Triplet Population Research Articles

Ultrafast electronic and vibrational relaxations in mixed-ligand dithione-dithiolato Ni, Pd, and Pt complexes.

Ultrafast excited-state dynamics of planar Pt, Pd, and Ni dithione-dithiolato complexes were investigated by transient absorption spectroscopy on the femtosecond-picosecond timescale. All studied complexes show a common photobehaviour, although individual kinetics parameters and quantum yields vary with the metal, the dithione ligand and, namely the solvent (DMF, MeCN). Laser pulse irradiation at 800 nm populates the lowest singlet excited state of a dithiolato → dithione charge transfer character, (1)LL'CT. The optically excited state undergoes a solvation-driven sub-picosecond electronic relaxation that enhances the dithione/dithiolato charge separation. The (1)LL'CT state decays with a 1.9-4.5 ps lifetime by two simultaneous pathways: intersystem crossing (ISC) to the lowest triplet state (3)LL'CT and non-radiative decay to the ground state. ISC occurs on a ∼6 ps timescale, virtually independent of the metal, whereas the rate of the non-radiative decay to the ground state decreases on going from Ni (2 ps) to Pd (3 ps) and Pt (∼10 ps). (3)LL'CT is initially formed as a vibrationally excited state. Its equilibration (cooling) takes place on a picosecond timescale and is accompanied by a competitive decay to the ground state. Equilibrated (3)LL'CT is populated with a quantum yield of less than 50%, depending on the metal: Pt > Pd > Ni. (3)LL'CT is long-lived for Pt and Pd (≫500 ps) and short-lived for Ni (∼15 ps). Some of the investigated complexes also exhibit spectral changes due to vibrational cooling of the singlet (2-3 ps, depending on the solvent). Rotational diffusion occurs with lifetimes in the 120-200 ps range. Changing the dithione (Bz2pipdt/(i)Pr2pipdt) as well as dithiolate/diselenolate (dmit/dsit) ligands has only small effects on the photobehavior. It is proposed that the investigated dithione-dithiolato complexes could act as photooxidants (*E(o) ≈ +1.2 V vs. NHE) utilizing their lowest excited singlet ((1)LL'CT), provided that the excited-state electron transfer is ultrafast, competitive with the picosecond decay. On the other hand, the efficiency of any triplet-based processes would be severely limited by the low quantum yield of the triplet population.

Competing ultrafast intersystem crossing and internal conversion: a time resolved picture for the deactivation of 6-thioguanine

In this paper we simulate the deactivation dynamics of photoexcited 6-thioguanine, a cytotoxic analogue of the canonical DNA/RNA base guanine, using a direct surface hopping dynamics approach. Our aim is to investigate the mechanism for triplet population, which was found to take place on a similar time scale as internal conversion. The surface hopping calculations were based on potential energy surfaces and couplings obtained on the fly using a semiempirical Hamiltonian, reparameterized on accurate ab initio data. We show that for the full description of the deactivation dynamics of 6-thioguanine, it is important to take into account both the dynamic and the spin–orbit couplings. The main deactivation pathway involves the sequence of ultrafast radiationless transitions S2 → S1 → T2 → T1. The very efficient population and long lifetime of the final T1 state, from where singlet oxygen is generated, would explain the high phototoxicity of the nucleotides of 6-thioguanine in DNA. To our knowledge, this is the first nonadiabatic dynamics simulation for a system showing strong spin–orbit couplings (due to the presence of a third row atom, sulfur) and a complex pattern of intermultiplet crossings.

Primary Photochemistry of the Dark- and Light-Adapted States of the YtvA Protein from Bacillus subtilis

The primary (100 fs to 10 ns) and secondary (10 ns to 100 μs) photodynamics in the type II light-oxygen-voltage (LOV) domain from the blue light YtvA photoreceptor extracted from Bacillus subtilis were explored with transient absorption spectroscopy. The photodynamics of full-length YtvA were characterized after femtosecond 400 nm excitation of both the dark-adapted D447 state and the light-adapted S390 state. The S390 state relaxes on a 43 min time scale at room temperature back into D447, which is weakly accelerated by the introduction of imidazole. This is ascribed to an obstructed cavity in YtvA that hinders access to the embedded FMN chromophore and is more open in type I LOV domains. The primary photochemistry of dark-adapted YtvA is qualitatively similar to that of the type I LOV domains, including AsLOV2 from Avena sativa, but exhibits an appreciably higher (60% greater) terminal triplet yield, estimated near the maximal ΦISC value of ≈78%; the other 22% decays via non-triplet-generating fluorescence. The subsequent secondary dynamics are inhomogeneous, with three triplet populations co-evolving: the faster-decaying (I)T* population (38% occupancy) with a 200 ns decay time is nonproductive in generating the S390 adduct state, a slower (II)T* population (57% occupancy) exhibits a high yield (Φadduct ≈ 100%) in generating S390 and a third (5%) (III)T*population persists (>100 μs) with unresolved photoactivity. The ultrafast photoswitching dynamics of the S390 state appreciably differ from those previously resolved for the type I AcLOV2 domain from Adiantum capillus-veneris [Kennis, J. T., et al. (2004) J. Am. Chem. Soc. 126, 4512], with a low-yield dissociation (Φdis ≈ 2.5%) reaction, which is due to an ultrafast recombination reaction, following photodissociation, and is absent in AcLOV2, which results in the increased photoswitching activity of the latter domain.

Photophysics and morphology of a polyfluorene donor–acceptor triblock copolymer for solar cells

ABSTRACTWe present a study of the optical, structural and device properties of a polyfluorene (PFM)‐based (PFM‐F8BT‐PFM) donor–acceptor triblock copolymer for use in an organic solar cell. Neutron reflectivity is employed to probe the vertical composition profile before and after thermal annealing while the crystallinity was examined using grazing incidence wide‐angle X‐ray. The absorption spectra and photoluminescence emission for the triblock and analogous blend of PFM with F8BT reveal a greater degree of intermixing in the triblock. However, the triblock copolymer exhibits exciplex emission, which necessitates a geminate polar pair; long‐lived exciplex states are detrimental in organic photovoltaic devices. The triplet yield in the triblock and the blend is estimated using photoinduced absorption, with the triblock copolymer generating a triplet population 20 times that of the blend. This is far from ideal as triplets are wasted states in organic photovoltaic devices and they can also act as scavengers of polarons reducing the efficiency even more. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys.2013,51, 1705–1718

Singlet and Triplet Carrier Dynamics in Rubrene Single Crystal

We systematically investigate the singlet and triplet carrier dynamics in rubrene single crystal in the time scale from femtosecond (fs) up to microsecond (μs) using time-resolved and temperature-dependent photoluminescence (PL) techniques. Five PL bands were observed between 1.60 and 2.14 eV, and they are assigned to exciton peak, zero phonon intrinsic transition, and vibronic replicas, respectively. The ultrafast carrier scattering results in a broad distribution of hot carriers with a time constant as fast as 100 fs. The singlet fission and phonon scattering lead to 6.2 and 47 ps relaxation, respectively. The radiative recombination of singlet carriers exhibits wavelength-dependent lifetimes. The delayed fluorescence was observed on the microsecond time scale. The temperature-dependent and excitation intensity-dependent lifetime measurements confirmed that the delayed fluorescence is due to triplet–triplet annihilation that can be well described by rate equations of the triplet population.

Magnetoconductance response due to the triplet exciton–charge interaction in organic light-emitting diodes

The magnetoconductance (MC) effects in three organic light-emitting diodes have been measured over a range of operating current and temperatures. The peculiar roles played by the hyperfine field and triplet excitons are outlined by fitting the MC traces using the sum of two non-Lorentzian functions. The MC response evident at large magnetic fields is confirmed to be resulted from the triplet exciton–charge interaction by investigating its variation with the triplet population. The remarkable agreement between the experimental data and fit lines demonstrates that the method used in this work could help to identify the correct models for understanding the fundamental mechanism behind the magnetic field effects universally observed in organic devices.

Spectroscopic properties and singlet oxygen production by the compound ethyl 3,12-dioxopyran[3,2-a]xanthone-2-carboxylate

The steady state and time resolved experiments together with absorption and emission spectroscopies and quantum chemical calculations have been employed to investigate spectroscopic properties of a xanthone-type compound (ethyl 3,12-dioxopyran[3,2-a]xanthone-2-carboxylate). The spectroscopic data show good agreement with results obtained from quantum chemical calculations. Additionally, this compound shows expressive quantum efficiency for triplet population and a quantum efficiency of singlet oxygen generation very close to unity. Correlations between the nature of singlet and triplet excited states and spectroscopic properties were performed in order to understand the high quantum efficiency of singlet oxygen generation by this compound.

Theoretical study of the photochemical generation of triplet acetophenone

Acetophenone has a rich photochemistry, which strongly depends on the absorbing state. For example, the excitation to the lowest singlet excited state (S1) leads to a triplet population with a phosphorescence quantum yield of one, while the excitation to S2 leads to photocleavage reactions. Here, we rationalize the photochemistry of acetophenone after being absorbed into the S1, S2 and S3 states by performing a systematic study of all the singlet and triplet minimum energy structures and state crossings between the relevant electronic states. We calculate these structures at the complete-active space self-consistent field (CASSCF) level of theory and at the correlated extended second-order quasi-degenerate multi-reference perturbation theory (XMCQDPT2), emphasizing the importance of correlation effects in the determination of structures.

Femtosecond Intersystem Crossing in the DNA Nucleobase Cytosine.

Ab initio molecular dynamics including nonadiabatic and spin-orbit couplings on equal footing is used to unravel the deactivation of cytosine after UV light absorption. Intersystem crossing (ISC) is found to compete directly with internal conversion in tens of femtoseconds, thus making cytosine the organic compound with the fastest triplet population calculated so far. It is found that close degeneracy between singlet and triplet states can more than compensate for very small spin-orbit couplings, leading to efficient ISC. The femtosecond nature of the ISC process highlights its importance in photochemistry and challenges the conventional view that large singlet-triplet couplings are required for an efficient population flow into triplet states. These findings are important to understand DNA photostability and the photochemistry and dynamics of organic molecules in general.

Curcumin Prevents Aggregation in α-Synuclein by Increasing Reconfiguration Rate

α-Synuclein is a protein that is intrinsically disordered in vitro and prone to aggregation, particularly at high temperatures. In this work, we examined the ability of curcumin, a compound found in turmeric, to prevent aggregation of the protein. We found strong binding of curcumin to α-synuclein in the hydrophobic non-amyloid-β component region and complete inhibition of oligomers or fibrils. We also found that the reconfiguration rate within the unfolded protein was significantly increased at high temperatures. We conclude that α-synuclein is prone to aggregation because its reconfiguration rate is slow enough to expose hydrophobic residues on the same time scale that bimolecular association occurs. Curcumin rescues the protein from aggregation by increasing the reconfiguration rate into a faster regime.

Competitive Binding of the SecA ATPase and Ribosomes to the SecYEG Translocon

During co-translational membrane insertion of membrane proteins with large periplasmic domains, the bacterial SecYEG complex needs to interact both with the ribosome and the SecA ATPase. Although the binding sites for SecA and the ribosome overlap, it has been suggested that these ligands can interact simultaneously with SecYEG. We used surface plasmon resonance and fluorescence correlation spectroscopy to examine the interaction of SecA and ribosomes with the SecYEG complex present in membrane vesicles and the purified SecYEG complex present in a detergent-solubilized state or reconstituted into nanodiscs. Ribosome binding to the SecYEG complex is strongly stimulated when the ribosomes are charged with nascent chains of the monotopic membrane protein FtsQ. This binding is competed by an excess of SecA, indicating that binding of SecA and ribosomes to SecYEG is mutually exclusive.

Absence of Singlet Fission and Carrier Multiplication in a Model Conjugated Polymer: Tracking the Triplet Population through Phosphorescence

Singlet fission, or multiple exciton generation, has been purported to occur in a variety of material systems. Given the current interest in exploiting this process in photovoltaics, we search for the direct signature of singlet fission, phosphorescence from the triplet state, in a model polymeric organic semiconductor for which photoinduced absorption experiments have implied a tripling of the intersystem crossing yield at the onset of fission. Fluorescence and phosphorescence are clearly discriminated using a picosecond gated photoluminescence excitation technique, at variable temperature. At low excitation densities, in a quasi-steady-state experiment, we detect no change of the relative triplet yield to within 4% for photon energies of almost three times the triplet energy of 2.1 eV. Identical results are obtained under nonlinear two-photon excitation. We conclude that assignments of singlet fission based on induced absorptions alone should be treated with caution and may substantially overestimate excited-state intersystem crossing yields, raising questions with regards to the applicability of the process in devices.

Time resolved EPR of [70]fullerene monoadducts in the photoexcited triplet state

Triplet excited states of isomers α, β and γ of N-methyl-[70]fulleropyrrolidine in glassy toluene (T = 120 K) are investigated with Time Resolved EPR (TR-EPR) spectroscopy using pulsed laser photoexcitation. Both the zero field splitting (ZFS) parameters D, E and the anisotropic triplet population rates are measured. Results reveal a strong dependence of the triplet state wavefunction on the position (α, β or γ) of the pyrrolidine addend with respect to the pole of the [70]fullerene unit. The relevant molecular orbitals have been calculated giving support to this finding. The dipolar tensor principal axes are located at the molecular reference frame from the inspection of the EPR spectra in a frozen liquid crystal (E7). Time evolution of the triplet EPR signals is different among the isomers, suggesting different triplet lifetimes and/or spin relaxation properties. The spin-density distribution in the first triplet state for N-methyl-[70]fulleropyrrolidine is compared with that previously observed for pristine C(70).

Enhanced efficiency in high-brightness fluorescent organic light emitting diodes through triplet management

We demonstrate suppressed singlet-triplet (S-T) quenching, and hence increased quantum efficiency, in high-brightness fluorescent organic light emitting diodes (OLEDs) by reducing the guest triplet population through the introduction of a triplet manager molecule into the emission layer (EML). As an example, an OLED whose EML consists of the red fluorophore, 4-(dicyanomethylene)-2-methyl-6-julolidyl-9-enyl-4H-pyran doped into the host, tris(8-hydroxyquinoline) Al (Alq3) is blended with the triplet manager, 9,10-di(naphtha-2-yl)anthracene. The manager triplet energy is less than that of the host or dopant, leading to efficient triplet removal from the dopant without affecting the radiative singlet population. Measurements suggest the complete suppression of S-T quenching using the triplet management strategy, leading to >100% increase in the steady-state OLED external quantum efficiency.

Organic light-emitting diodes under high currents explored by transient electroluminescence on the nanosecond scale

We investigate organic light-emitting diodes (OLEDs) comprising the singlet emitter system 4-dicyanomethylene-2-methyl-6-p-dimethylaminostyryl-4H-pyran (DCM) doped into aluminium tris(8-hydro-xyquinoline) (Alq${}_{3}$) at high excitation densities. With the OLED active area reduced to $100\ifmmode\times\else\texttimes\fi{}100\phantom{\rule{0.28em}{0ex}}\ensuremath{\mu}$m${}^{2}$, current densities up to 800 A/cm${}^{2}$ are achieved in pulsed operation. These devices exhibit an intense electroluminescence (EL) turn-on peak on the nanosecond time scale. With the help of streak camera measurements, we prove that the steady state EL of the fluorescent OLEDs is reduced due to singlet-triplet quenching. We demonstrate that short electrical pulses with a rise time of 10 ns make the separation of singlet emission and singlet-triplet quenching in time domain possible. By modeling the singlet and triplet population dynamics in the emission layer, we find that the triplet-triplet annihilation-rate coefficient in doped fluorescent materials is triplet-density dependent at high excitation density. The increased triplet lifetime usually observed in host:guest systems due to triplet trapping on guest molecules vanishes at high current densities. An increase in current density leads to an increased triplet-triplet annihilation rate, while the triplet density in the emission layer stays constant.

Triplet Thermal Relaxation Study as a Probe of Weak Interdimers of Porphyrin Derivatives

This article deals with results concerning the study of interacting dyes which are able to create weak interdimers. Two groups of organic systems: phthalocyanines (di-ethanol-amine and di-octane-amine) and pyridyl porphyrins (zinc, copper, and free-base) covalently linked to polyethylene glycol (PEG) in water and organic solvents (dioxane, dimethylsulfoxide) were investigated. Absorption, fluorescence, and photoacoustics were used as experimental methods but particular attention was paid to light-induced optoacoustic spectroscopy to follow the dye’s triplet population and triplet thermal relaxation to study intermolecular interactions. It has been shown that even the weak interactions of the organic dyes under study is not detectable by absorption and only slightly by fluorescence is it possible to follow interactions by complementary photothermal methods. The results obtained for selected phthalocyanines and covalent porphyrin–polymer samples evidently show that the light-induced optoacoustic experiment is a perfect tool in the detection of weakly interacting aggregates.

Birth weight in a large series of triplets.

BackgroundTriplets are often born premature and with a low birth weight. Because the incidence of triplet births is rare, there are relatively few studies describing triplet birth weight characteristics. Earlier studies are often characterized by small sample sizes and lack information on important background variables such as zygosity. The objective of this study is to examine factors associated with birth weight in a large, population-based sample of triplets registered with the Netherlands Twin Register (NTR).MethodsIn a sample of 1230 triplets from 410 families, the effects of assisted reproductive techniques, zygosity, birth order, gestational age, sex, maternal smoking and alcohol consumption during pregnancy on birth weight were assessed. The resemblance among triplets for birth weight was estimated as a function of zygosity. Birth weight discordance within families was studied by the pair-wise difference between triplets, expressed as a percentage of the birth weight of the heaviest child. We compare data from triplets registered with the NTR with data from population records, which include live births, stillbirths and children that have deceased within days after birth.ResultsThere was no effect of assisted reproductive techniques on triplet birth weight. At gestational age 24 to 40 weeks triplets gained on average 130 grams per week; boys weighed 110 grams more than girls and triplets of smoking mothers weighted 104 grams less than children of non-smoking mothers. Monozygotic triplets had lower birth weights than di- and trizygotic triplets and birth weight discordance was smaller in monozygotic triplets than in di- and trizygotic triplets. The correlation in birth weight among monozygotic and dizygotic triplets was 0.42 and 0.32, respectively. In nearly two-thirds of the families, the heaviest and the lightest triplet had a birth weight discordance over 15%. The NTR sample is representative for the Dutch triplet population that is still alive 28 days after birth.ConclusionBirth weight is an important determinant of childhood development. Triplet status, gestational age, sex, zygosity and maternal smoking affect birth weight. The combined effects amount to a difference of 364 grams between monozygotic girl triplets of smoking mothers compared to dizygotic boy triplets of non-smoking mothers of the same gestational age. Birth weight in triplets is also influenced by genetic factors, as indicated by a larger correlation in monozygotic than in di- and trizygotic triplets.

Sensitive triplet exciton detection in polyfluorene using Pd-coordinated porphyrin

We developed a sensitive spectroscopic method to probe triplet concentration in thin films of polyfluorene (PF) at room temperature. The energy of photoexcited triplet excitons is transferred to the guest metal-organic complex, meso-tetratolylporphyrin-Pd (PdTPP), and detected as phosphorescent emission. The phosphorescence intensity of PdTPP-PF blends is proportional to the independently measured triplet concentration using photoinduced absorption experiments. The high sensitivity of this method allows room temperature detection of triplet excitons in spin-coated polymer films as thin as 10 nm. We found that the triplet lifetime is independent of PdTPP concentration and therefore this method is nearly non-perturbing for the triplet population.

Modelling of organic magnetoresistance as a function of temperature using the triplet polaron interaction

The organic magnetoresistance (OMR) of 50 nm aluminium tris(8-hydroxyquinoline) organic light emitting diodes (OLEDs) has been measured over a range of temperatures and operating voltages. The OMR data for this device, the current change through the device with applied field, have been fitted using the triplet polaron interaction (TPI) model that includes two independent processes, namely the exciton trapping and the triplet polaron interaction. Two Lorentzian functions were used to fit the data, and the prefactors for the two processes were found to scale linearly with the triplet population. Over the whole temperature range the data appears to fall on a single line which covers nearly six orders of magnitude of exciton concentration. This work demonstrates that the magnitude and shape of the OMR can be predicted and will be useful for understanding the fundamental mechanism behind the OMR.

Determining the influence of excited states on current transport in organic light emitting diodes using magnetic field perturbation

The perturbation of the current transport in aluminum tris(8-hydroxyquinoline) $({\text{Alq}}_{3})$-based organic light emitting diodes has been investigated as a function of magnetic field. The change in current, or organic magnetoresistance, with applied field has been fitted using two Lorentzian functions corresponding to polaron trapping by triplets and the interaction between polarons and triplets as suggested in the triplet polaron interaction model. The model has been applied to a number of devices with ${\text{Alq}}_{3}$ thicknesses from 50 to 90 nm and with two different cathodes. In all cases the data could be fitted using just these two processes, the prefactors for which were found to scale linearly with the triplet population over 6 orders of magnitude. This work demonstrates that the magnitude and shape of the organic magnetoresistance can be predicted and illustrates the importance of magnetic field measurements as a tool for understanding the processes affecting current transport in organic devices.