence emission and internal conversion, respectively. Values of the intrisic rate constant of internal conversion are also presented.     

COMPARISON OF THE SOLID-MATRIX LUMINESCENCE PROPERTIES and PHOTOPHYSICAL PARAMETERS OF TWO PRODUCTS FROM BENZO(a)PYRENE-DNA ADDUCTS

Abstract The solid-matrix luminescence properties and several calculated photophysical parameters of two important products from the benzo(a)pyrene-DNA adducts were compared. The products were benzo(a)pyrene-r-7,t-8,9,c-10-tetrahydrotetrol (I-1) and 7R,8S,9S-trihydroxy-10R-(A^p-deoxyguanosyl-3'-phosphate)-7,8,9,1O-tetrahydroben-zo(a)pyrene (BPDE-dG). The solid-matrix luminescence data were obtained for 1–1and BPDE-dG adsorbed on two different solid matrices, namely, 1% a-cyclodextrin (CD)/NaCl and 25% trehalose/NaCl and at two different temperatures (93 K and 296 K). The 25% trehalose/NaCl gave higher fluorescence and phosphorescence quantum yields from both 1–1and BPDE-dG in contrast to the 1%α-CD/NaCl matrix. The BPDE-dG showed lower fluorescence quantum yields on the solid matrices compared to 1–1. The lower fluorescence quantum yields for BPDE-dG were attributed to a photoinduced electron transfer mechanism. In contrast to the room-temperature solution fluorescence of BPDE-dG, BPDE-dG gave rather high fluorescence quantum yields at room temperature when adsorbed on the two solid matrices. From solid-matrix luminescence quantum yields and solid-matrix luminescence lifetimes, many photophysical parameters were calculated and compared. Several differences among the rate constants were noted with the two solid matrices for BPDE-dG and 1–1. For example, BPDE-dG showed internal conversion at 296 K with 25% trehalose/NaCl, but no internal conversion was observed at 93 K with this solid matrix. Also, for BPDE-dG the phosphorescence rate constants at 296 K and 93 K. were very small with 25% trehalose/NaCl, but the intersystem crossing rate constants from the triplet state to the ground state were very large. The results from this work show how solid-matrix luminescence can be employed to obtain unique luminescence information from the 1–1and BPDE-dG systems.     

Photophysical Behavior of Angelicins and Thioangelicins: Semiempirical Calculations and Experimental Study

The decay processes of the lowest excited singlet and triplet states of five methylated angelicins (4,6,4′-trimethyl-angelicin, MA, and four methylated thioangelicins, MTA; see Scheme 1) were investigated in live solvents by stationary and pulsed fluorometric and flash photolytic techniques. In particular, the solvent effects on absorption, fluorescence, quantum yields of fluorescence (φ_F) and triplet formation (φ_T), lifetimes of fluorescence (τ_F) and the triplet state (τ_T) and the quantum yields of singlet oxygen production (φ_Δ) were investigated. Semiempirical (ZINDO/S-CI) calculations were carried out to obtain information (transition probabilities and nature) on the lowest excited singlet and triplet states. The quantum mechanical calculations and the solvent effect on the photophysical properties showed that the lowest excited singlet state (S¹) is a partially allowed π,π* state, while the close-lying S₂ state is n,π* in nature. The efficiencies of fluorescence, S₁→T₁ intersystem crossing (ISC) and S₁→ S₀ internal conversion (IC) strongly depend on the energy gap between S₁, and S₂ and are explained in terms of the so-called proximity effect. In fact, for MA in cyclohexane, only the S₁→ S₀ internal conversion is operative, while in acetonitrile and ethanol, where the n.π* state is shifted to higher energy, the efficiencies of fluorescence and ISC increase significantly. The energy gap between S₁ and S₂ increases in MTA, where the furanic oxygen is replaced by a sulfur atom. Consequently, the solvent effect on the photophysical parameters of MTA is less marked than for MA; e.g. fluorescence and triplet-triplet absorption are also detectable in the nonpolar cyclohexane. The lowest excited singlet state of molecular oxygen O₂(¹D_g) was produced efficiently in polar solvents by energy transfer from the T₁ state of MA and MTA.     

QUENCHING OF CHLOROPHYLL FLUORESCENCE BY NITROBENZENE

Abstract—Nitrobenzene quenching of chlorophyll fluorescence in ethanol has been investigated. Steady state relative quantum yields have been measured and fluorescence decay rates were determined using both nanosecond photon counting and picosecond pulses from a mode-locked Nd³⁺ glass laser.
The fluorescence decay is described by
1( t )= I ₀ exp (- t/τ−At^1/2 )
the form predicted for decay governed by the kinetics of the continuum model of diffusion controlled reactions. From the parameters of the fluorescence decay, the encounter distance is 5–7 A° the mutual diffusion coefficient is 0.62 × 10^--⁵ cm2s^-1± 12%.
Some of the fluorescence quenching is also attributed to static quenching by a nitrobenzene-chlorophyll, ground-state complex. The equilibrium constant for formation of this ground-state complex was determined to be 4.1 M ^-1. The combined dynamic and static quenching model allows calculation of quantum yields of fluorescence in good agreement with the experimentally determined quantum yields.