The first observation of the effect of dendritic structure to produce the triplet excited state of the core stilbene by dendron excitation

We report that both singlet and triplet energy transfers in stilbene-cored benzophenone dendrimers (trans-BPST) took place quite efficiently. On excitation (290 nm) of stilbene group, the intramolecular singlet energy transfer from the excited core stilbene to the benzophenone part (99.7%) was confirmed by quenching of the fluorescence from the core stilbene. The benzophenone in the excited singlet state is known to undergo intersystem crossing to give its excited triplet state quantitatively. However, the very weak phosphorescence from benzophenone part in trans-BPST was observed even at 77 K. The phosphorescence intensity of trans-BPST is only 1% of that of model compound (4-methylbenzophenone) at 77 K. During the irradiation, the absorption spectra also changed due to the trans-cis isomerization. This is probably due to the ultrafast triplet energy transfer from the benzophenone to produce the triplet state stilbene.     

Cyclam-based dendrimers as ligands for lanthanide ions

We have investigated the complexation of lanthanide ions (Nd3+, Eu3+, Gd3+, Tb3+, Dy3+) with three cyclam-based ligands (cyclam = 1,4,8,11-tetraazacyclotetradecane), namely 1,4,8,11-tetrakis(naphthylmethyl)cyclam (1), and two dendrimers consisting of a cyclam core appended with four dimethoxybenzene and eight naphthyl units (2) and twelve dimethoxybenzene and sixteen naphthyl units (3). In the free ligands the fluorescence of the naphthyl units is strongly quenched by exciplex formation with the cyclam nitrogens. Complexation with the metal ions prevents exciplex formation and revives the intense naphthyl fluorescence. Fluorescence and NMR titration experiments have revealed the formation of complexes with different metal/ligand stoichiometries in the case of 1, 2 and 3. Surprisingly, the large dendrimer 3 gives rise to a stable [M(3)3]3+ species. Energy transfer from the lowest singlet and triplet excited states of the peripheral naphthyl units to the lower lying excited states of Nd3+, Eu3+, Tb3+, Dy3+ coordinated to the cyclam core does not take place.     

Efficient synthesis of porphyrin-containing,benzoquinone-terminated,rigid polyphenylene dendrimers

A series of rigid polyphenylene, free-base porphyrin-containing dendrimers terminated with either dimethoxybenzene or benzoquinone end-groups were prepared by a combined divergent and convergent synthesis. Unlike previous routes for preparing polyphenylene dendrimers that are incompatible with end-groups bearing certain functional moieties, the synthetic methodology chosen for this work enables incorporation of functional groups on the dendrimer end-groups during preparation of the dendrimer wedges and during synthesis of the final dendrimer. The basic strategy utilized a convergent preparation of dendrimer wedges using Suzuki coupling conditions, which were then either attached to a porphyrin core in a divergent coupling step or cyclized to form the porphyrin dendrimer in a convergent step. The latter approach was found to be more general and resulted in higher yields and more readily separated products. Steady-state absorption measurements for these dendrimers showed Soret and Q-band absorptions typical of free-base porphyrins. Preliminary steady-state fluorescence measurements of these dendrimers indicate quenching of the S1 state of the free-base porphyrin in all benzoquinone-containing dendrimers that is attributed to efficient electron-transfer from the excited porphyrin to the benzoquinone end-groups. The amount of fluorescence quenching was in good agreement with the number of benzoquinone groups at the dendrimer periphery and the distance between the porphyrin and benzoquinone groups as calculated by semiempirical (AM1) molecular orbital calculations.     

Energy and electron transfer in bifunctional non-conjugated dendrimers

Nonconjugated dendrimers, which are capable of funneling energy from the periphery to the core followed by a charge-transfer process from the core to the periphery, have been synthesized. The energy and electron donors involve a diarylaminopyrene unit and are incorporated at the periphery of these dendrimers. The energy and electron acceptor is at the core of the dendrimer, which involves a chromophore based on a benzthiadiazole moiety. The backbone of the dendrimers is benzyl ether based. A direct electron-transfer quenching of the excited state of the periphery or a sequential energy transfer-electron-transfer pathway are the two limiting mechanisms of the observed photophysical properties. We find that the latter mechanism is prevalent in these dendrimers. The energy transfer occurs on a picosecond time scale, while the charge-transfer process occurs on a nanosecond time scale. The lifetime of the charge separated species was found to be in the range of microseconds. Energy transfer efficiencies ranging from 80% to 90% were determined using both steady-state and time-resolved measurements, while charge-transfer efficiencies ranging from 70% to 80% were deduced from fluorescence quenching of the core chromophore. The dependence of the energy and charge-transfer processes on dendrimer generation is analyzed in terms of the backfolding of the flexible benzyl ether backbone, which leads to a weaker dependence of the energy and charge-transfer efficiencies on dendrimer size than would be expected for a rigid system.     

Intramolecular interactions in the triplet excited states of benzophenone-thymine dyads

Time-resolved and product studies on the synthesized dyads 1 and 2 have provided evidence that the benzophenone-to-thymine orientation strongly influences intramolecular photophysical and photochemical processes. The prevailing reaction mechanism has been established as a Paterno-Büchi cycloaddition to give oxetanes 3-6; however, the ability of benzophenone to achieve a formal hydrogen abstraction from the methyl group of thymidine has also been evidenced by the formation of photoproducts 7 and 8. These processes have been observed only in the case of the cisoid dyad 1. Adiabatic photochemical cycloreversion of the oxetane ring is achieved upon direct photolysis to give the starting dyad 1 in its excited triplet state. The photobiological implications of the above results are discussed with respect to benzophenone-photosensitized damage of thymidine.     

Photochemistry of thioxanthones—IV. Spectroscopic and flash photolysis study on novel n-propoxy and methyl,n-propoxy derivatives

The spectroscopic properties of seven oil soluble n-propoxy and methyl, n-propoxy substituted thioxanthone structures have been examined in various solvents and the data compared to their photopolymerization efficiencies, photochemical stabilities and flash photolysis behaviours in solution. Absorption maxima, extinction coefficients, fluorescence and phosphorescence spectra and quantum yields have been measured. Generally, all the compounds exhibit low fluorescence and high phosphorescence quantum yields but the ratio is solvent dependent. These observations are consistent with the high photoreactivity of the molecules operating in the lowest excited triplet state which is nπ* in character. Photopolymerization rates of n-butyl methacrylate with N-diethylmethylamine co-initiator correlate with the absorption maxima and extinction coefficients of the thioxanthones and also the degree of quenching of their fluorescence by the amine, indicating the importance of electron transfer. In the absence of a tertiary amine, transient formation on micro-second flash photolysis in 2-propanol is associated with the ketyl radical formed by the lowest excited triplet state abstracting a hydrogen atom from the solvent. In the presence of a tertiary amine, both ketyl radical and radical anion (at longer wavelengths) are observed, the latter being formed via abstraction of an electron from the amine. This is confirmed by a flash photolysis study using amines of various ionization potentials where a correlation is observed with radical anion absorbance. A pH study confirms the identity of the transient species. Activation of the thioxanthone molecule in the 3 and 4 positions with a methyl group enhances initiator activity whereas substitution in the t-position deactivates the molecule through intra-molecular hydrogen atom abstraction.     

Ground and excited-state electronic interactions in poly(propylene amine) dendrimers functionalized with naphthyl units: effect of protonation and metal complexation.

We report the absorption spectra and the photophysical properties (fluorescence spectrum, quantum yield, and lifetime) of four dendrimers of the poly(propylene amine) family (POPAMs) functionalized at the periphery with naphthylsulfonamide (hereafter called naphthyl) units. Each dendrimer Gn, where n = 1 to 4 is the generation number, comprises 2n + 1 (i.e., 32 for G4) naphthyl functions in the periphery and 2n + 1--2 (i.e., 30 for G4) tertiary amine units in the branches. All the experiments have been carried out in acetonitrile solutions. Comparison with two reference compounds (N-methyl-naphthalene-2-sulfonamide, A, and N-(3-dimethylamino-propyl)-2-naphthalene-1-sulfonamide, B) has shown that the absorption spectra of the dendrimers are significantly different from those expected from the component units. Furthermore, the intense fluorescence band of the naphthyl unit (lambda max = 343 nm; phi = 0.15, tau = 8.5 ns) is strongly quenched in the dendrimers. The quenching effect increases with increasing generation and is accompanied by the appearance of a weak and broad emission tail at lower energy. Protonation of the amine units of the dendrimers by addition of CF3SO3H (triflic) acid causes a strong increase in the intensity of the naphthyl luminescence and a change in the form of the emission tail. The shapes of the titration curves depend on dendrimer generation, but in any case, the effect of the acid can be fully reversed by successive addition of a base (tributylamine). The results obtained show that in the dendrimers there are interactions (both in the ground and excited states) between naphthyl units as well as between naphthyl units and amine units of the branches; this gives rise to dimer/excimer and charge-transfer/exciplex excited states. Titration with Zn(CF3SO3)2 has the same effect as acid titration, as far as the final emission spectrum is concerned, but a much higher concentration of Zn(CF3SO3)2 has to be used and the shapes of the titration plots are very different. Titration with Co(NO3)2.6H2O causes a much smaller increase in the intensity of the naphthyl fluorescence compared with Zn(CF3SO3)2. The results obtained have shown that protonation and metal coordination can reveal the presence of ground and excited state electronic interactions in functionalized poly(propylene amine) dendrimers, and that the presence of photo-active units in the dendrimers can be useful to reveal some peculiar aspects of the protonation and metal coordination processes.     

Photolysis of benzophenone with two-step two-laser excitation

The first laser excites a molecule to a lower triplet state and another sequential laser excites it resonantly to higher triplet states or makes it ionization. This two-step two-laser method provides a novel way to study the electron transfer or charge transfer of excited molecules. The higher excited benzophenone and its radical cation can be observed under the time-resolved absorption method when it was excited to lower triplet state by one laser and another one exciting it to higher triplet states resonantly. The higher excited benzophenone molecules undergoing inter-molecular hydrogen abstraction with iso-propylalcohol molecules are faster than the lower ones.     

Photoinitiated grafting of maleic anhydride onto polypropylene

The photoinitiated grafting of maleic anhydride (MAH) onto polypropylene with the use of benzophenone (BP) as the initiator has been investigated. In comparison with the process of thermally initiated grafting with peroxide as the initiator, photoinitiated grafting affords a higher grafting efficiency. The efficient photografting sensitized by BP can be explained by two possible mechanistic processes: the sensitization of the formation of the excited triplet state of MAH by BP and electron transfer followed by proton transfer between MAH and the benzopinacol radical, which may operate together. In the former case, the generated MAH excited triplet state abstracts a hydrogen from the polymer substrate to initiate grafting. A rate constant of 3.6 × 10⁹ M ^?1 s ^?1 has been determined by laser flash photolysis for the process of quenching the excited triplet state of BP with ground‐state MAH. In comparison, the rate constant for the quenching of the excited triplet state of BP by hydrogen abstraction has been determined to be 4.1 × 10⁵ M ^?1 s ^?1. In a study of photografting using a model compound, 2,4‐dimethylpentane, as a small‐molecule analogue of polypropylene, the loss of BP was significantly reduced upon the addition of MAH, and this is consistent with the proposed mechanistic processes. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1953–1962, 2004     

PHOTOCHEMISTRY ON SURFACES: TRIPLET-TRIPLET ENERGY TRANSFER ON MICROCRYSTALLINE CELLULOSE STUDIED BY DIFFUSE REFLECTANCE TRANSIENT ABSORPTION and EMISSION SPECTROSCOPY*

Triplet-triplet energy transfer has been studied between benzophenone and an oxazine dye (2,7-bis(diethyl-amino)-phenazoxonium chloride) co-adsorbed on the surface of microcrystalline cellulose. Ground state absorption and fluorescence measurements provide evidence for dimer formation of the oxazine dye when adsorbed on cellulose in contrast to the behaviour in ethanol solution where no dimerization is observed. The equilibrium constant for dimerization, which is found to be (1.0 × 0.1) × 10⁶ mol^?1 g (2560 × 250 dm³ mol^?1) for oxazine alone on cellulose decreases in the presence of co-adsorbed benzophenone. Fluorescence is detected from excited monomeric but not from excited dimeric oxazine. The absorption spectrum of the triplet state of oxazine adsorbed on cellulose was obtained and its extinction coefficient evaluated relative to that of triplet benzophenone which was used as a sensitizer. The lifetime of adsorbed triplet oxazine is 4.3 ms which is 300 times longer than that in acetonitrile solution. The efficiency of energy transfer from triplet benzophenone to oxazine on cellulose was studied using both time resolved sensitized absorption and phosphorescence intensity measurements as a function of oxazine concentration. Lifetime measurements show that the energy transfer process involves static quenching since the benzophenone lifetime is independent of oxazine loading at the surface. A mechanism is proposed to explain the results in which one oxazine molecule is suggested as being able to quench phosphorescence from a “pool” consisting of 2 to 3 benzophenone molecules.     

THE USE OF BENZOPHENONE AS A PHOTOAFFINITY LABEL, LABELING IN p-BENZOYLPHENYLACETYL CHYMOTRYPSIN AT UNIT EFFICIENCY

Abstract— p -Benzoylphenylacetyl chymotrypsin, an acyl enzyme derivative containing the benzophenone group in the hydrophobic binding pocket, was prepared and is indefinitely stable at low pH. Photolysis of this covalent derivative leads to loss of enzymic activity and incorporation of the labeling group via formation of a second covalent bond. The efficiency of the photochemical processes is exceptionally high, producing 100% incorporation and at least 92% inactivation. Analysis of active site titration data for the photolyzed enzyme show that at least two different photochemical processes must be involved. Elimination of phosphorescence emission and reduction of UV absorption upon photolysis are consistent with initial hydrogen abstraction by benzophenone triplet state, followed by radical coupling, much as has been observed for the photoreaction of benzophenone with model systems. Photoaffinity labeling of chymotrypsin is also efficiently accomplished using two benzophenone derivatives which bind noncovalently to the enzyme's active site, although the rates of labeling are somewhat less than in the covalent complex.     

A Photophysical Study of Terphenyl Core Oligosulfonimide Dendrimers Exhibiting High Steady‐State Anisotropy

The photophysical properties of three dendrimers containing a p‐terphenyl core with appended sulfonimide branches of different size and n‐octyl chains have been investigated in dichloromethane solution. In the dendrimer absorption spectra contributions from both the branches and the core are clearly identified. The fluorescence spectra show only the characteristic fluorescence of the terphenyl unit. Energy transfer from the appended chromophoric groups to the core does not occur. In the dendrimers, the terphenyl core exhibits a very high fluorescence quantum yield (ca. 0.75) and a short emission lifetime (0.8 ns). These properties allowed investigations of the fluorescence depolarization caused by rotation of the dendrimers. The dendrimers show a very high steady‐state anisotropy in dichloromethane solution at room temperature (0.24 for the largest one), compared to that of the parent terphenyl under the same experimental conditions (<0.01) and in rigid matrix (0.33). Both the n‐octyl chains and the sulfonimide branches play important roles to slow down the molecular rotation.     

Mechanisms for fluorescence depolarization in dendrimers

We have investigated the fluorescence properties of dendrimers (Gn is the dendrimer generation number) containing four different luminophores, namely terphenyl (T), dansyl (D), stilbenyl (S), and eosin (E). In the case of T, the dendrimers contain a single p-terphenyl fluorescent unit as a core with appended sulfonimide branches of different size and n-octyl chains. In the cases of D and S, multiple fluorescent units are appended in the periphery of poly(propylene amine) dendritic structures. In the case of E, the investigated luminophore is noncovalently linked to the dendritic scaffold, but is encapsulated in cavities of a low luminescent dendrimer. Depending on the photophysical properties of the fluorescent units and the structures of the dendrimers, different mechanisms of fluorescence depolarization have been observed: (i) global rotation for GnT dendrimers; (ii) global rotation and local motions of the dansyl units at the periphery of GnD dendrimers; (iii) energy migration among stylbenyl units in G2S; and (iv) restricted motion when E is encapsulated inside a dendrimer, coupled to energy migration if the dendrimer hosts more than one eosin molecule.     

Light-harvesting and photoisomerization in benzophenone and norbornadiene-labeled poly(aryl ether) dendrimers via intramolecular triplet energy transfer

A series of benzophenone (BP) and norbornadiene (NBD)-labeled poly(aryl ether) dendrimers (Gn-NBD), generations 1-4, were synthesized, and their photophysical and photochemical properties were examined. The phosphorescence of the peripheral BP (donor) chromophore was efficiently quenched by the NBD (acceptor) group attached to the focal point. Time-resolved spectroscopic measurements indicated that the lifetime of the triplet state of the BP chromophore was shortened due to the proximity of the NBD group. Selective excitation of the BP chromophore resulted in isomerization of the NBD group to quadricyclane (QC). All of these observations suggest that an intramolecular triplet energy transfer occurs in Gn-NBD molecules. The light-harvesting ability of these molecules increases with generation due to an increase in the number of peripheral chromophores. The energy transfer efficiencies are ca. 0.97, 0.54, 0.45, and 0.37 for generations 1-4, respectively, and the rate constant of the triplet-triplet energy transfer is ca. 10(6)-10(7) s(-1), which decreases inconspicuously with increasing generation. The intramolecular triplet energy transfer is proposed to proceed mainly via a through-space mechanism involving the closest donor (folding back conformation) and acceptor groups.     

Polarity effects on the photophysics of dendrimers with an oligophenylenevinylene core and peripheral fullerene units

Highly soluble dendritic branches with fullerene subunits at the periphery and a carboxylic acid function at the focal point have been prepared by a convergent approach. They have been attached to an oligophenylenevinylene (OPV) core bearing two alcohol functions to yield dendrimers with two, four or eight peripheral C60 groups. Their photophysical properties have been systematically investigated in solvents of increasing polarity; that is, toluene, dichloromethane, and benzonitrile. Ultrafast OPV-->C60 singlet energy transfer takes place for the whole series of dendrimers, whatever the solvent. Electron transfer from the fullerene singlet is thermodynamically allowed in CH2Cl2 and benzonitrile, but not in apolar toluene. For a given solvent, the extent of electron transfer, signaled by the quenching of the fullerene fluorescence, is not the same along the series, despite the fact that identical electron transfer partners are present. By increasing the dendrimer size, electron transfer is progressively more difficult due to isolation of the central OPV core by the dendritic branches, which hampers solvent induced stabilization of charge separated couples. Compact structures of the hydrophobic dendrimers are favored in solvents of higher polarity. These structural effects are also able to rationalize the unexpected trends in singlet oxygen sensitization yields.     

Remote Sensitized Photoisomerization via Through‐Bond Triplet–Triplet Energy Transfer Mediated by a Salt Bridge in a Supramolecular Dyad

A supramolecular dyad, BP‐(amidinium‐carboxylate)‐NBD is constructed, in which benzophenone (BP) and norbornadiene (NBD) are connected via an amidinium‐carboxylate salt bridge. The photophysical and photochemical properties of the assembled BP‐(amidinium‐carboxylate)‐NBD dyad are examined. The phosphorescence of the BP chromophore is efficiently quenched by the NBD group in BP‐(amidinium‐carboxylate)‐NBD via the salt bridge. Time‐resolved spectroscopy measurements indicate that the lifetime of the BP triplet state in BP‐(amidinium‐carboxylate)‐NBD is shortened due to the quenching by the NBD group. Selective excitation of the BP chromophore results in isomerization of the NBD group to quadricyclane (QC). All of these observations suggest that the triplet–triplet energy transfer occurs efficiently in the BP‐(amidinium‐carboxylate)‐NBD salt bridge system. The triplet–triplet energy transfer process proceeds with efficiencies of approximately 0.87, 0.98 and the rate constants 1.8×10³ s^?1, and 1.3×10⁷ s^?1 at 77 K and room temperature, respectively. The mechanism for the triplet–triplet energy transfer is proposed to proceed via a “through‐bond” electron exchange process, and the non‐covalent bonds amidinium‐carboxylate salt bridge can mediate the triplet–triplet energy transfer process effectively for photochemical conversion.     

Molecular Size and Electronic Structure Combined Effects on the Electrogenerated Chemiluminescence of Sulfurated Pyrene‐Cored Dendrimers

The electrochemistry, photophysics, and electrochemically generated chemiluminescence (ECL) of a family of polysulfurated dendrimers with a pyrene core have been thoroughly investigated and complemented by theoretical calculations. The redox and luminescence properties of dendrimers are dependent on the generation number. From low to higher generation it is both easier to reduce and oxidize them and the emission efficiency increases along the family, with respect to the polysulfurated pyrene core. The analysis of such data evidences that the formation of the singlet excited state by cation–anion annihilation is an energy‐deficient process and, thus, the ECL has been justified through the triplet–triplet annihilation pathway. The study of the dynamics of the ECL emission was achieved both experimentally and theoretically by molecular mechanics and quantum chemical calculations. It has allowed rationalization of a possible mechanism and the experimental dependence of the transient ECL on the dendrimer generation. The theoretically calculated Marcus electron‐transfer rate constant compares very well with that obtained by the finite element simulation of the whole ECL mechanism. This highlights the role played by the thioether dendrons in modulating the redox and photophysical properties, responsible for the occurrence and dynamics of the electron transfer involved in the ECL. Thus, the combination of experimental and computational results allows understanding of the dendrimer size dependence of the ECL transient signal as a result of factors affecting the annihilation electron transfer.     

The role of the triplet state in the photosensitization of cationic polymerizations by anthracene

The photosensitization mechanism for cationic polymerizations initiated by diaryliodonium salts photosensitized by anthracene was investigated using fluorescence and phosphorescence spectroscopy. In situ photosensitizer fluorescence measurements confirmed that the photosensitization reaction proceeds by an electron transfer process. Transient phosphorescence studies demonstrated that electron transfer occurred from the triplet excited state of anthracene to the initiator, with an intrinsic kinetic rate constant of 2 × 10⁸ L/mol s. Further evidence for the role of the triplet state was provided by an observed seven-fold decrease in the polymerization rate upon addition of a triplet state quencher. Finally, numerical solution of the photophysical kinetic equations indicated that the triplet state concentration was approximately three orders of magnitude higher than that of the singlet state, and that 94-96% of the active cationic centers are produced by reaction of the initiator with the triplet state. These results indicate that the electron transfer occurs primarily from the triplet state of anthracene, with the singlet state providing only a minor contribution to the photosensitization reaction. © 1995 John Wiley & Sons, Inc.     

Inherent Photon Energy Recycling Effects in the Up‐Converted Delayed Luminescence Dynamics of Poly(fluorene)–PtIIoctaethyl Porphyrin Blends

We present results of steady‐state and transient photoluminescence studies of molecularly doped poly(fluorene) films. We study blends with increasing content of the triplet emitter (2,3,7,8,12,13,17,18‐octaethyl‐porphyrinato)Pt^II (PtOEP) when dispersed in the polymeric poly(fluorene) matrix of the poly[9,9‐di‐(2‐ethylhexyl)‐fluorenyl‐2,7‐diyl] (PF26) derivative. We carry out a unified study of the photophysical reactions that are involved in the energy transfer processes in this system by probing the three luminescence processes of a) PF26 fluorescence, b) triplet–triplet annihilation (TTA) induced up‐converted PF26 delayed fluorescence and c) PtOEP phosphorescence. With increasing PtOEP content, the process of photon energy recycling in the PF26:PtOEP system is manifested from the quenching of the TTA‐induced up‐converted PF26 delayed fluorescence and it is rationalized with the use of Forster theory of resonant energy transfer. Based on the combined results of the photophysical and the transmission electron microscopy characterization of the as‐spun PF26:PtOEP films, we determine the onset of PtOEP aggregation at 2–3 wt % PtOEP content. The analysis of the photophysical data is based on the use of modified Stern–Volmer photokinetic models that are appropriate for the solid state. A static component in the PL quenching of PF26 is revealed for PtOEP contents below 2 wt %. The modified Stern–Volmer kinetic scheme further suggests that co‐aggregation effects between PF26 and PtOEP are operative with an association constant of ground state complex formation k_bind ～15–17 M ^?1. The involvement of the ground state heterospecies in the TTA‐mediated PF26 up‐converted luminescence is discussed. The participation of an electron‐exchange step, in the excited state energy transfer pathway between PtOEP and PF26, is proposed for the activation mechanism of the PF26 up‐converted fluorescence.     

A blocked diketo form of avobenzone: photostability, photosensitizing properties and triplet quenching by a triazine-derived UVB-filter

Novel sunscreens are required providing active protection in the UVA and UVB regions. On the other hand, there is an increasing concern about the photosafety of UV filters, as some of them are not sufficiently photostable. Avobenzone is one of the most frequently employed sunscreen ingredients, but it has been reported to partially decompose after irradiation. In the present work, photophysical and photochemical studies on a methylated avobenzone-derivative have shown that the diketo form is responsible for photodegradation. A transient absorption was observed at 380 nm after laser flash photolysis excitation at 308 nm. It was assigned to the triplet excited state of the diketo form, as inferred from quenching by oxygen and β-carotene. This transient also interacted with key building blocks of biomolecules by triplet–triplet energy transfer (in the case of thymidine) or electron transfer processes (for 2'-deoxyguanosine, tryptophan and tyrosine). Irradiation of the avobenzone derivative in the presence of a triazine UV-B filter (E-35852) diminished the undesirable effects of the compound by an efficient quenching of the triplet excited state. Thus, sunscreen formulations including triplet quenchers could provide effective protection from the potential phototoxic and photoallergic effects derived from poor photostability of avobenzone.