Showing papers on "Triplet state published in 2007"

Major signal increase in fluorescence microscopy through dark-state relaxation

Abstract: We report a substantial signal gain in fluorescence microscopy by ensuring that transient molecular dark states with lifetimes >1 μs, such as the triplet state relax between two molecular absorption events. For GFP and Rhodamine dye Atto532, we observed a 5–25-fold increase in total fluorescence yield before molecular bleaching when strong continuous-wave or high-repetition-rate pulsed illumination was replaced with pulses featuring temporal pulse separation >1 μs. The signal gain was observed both for one- and two-photon excitation. Obeying dark or triplet state relaxation in the illumination process signifies a major step toward imaging with low photobleaching and strong fluorescence fluxes. Please visit methagora to view and post comments on this article

Internal conversion to the electronic ground state occurs via two distinct pathways for pyrimidine bases in aqueous solution.

Abstract: The femtosecond transient absorption technique was used to study the relaxation of excited electronic states created by absorption of 267-nm light in all of the naturally occurring pyrimidine DNA and RNA bases in aqueous solution. The results reveal a surprising bifurcation of the initial excited-state population in < 1p s to two nonradiative decay channels within the manifold of singlet states. The first is the subpicosecond internal conversion channel first characterized in 2000. The second channel involves passage through a dark intermediate state assigned to a lowest-energy 1 n* state. Approximately 10 –50% of all photoexcited pyrimidine bases decay via the 1 n* state, which has a lifetime of 10 –150 ps. Three- to 6-fold-longer lifetimes are seen for pyrimidine nucleotides and nucleosides than for the corresponding free bases, revealing an unprecedented effect of ribosyl substitution on electronic energy relaxation. A small fraction of the 1 n* population is proposed to undergo intersystem crossing to the lowest triplet state in competition with vibrational cooling, explaining the higher triplet yields observed for pyrimidine versus purine bases at room temperature. Some simple correlations exist between yields of the 1 n* state and yields of some pyrimidine photoproducts, but more work is needed before the photochemical consequences of this state can be definitively determined. These findings lead to a dramatically different picture of electronic energy relaxation in single pyrimidine bases with important ramifications for understanding DNA photostability. conical intersection DNA photophysics excited-state dynamics

Characterization of triplet-triplet annihilation in organic light-emitting diodes based on anthracene derivatives

Abstract: We report that the steady-state electroluminescence in organic light-emitting diodes (OLEDs) based on anthracene derivatives has a substantial contribution from annihilation of triplet states generated by recombining charge carriers. For the OLED devices of the following general structure: indium tin oxide∕N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine∕9,10-bis(2-naphthyl)-2-t-butylanthracene∕Alq3 (tris(8-hydroxyquinolate)aluminum)∕LiF∕Al, triplet-triplet annihilation contributes as much as 3%–6% of the overall electroluminescence. The intensity of triplet-triplet annihilation-related emission strongly varies with the current density and pulse width, being quadratic and linear functions of current density at low ( 10mA∕cm2) current density regimes, respectively. We find that quenching by charge carriers is the dominant decay process for the triplet states under a wide range of operating conditions, yielding triplet-state lifetimes from tens to hundreds of microseconds. T...

Inhibition of humic substances mediated photooxygenation of furfuryl alcohol by 2,4,6-trimethylphenol. Evidence for reactivity of the phenol with humic triplet excited states.

Abstract: To probe the reactivity of 2,4,6-trimethylphenol with humic triplet excited states, we investigated its influence on the humic substances-mediated photooxygenation offurfuryl alcohol. Elliott soil humic and fulvic acids were employed for these experiments. When added in the concentration range of 10(-4) - 10(-3) M, 2,4,6-trimethylphenol inhibited furfuryl alcohol photooxygenation to an extent depending on its concentration. The inhibiting effect decreased as the oxygen concentration was increased. By postulating that 2,4,6-trimethylphenol competes with oxygen for reaction with humic triplet excited states and with furfuryl alcohol for reaction with singlet oxygen, we obtained kinetic laws describing the consumption profiles of furfuryl alcohol and 2,4,6-trimethylphenol. Experimental rates of 2,4,6-trimethylphenol and furfuryl alcohol loss could be satisfactorily fitted with 1.09-1.16 for the ratio k2/k3, where k2 and k3 are the reaction rate constants of humic triplet excited states with oxygen and 2,4,6-trimethylphenol, respectively. These types of experiments could be extended to a variety of substrates to measure their reaction rate constants with humic triplet excited states.

Synthesis, photophysical and photochemical properties of substituted zinc phthalocyanines

Abstract: The synthesis, photophysical and photochemical properties of the 4-({3,4,5-tris-[2-(2-ethoxyethoxy)ethyloxy]benzyl}oxy) and 4-({3,4,5-tris-[2-(2-ethoxyethoxy)ethyloxy]benzyl}thio) zinc(II) phthalocyanines are reported for the first time. The new compounds have been characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy, electronic spectroscopy and mass spectra. General trends are described for photodegradation, singlet oxygen, fluorescence and triplet excited state quantum yields, and triplet state and fluorescence lifetimes of these compounds in dimethylsulfoxide (DMSO). The fluorescence of the complexes was quenched by benzoquinone (BQ). The effects of the substitution on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (6, 7 and 8) are also reported. Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications. The substituted Zn(II) phthalocyanines showed high triplet and singlet oxygen quantum yields. High singlet oxygen quantum yields are very important for Type II mechanism. Thus, these complexes show potential as Type II photosensitizers.

Origin of the large spectral shift in electroluminescence in a blue light emitting cationic iridium(III) complex

Abstract: A new, but archetypal compound [Ir(ppy-F2)2Me4phen]PF6, where ppy-F2 is 2-(2′,4′-fluorophenyl)pyridine and Me4phen is 3,4,7,8-tetramethyl-1,10-phenanthroline, was synthesized and used to prepare a solid-state light-emitting electrochemical cell (LEEC). This complex emits blue light with a maximum at 476 nm when photoexcited in a thin film, with a photoluminescence quantum yield of 52%. It yields an efficient single-component solid-state electroluminescence device with a current efficiency reaching 5.5 cd A−1 and a maximum power efficiency of 5.8 Lm Watt−1. However, the electroluminescence spectrum is shifted with respect to the photoluminescence spectrum by 80 nm resulting in the emission of green light. We demonstrate that this unexpected shift in emission spectrum does not originate from the mode of excitation, nor from the presence of large concentrations of ions, but is related to the concentration of the ionic transition metal complex in the thin film. The origin of the concentration-dependent emission is extensively commented on and argued to be related to the population of either 3LC π–π* or 3MLCT triplet states, in diluted and concentrated films, respectively. Using quantum chemical calculations we demonstrate that three low-energy triplet states are present with only 0.1 eV difference in energy and that their associated emission wavelengths differ by as much as 60 nm from each other.

Intersystem crossing driven by vibronic spin–orbit coupling: a case study on psoralen

Abstract: For 7H-furo[3,2-g][1]benzopyran-7-one (psoralen), intersystem crossing (ISC) rate constants have been computed. Employing the Fermi golden rule, the harmonic approximation, and a pure-spin Born–Oppenheimer basis, both direct and vibronic spin–orbit (SO) coupling has been taken into account. Necessary data on electronic excitation energies and potential energy hypersurfaces originate from correlated all-electron calculations applying (time-dependent) density functional theory and the density functional theory/multireference configuration interaction approach. SO coupling has been treated by means of the one-center mean-field approximation. Vibronic SO couplings have been evaluated via numerical differentiation of SO matrix elements. Accounting only for direct SO coupling, rate constants of the order of kISC ≈ 1010 s−1 result for S2(n → π*) T1(π → π*) ISC, whereas the rates of the channels S1(π → π*) T{1,2,3}(π → π*) do not exceed kISC ≈ 105 s−1. Including vibronic SO coupling, rate constants of kISC ≈ 3 × 108 s−1 are obtained for the S1(π → π*) T1(π → π*) ISC. The radiationless transition from the S1(π → π*) state to the nearly degenerate T3(π → π*) state has been estimated to be slightly less efficient (kISC ≈ 107 s−1). Based on our computed rates of ISC and excited state solvent shifts, we conclude that the experimentally observed appreciable triplet quantum yields of psoralen in polar protic media are primarily due to S1(π → π*) T(π → π*) channels. For heteroaromatic systems, (π → π*)/(π → π*) ISC driven by vibronic SO coupling is expected to be a common triplet state population mechanism.

Slow electron injection on Ru-Phthalocyanine sensitized TiO2.

Abstract: Photoinduced electron injection in dye sensitized TiO2 is a critical step in the function of dye sensitized solar cells. High electron injection quantum yields are a requirement to obtain efficient devices. While high electron injection quantum yields are usually linked to ultrafast electron-transfer dynamics (in the fs−ps timescales), the latter are not a requirement. We present here a system, Ru-phthalocyanine sensitized TiO2, where slow electron injection (kinj ≈ 450 ns-1) and efficient electron injection are compatible owing to the long lifetime of the injecting state, the Ru-phthalocyanine triplet state. Ru-phthalocyanine dyes are attractive sensitizers because they absorb strongly in the red and their axial ligands hinder the formation of aggregates.

On the role of aromatic side chains in the photoactivation of BLUF domains.

Abstract: BLUF (blue-light sensing using FAD) domain proteins are a novel group of blue-light sensing receptors found in many microorganisms. The role of the aromatic side chains Y21 and W104, which are in close vicinity to the FAD cofactor in the AppA BLUF domain from Rhodobacter sphaeroides ,i s investigated through the introduction of several amino acid substitutions at these positions. NMR spectroscopy indicated that in the W104F mutant, the local structure of the FAD binding pocket was not significantly perturbed as compared to that of the wild type. Time-resolved fluorescence and absorption spectroscopy was applied to explore the role of Y21 and W104 in AppA BLUF photochemistry. In the Y21 mutants, FADH ¥ -W ¥ radical pairs are transiently formed on a ps time scale and recombine to the ground state on a ns time scale. The W104F mutant shows a spectral evolution similar to that of wild type AppA but with an increased yield of signaling state formation. In the Y21F/W104F double mutant, all light-driven electron-transfer processes are abolished, and the FAD singlet excited-state evolves by intersystem crossing to the triplet state. Our results indicate that two competing light-driven electron- transfer pathways are available in BLUF domains: one productive pathway that involves electron transfer from the tyrosine, which leads to signaling state formation, and one nonproductive electron-transfer pathway from the tryptophan, which leads to deactivation and the effective lowering of the quantum yield of the signaling state formation. Our results are consistent with a photoactivation mechanism for BLUF domains where signaling state formation proceeds via light-driven electron and proton transfer from the conserved tyrosine to FAD, followed by a hydrogen-bond rearrangement and radical-pair recombination.

Two pathways for photon upconversion in model organic compound systems

Abstract: We have studied the phenomenon of photon upconversion in systems of two model compounds as highly efficient blue emitters sensitized with metallated macrocycle molecules in thin films. The bimolecular upconversion process in these systems is based on the presence of a metastable triplet excited state of the macrocycles giving rise to dramatically different photophysical characteristics relative to the other known methods for photon upconversion such as two-photon absorption, parametric processes, second harmonic generation, and sequential multiphoton absorption. The chosen blue emitter molecules have suitably positioned triplet levels: in the case of an oligofluorine—essentially higher and in the case of diphenylanthracene—lower than the sensitizer porphyrin platinum triplet level and thus two excitation pathways for photon upconversion were observed and investigated.

Experimental signature of phonon-mediated spin relaxation in a two-electron quantum dot.

Abstract: We observe an experimental signature of the role of phonons in spin relaxation between triplet and singlet states in a two-electron quantum dot. Using both the external magnetic field and the electrostatic confinement potential, we change the singlet-triplet energy splitting from 1.3 meV to zero and observe that the spin relaxation time depends nonmonotonously on the energy splitting. A simple theoretical model is derived to capture the underlying physical mechanism. The present experiment confirms that spin-flip energy is dissipated in the phonon bath.

Rapid intersystem crossing in closely-spaced but orthogonal molecular dyads

Abstract: A borondipyrromethene (bodipy) dye is equipped with a 4-pyridine residue attached via the meso position. The strong fluorescence inherent to this class of dye is extinguished on protonation of the pyridine N atom. For the corresponding N-methylpyridinium derivative, fluorescence from the dye fragment is also extensively quenched due to the onset of a light-induced charge-shift reaction. The resultant charge-transfer state (CTS) is weakly fluorescent and decays primarily by way of population of the triplet excited state localized on the bodipy dye. Time-resolved spectral studies provide rate constants for all the steps involved in the forward and reverse charge-shift reactions. An interesting feature is that the lifetime of the CTS, around 1 ns, correlates with the viscosity of the solvent as might be expected if the rate-limiting step involves a substantial change in geometry. There is an unexpectedly small activation energy for the reverse charge-shift reaction, even allowing for the fact that this involves triplet formation. Local fluorescence is restored on cooling to 77 K.

Triplet Excited State in Platinum−Acetylide Oligomers: Triplet Localization and Effects of Conformation

Abstract: An experimental and theoretical investigation was carried out on a series of platinum-acetylide oligomers of the general structure Ph-CC-[PtL2-CC-(1,4-Ph)-CC-]n-PtL2-CC-Ph (where n = 1, 2, 3, 4, 6; Ph = phenyl, 1,4-Ph = 1,4-phenylene; L = P(n-Bu)3, and the geometry at Pt = trans). The objective of this work is to understand the geometry and electronic structure of the ground and triplet excited states of Pt-acetylide oligomers. The experiments carried out include temperature-dependent absorption and photoluminescence spectroscopy (80-298 K range) and ambient temperature transient absorption spectroscopy. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were carried out on several of the oligomers using the hybrid Becke's three-parameter functional with the B3LYP correlation functional and the SDD basis set. The combined experimental and theoretical results provide very clear evidence that the triplet excited state is localized on a chromophore consisting approximately of a single -[PtL2-CC-(1,4-Ph)-CC-PtL2]- repeat unit. DFT calculations indicate that in the ground state conformers that differ in the (rotational) orientation of the 1,4-phenylenes with respect to the plane defined by the PtL2(C)2 units (twisted = t and planar = p) are very close in energy (difference of <1 kcal.mol-1). By contrast, in the triplet excited state, the p conformer is 3 kcal.mol-1 lower in energy than the t conformer. The torsional geometry change in the triplet state is reflected in the low-temperature phosphorescence spectra of the short oligomers, where separate emission bands are seen from the t and p conformers.

Thermally activated delayed fluorescence as a cycling process between excited singlet and triplet states: Application to the fullerenes

Abstract: In efficient thermally activated delayed fluorescence (TADF) the excited chromophore alternates randomly between the singlet and triplet manifolds a large number of times before emission occurs. In this work, the average number of cycles n is obtained and is shown to have a simple experimental meaning: n+1 is the intensification factor of the prompt fluorescence intensity, owing to the occurrence of TADF. A new method of data analysis for the determination of the quantum yield of triplet formation, combining steady-state and time-resolved data in a single plot, is also presented. Application of the theoretical results to the TADF of [70]fullerenes shows a general good agreement between different methods of fluorescence analysis and allows the determination of several photophysical parameters.

Triplet State Properties of the OLED Emitter Ir(btp)2(acac): Characterization by Site-Selective Spectroscopy and Application of High Magnetic Fields

Abstract: The well-known red emitting complex Ir(btp)2(acac) (bis(2-(2‘-benzothienyl)-pyridinato-N,C3‘)iridium(acetylacetonate)), frequently used as emitter material in OLEDs, has been investigated in a polycrystalline CH2Cl2 matrix. The studies were carried out under variation of temperature down to 1.2 K and at magnetic fields up to B = 10 T. Highly resolved emission and excitation spectra of several specific sites are obtained by site-selective spectroscopy. For the preferentially investigated site (I → 0 at 16268 cm-1), the three substates I, II, and III of the T1 triplet state are separated by ΔEII-I = 2.9 cm-1 and ΔEIII-I = 25.0 cm-1, respectively. ΔEIII-I represents the total zero-field splitting (ZFS). The individual decay times of these substates are τI = 150 μs, τII = 58 μs, and τIII = 2 μs, respectively. The long decay time of the lowest substate I indicates its almost pure triplet character. The time for relaxation from state II to state I (spin−lattice relaxation, SLR) is as long as 22 μs at T = 1.5 K,...

Characterization of Photoinduced Isomerization and Intersystem Crossing of the Cyanine Dye Cy3

Abstract: Several important photophysical properties of the cyanine dye Cy3 have been determined by laser flash photolysis. The triplet-state absorption and photoisomerization of Cy3 are distinguished by using the heavy-atom effects and oxygen-induced triplet → triplet energy transfer. Furthermore, the triplet-state extinction coefficient and quantum yield of Cy3 are also measured via triplet−triplet energy-transfer method and comparative actinometry, respectively. It is found that the triplet → triplet (T1→Tn) absorptions of trans-Cy3 largely overlap the ground-state absorption of cis-Cy3. Unlike what occurred in Cy5, we have not observed the triplet-state T1→Tn absorption of cis-Cy3 and the phosphorescence from triplet state of cis-Cy3 following a singlet excitation (S0−S1) of trans-Cy3, indicating the absence of a lowest cis-triplet state as an isomerization intermediate upon excitation in Cy3. The detailed spectra of Cy3 reported in this paper could help us interpret the complicated photophysics of cyanine dyes.

Imidazole-based excited-state intramolecular proton-transfer (ESIPT) materials: observation of thermally activated delayed fluorescence (TDF).

Abstract: We report the first observation of thermally activated delayed fluorescence (TDF) from an excited-state intramolecular proton-transfer (ESIPT) molecule, a hydroxyl-substituted tetraphenyl imidazole derivative (HPI−Ac), in degassed solutions as well as in low-temperature organic matrixes. In the absence of oxygen, the blue emission of an identical spectral feature was observed in the nanosecond (∼4.4 ns) and microsecond (∼25 μs) time domains, and the fluorescence intensity increased with temperature. From the temperature dependence of the time-resolved spectra of HPI−Ac, the energy gap between the first-excited singlet state and the lowest triplet state was determined to be 7.6 ± 0.3 kJ/mol (630 ± 25 cm-1), and the limiting rate constant of intrinsic reverse intersystem crossing was estimated to be 1.3 (±0.5) × 107 s-1.

Singlet excited-state dynamics of nitropolycyclic aromatic hydrocarbons: direct measurements by femtosecond fluorescence up-conversion.

Abstract: Understanding the dynamics of the electronically excited states of nitrated polycyclic aromatic hydrocarbons (NPAHs) is of great importance since photochemical reactions determine the atmospheric stability of these toxic pollutants. From previous studies, it is known that electronically excited NPAHs evolve through two parallel pathways: The formation of the first triplet state and the dissociation of nitrogen (II) oxide. In this contribution, we present the first time-resolved emission measurements of the singlet excited states which are the precursors in the aforementioned photoprocesses. We analyzed 1-nitronaphthalene, 9-nitroanthracene, 1-nitropyrene, 6-nitrochrysene, and 3-nitrofluoranthene in solution samples. Although these compounds are considered nonfluorescent, with the frequency up-conversion method it was possible to detect the emission from the S1 states despite their femtosecond and picosecond lifetimes. Except for 1-nitronapthalene, where a single exponential is observed, for the rest of the compounds, the emission shows double-exponential decays indicating ultrafast structural changes in the excited states. From anisotropy measurements, we conclude that no significant internal conversion occurs in the singlet manifold after excitation in the first absorption band. In accord with El-Sayed rules and with previous calculations, the highly efficient intersystem crossing implied by the large triplet yields and the ultrafast S1 decays is accounted by the pi-pi* nature of the S1 and T1 states together with the existence of higher triplet configurations which act as receiver states. Our measurements show that NPAHs have the largest intersystem crossing rates observed to date in an organic molecule.

Theoretical study on the second hyperpolarizabilities of phenalenyl radical systems involving acetylene and vinylene linkers: diradical character and spin multiplicity dependences.

Abstract: We have investigated the static second hyperpolarizabilities (gamma) of the singlet diradical systems with intermediate diradical character involving phenalenyl radicals connected by acetylene and vinylene pi-conjugated linkers, 1 and 2, using the hybrid density functional theory. For comparison, we have also examined the gamma values of the closed-shell and pure diradical systems with almost the same molecular size as 1 and 2. In agreement with our previous prediction of the diradical character dependence of gamma, it turns out that the gamma values of 1 and 2 are significantly enhanced compared to those of the closed-shell and pure diradical systems. In the present case, distinct differences in gamma values are not observed between the two pi-conjugated linkers, though the diradical character is found to depend on the kind of linker. Furthermore, we have investigated the spin multiplicity effect on gamma. Changing from the singlet to the triplet state, the gamma values of the systems with intermediate diradical character in the singlet state are quite reduced, though those of the pure diradical systems are hardly changed. Such spin multiplicity dependence of gamma is understood by considering the difference of diradical character between their singlet states together with the Pauli principle. The present results provide a possibility of a novel control scheme of gamma for phenalenyl radical systems involving pi-conjugated linkers by adjusting the diradical character through the change of the linked position of pi-conjugated linkers and the spin multiplicity.

Photochemistry, photophysics and nonlinear optical parameters of phenoxy and tert-butylphenoxy substituted indium(III) phthalocyanines

Abstract: This work hereby presents the syntheses, photochemistry and photophysics of octaphenoxy ((Cl)InOPPc) and octakis(4-tert-butylphenoxy)chloroindium ((Cl)InOTBPPc) phthalocyanines. Calculated nonlinear parameters of these complexes are compared with those of the corresponding GaPc derivatives and tetrasubstituted GaPc and InPc complexes. Fluorescence quantum yields do not vary much between (Cl)InOPPc and (Cl)InOTBPPc complexes in different solvents. High quantum yields of triplet state (ΦT ranging from 0.70 to 0.91 in dimethysulphoxide, DMSO) and singlet oxygen generation (ΦΔ, ranging from 0.61 to 0.79 in DMSO) were obtained. Short triplet lifetimes 50–60 μs were obtained in DMSO). The optical limiting threshold intensity (Ilim) for the InPc derivatives were calculated and compared with those of corresponding tetrasubstituted InPc and GaPc complexes. The latter were found to be better optical limiters.

Triplet state absorption in carbon nanotubes: a TD-DFT study.

Abstract: We predict properties of triplet excited states in single-walled carbon nanotubes (CNTs) using a time-dependent density-functional theory (TD−DFT). We show that the lowest triplet state energy in CNTs to be about 0.2−0.3 eV lower than the lowest singlet state energies. Like in π-conjugated polymers, the lowest CNT triplets are spatially localized. These states show strong optical absorption at about 0.5−0.6 eV to the higher lying delocalized triplet states. These results demonstrate striking similarity of the electronic features between CNTs and π-conjugated polymers and provide explicit guidelines for spectroscopic detection of CNT triplet states.

The role of magnetic fields on the transport and efficiency of aluminum tris(8-hydroxyquinoline) based organic light emitting diodes

Abstract: Magnetoresistance and efficiency measurements of aluminum tris(8-hydroxyquinoline) (Alq3) based organic light emitting diode structures have been made as a function of magnetic field and Alq3 thickness. Both positive and negative magnetoresistances can be observed depending on the thickness of the Alq3 layer, the drive voltage, and the applied field. In all devices, large increases in device efficiency are observed. We suggest that the increase in device efficiency is due to conversion of triplet states into singlets through a hyperfine scale interaction. The changes in the magnetoresistance are a result of the reduction in the triplet concentration and operate either through the reduced role of free carrier trapping at triplet states or through the reduction in triplet dissociation at the cathode interface depending on the Alq3 thickness.

On the intrinsic population of the lowest triplet state of thymine.

Abstract: The population of the lowest triplet state of thymine after near-UV irradiation has been established, on the basis of CASPT2//CASSCF quantum chemical calculations, to take place via three distinct intersystem crossing mechanisms from the initially populated singlet bright 1pipi* state. Two singlet-triplet crossings have been found along the minimum-energy path for ultrafast decay of the singlet state at 4.8 and 4.0 eV, involving the lowest 3npi* and 3pipi* states, respectively. Large spin-orbit coupling elements predict efficient intersystem crossing processes in both cases. Another mechanism involving energy transfer from the lowest 1npi* state with much larger spin-orbit coupling terms can also be proposed. The wavelength dependence measured for the triplet quantum yield of pyrimidine nucleobases is explained by the location and accessibility of the singlet-triplet crossing regions.

Scope and Limitations of Baird's Theory on Triplet State Aromaticity: Application to the Tuning of Singlet–Triplet Energy Gaps in Fulvenes

Abstract: Utilizing Baird's theory on triplet state aromaticity, we show that the singlet-triplet energy gaps (DeltaE(ST)) of pentafulvenes are easily varied through substitution by as much as 36 kcal mol(-1). This exploits the fact that fulvenes act as aromatic chameleons in which the dipoles reverse on going from the singlet ground state (S(0)) to the lowest pipi* triplet state (T1); thus, their electron distributions are adapted so as to achieve some aromaticity in both states. The results are based on quantum chemical calculations with the OLYP density functional theory method and the CASPT2 ab initio method, as well as spectroscopic determination of DeltaE(ST) by triplet sensitization. The findings can also be generalized to fulvenes other than the pentafulvenes, even though the effect is attenuated as the size of the fulvene increases. Our studies thus reveal that triplet-state aromaticity can greatly influence the properties of conjugated compounds in the T1 state.

Bactericidal nanofabrics based on photoproduction of singlet oxygen

Abstract: We present novel photofunctional nanofabrics that produce singlet oxygen on irradiation and have a bactericidal effect

Excitonic effects in a time-dependent density functional theory

Abstract: Excited state properties of one-dimensional molecular materials are dominated by many-body interactions resulting in strongly bound confined excitons. These effects cannot be neglected or treated as a small perturbation and should be appropriately accounted for by electronic structure methodologies. We use adiabatic time-dependent density functional theory to investigate the electronic structure of one-dimensional organic semiconductors, conjugated polymers. Various commonly used functionals are applied to calculate the lowest singlet and triplet state energies and oscillator strengths of the poly(phenylenevinylene) and ladder-type (poly)(para-phenylene) oligomers. Local density approximations and gradient-corrected functionals cannot describe bound excitonic states due to lack of an effective attractive Coulomb interaction between photoexcited electrons and holes. In contrast, hybrid density functionals, which include long-range nonlocal and nonadiabatic corrections in a form of a fraction of Hartree-Fock exchange, are able to reproduce the excitonic effects. The resulting finite exciton sizes are strongly dependent on the amount of the orbital exchange included in the functional.

Photochemical behaviour of triclosan in aqueous solutions: Kinetic and analytical studies

Abstract: The mechanism of the direct photolysis of the anti-microbial triclosan in aqueous solutions was investigated by using steady state and laser flash photolysis. Quantum yields were determined for the disappearance of triclosan and formation of chloride anions in steady state irradiations in the absence and in the presence of oxygen as well as a function of pH. The photoreactivity was found to be efficient with the anionic form and in the absence of oxygen. Following laser flash photolysis (226 nm), three transients were found (triclosan triplet state, solvated electron and phenoxyl radical). Several primary and secondary stable photoproducts were elucidated by means of LC/MS/MS data. They were found to arise from four main photochemical processes: isomerisation, cyclization (leading to the formation of dioxin derivatives), dimerisation of the phenolic moiety and hydrolysis. The ionic chromatography showed that the loss of chloride anion in triclosan phototransformation represents an important degradation pathway. The formation of oligomeric products was also observed for prolonged irradiation time. A detailed mechanism for the formation of the primary products is proposed and discussed. The very important photocyclization reaction is more likely involving the triplet state pathway and the homolytic dissociation of the ether bridge occurs from the singlet excited state pathway.

Excited states and two-photon absorption of some novel thiophenyl Pt(II)-ethynyl derivatives.

Abstract: The photophysical characterization of two new compounds related to bis((4-(phenylethynyl)phenyl)ethynyl)bis(tributylphosphine)platinum(II), here abbreviated Pt1, is reported. For the first new compound ATP1, the inner phenyl rings (closer to the Pt atom) in Pt1 are replaced by thiophene rings bridging at the 2,5-positions. In compound ATP2, the outer phenyl groups are replaced by thiophene rings bonded at the 2-position. Specifically, we report on the fluorescence quantum yield, two-photon absorption, triplet decay times and two-photon absorption induced emission spectra of the molecules in THF solutions. The results were compared with those of Pt1 and Pt1 capped with an acetonide-protected 2,2-bis(methylol)propionic acid (bis-MPA) ester group (Pt1-G1). The photophysical properties of the organic dye 7-(diethylamino)coumarin (Coumarin 110) were determined and used as a reference material. The two-photon absorption cross section around 720-740 nm of ATP1 and ATP2 was found to be of the same order of magnitude as for Pt1-G1, i.e., between 5 and 10 GM, but slightly larger for ATP1 than for ATP2 (1 GM = 1 Goppert-Mayer = 10(-50) (cm(4) s)/photon). The fluorescence decay time of all compounds was found to be very short (subnanosecond) with quantum yields 0.0045, 0.0007, 0.0011 and 0.0020 for ATP1, ATP2, Pt1-G1 and Pt1, respectively, measured at excitation wavelength 373 nm. Just as Pt1 and Pt1-G1, both thiophenyl derivatives showed large intersystem crossing capabilities and phosphorescence, characteristic for a triplet state that can enhance the nonlinear absorption and optical power limiting by triplet state absorption. The phosphorescence emission of the thiophenyl derivatives was red-shifted in comparison with Pt1 and Pt1-G1, and the phosphorescence decay times were on the order of 200-500 ns, as for the Pt1 compound.