Multiphoton Ionization/Dissociation of Molecular Sulfur S2 in the UV Region.

The multiphoton ionization/dissociation dynamics of molecular sulfur (S2) in the ultraviolet range of 205-300 nm is studied using velocity map ion imaging (VMI). In this one-color experiment, molecular sulfur (S2) is generated in a pulsed discharge and then photodissociated by UV radiation. At the three-photon level, superexcited states are accessed via two different resonant states: the B3Σu- (v' = 8-11) valence states at the one-photon level and a Rydberg state at the two-photon level. Among the decay processes of these superexcited states, dissociation to electronically excited S atoms is dominant as compared to autoionization to ionic states S2+ (X2Πg) at wavelengths λ < 288 nm. The anisotropy parameter extracted from these images reflects the parallel character of these electronic transitions. In contrast, autoionization is found to be particularly efficient at S(1D) and S(1S) detection wavelengths around 288 nm. Information obtained from the kinetic energy distributions of S atoms has revealed the existence of vibrationally excited S2+ (X2Πg (v+ > 11)) that dissociates to ionic products following one-photon absorption. This work also reveals many interesting features of S2 photodynamics compared to those of electronically analogous O2.

Synergy of Bulk Defects and Surface Defects on TiO2 for Highly Efficient Photocatalytic Production of H2O2.

Artificial photosynthesis of H2O2 by TiO2-based semiconductors is a promising approach for H2O2 production. However, the efficiency of pristine TiO2 is still limited by rapid charge separation and low O2 adsorption capacity. Here, we found that the synergy between bulk and surface defects on TiO2 could overcome this demanding bottleneck. The introduced bulk defects act as hole acceptors to induce directional hole transfer, efficiently boosting electron-hole separation. Furthermore, the adsorption of O2 is strengthened by the introduced surface defects. Consequently, this synergy of bulk and surface defects on TiO2 significantly improves the photocatalytic performance, with a H2O2 production rate of 4560 µmol h-1 g-1, outperforming most reported TiO2-based photocatalysts. This work not only provides a new insight into the mechanism of surface/bulk defects in photocatalysis but also highlights that surface/bulk regulation holds great promise for achiveing efficient photocatalytic conversion.

Efficient Red-to-Blue Triplet-Triplet Annihilation Upconversion Using the C70-Bodipy-Triphenylamine Triad as a Heavy-Atom-Free Triplet Photosensitizer.

Triplet-triplet annihilation upconversion (TTA-UC) with heavy-atom-free organic triplet photosensitizers has attracted extensive attention recently, however, the successful examples with absorption in red and first near-infrared (NIR-I, 650-900 nm) region are still insufficient. Herein, we conducted a new TTA-UC system of perylene using C70-bodipy-triphenylamine triad (C70-BDP-T) as the heavy-atom-free photosensitizer. Efficient red-to-blue (663 to 450 nm) TTA-UC was achieved in this system with an anti-Stokes shift of 0.88 eV and a quantum yield up to 5.2% (out of a 50% maximum) in deaerated toluene. Notably, this is the highest quantum yield to date in similar TTA-UC systems with heavy-atom-free organic photosensitizers. Using steady-state and transient absorption spectroscopy, together with cyclic voltammogram and quantum chemical calculations, photophysical and photochemical mechanisms were elucidated. Specifically, two triplet triads, C70-3BDP*-T and 3C70*-BDP-T, were produced efficiently upon photoexcitation, with lifetimes of 2.0 ± 0.1 and 32.2 ± 0.3 µs, respectively. Electron transfer and recombination mechanisms were confirmed to play crucial roles in the formation of these triplets, instead of intersystem crossing. Our results shed light on the superiority of fullerenes in the development of heavy-atom-free photosensitizers.

Charge Transfer Excited State Promoted Multiple Resonance Delayed Fluorescence Emitter for High-Performance Narrowband Electroluminescence.

Multiple resonance thermally activated delayed fluorescence (MR-TADF) emitters are promising candidates for narrowband organic light-emitting diodes, but their electroluminescent performance is typically hindered by the slow reverse intersystem crossing rate (kRISC). Herein, we present an effective strategy to introduce a multichannel reverse intersystem crossing (RISC) pathway with large spin-orbit coupling by orthogonally linking an electron-donating unit to the MR framework. Through delicate manipulation of the excited-state energy levels, an additional intersegmental charge transfer triplet state could be "silently" induced without perturbing the MR character of the lowest excited singlet state. The proof-of-concept emitter CzBN3 not only affords 23-fold increase of kRISC compared with its prototypical MR skeleton but also realizes close-to-unity photoluminescence quantum yield, large radiative rate constant, and very narrow emission spectrum. These merits enable high maximum external quantum efficiency (EQEmax) of up to 37.1% and alleviated efficiency roll-off in the sensitizer-free device (EQE1000 = 30.4%), and a further boost of efficiency (EQEmax/1000 = 42.3/34.1%) is realized in the hyperfluorescent device. The state-of-the-art electroluminescent performance validates the superiority of our molecular design strategy.

Photosensitive damage of dipeptides: mechanism and influence of structure.

We illustrate the influence of the dipeptide structure on photosensitive damage and the kinetic mechanism was investigated using acenaphthenequinone (ACQ) as a triplet photosensitizer. With tyrosine (Tyr) serving as the core structure, two classic dipeptides with double (trptophan-tyrosine, Trp-Tyr) and single (tyrosine-alanine, Tyr-Ala and Ala-Tyr) active reaction sites were constructed, and the underlying photodamage mechanisms were investigated carefully. According to the experimental results, the proton-coupled electron transfer processes between ACQ and numerous Trp-Tyr reaction sites have independent reaction properties. The bimolecular quenching rate (kq) value is roughly equivalent to the sum of the rates of two amino acid monomers, and a novel intramolecular dynamic channel between Trp/N˙-Tyr and Trp-Tyr/O˙ was observed. The ACQ/Tyr-Ala system demonstrated the key role of steric hindrance on the kq in bimolecular reactions.

Manipulating Exciton Dynamics toward Simultaneous High-Efficiency Narrowband Electroluminescence and Photon Upconversion by a Selenium-Incorporated Multiresonance Delayed Fluorescence Emitter.

Multiresonance thermal activated delayed fluorescence (MR-TADF) materials with an efficient spin-flip transition between singlet and triplet excited states remain demanding. Herein, we report an MR-TADF compound (BN-Se) simultaneously possessing efficient (reverse) intersystem crossing (ISC/RISC), fast radiative decay, close-to-unity quantum yield, and narrowband emission by embedding a single selenium atom into a common 4,4'-diazaborin framework. Benefitting from the high RISC efficiency accelerated by the heavy-atom effect, organic light-emitting diodes (OLEDs) based on BN-Se manifest excellent performance with an external quantum efficiency of up to 32.6% and an ultralow efficiency roll-off of 1.3% at 1000 cd m-2. Furthermore, the high ISC efficiency and small inherent energy loss also render BN-Se a superior photosensitizer to realize the first example of visible (λex > 450 nm)-to-UV (λem < 350 nm) triplet-triplet annihilation upconversion, with a high efficiency (21.4%) and an extremely low threshold intensity (1.3 mW cm-2). This work not only aids in designing advanced pure organic molecules with fast exciton dynamics but also highlights the value of MR-TADF compounds beyond OLED applications.

Investigation on the photoinduced chemical reaction between p-benzoquinone and tryptophan in homogeneous solution.

Photoinduced electron transfer (PET) and energy transfer between amino acids and bioquinones have become research hotspots, due to the important roles they play in a physiological environment. However, as classic benzoquinones and amino acids, the reaction mechanism of p-benzoquinone (PBQ) and tryptophan (Trp) is still unclear. In this work, the photoinduced chemical reaction of PBQ and Trp was investigated in homogeneous solution using time-resolved electron paramagnetic resonance and laser flash photolysis techniques. Under photoexcitation at 355 nm, the 3PBQ* produced via intersystem crossing (ISC) in ethylene glycol aqueous (EG-H2O) solution followed by the H-atom transfer (HAT) from EG to 3PBQ* was a significant process in competition with the non-radiative transition of 3PBQ*, which was clearly observed in the transient absorption spectra and chemically induced dynamic electron polarization spectra. When Trp was added into the PBQ/EG-H2O solution, a new decay channel of 3PBQ* was produced that reacted with Trp to form a p-benzoquinone anion radical (PBQ˙-) and a tryptophan cationic radical (Trp˙+), indicating that the photoinduced chemical reaction mechanism was the electron transfer. By fitting the decay dynamic curves, the quenching rate constant of 3PBQ* to Trp in homogeneous solution was determined as 6.8 × 108 M-1 s-1, which was close to the diffusion-controlled rate.

Determining the Energy Gap between the S1 and T1 States of Thermally Activated Delayed Fluorescence Molecular Systems Using Transient Fluorescence Spectroscopy.

The energy gap (ΔES-T) between the lowest single and triple excited states is a crucial parameter for thermally activated delayed fluorescence (TADF) molecular systems with high quantum yield. However, a reliable experimental approach to precisely determine this value is challenging. Here, we introduce a new, simple, and efficient strategy to accurately obtain the ΔES-T in TADF systems from time-resolved fluorescence spectroscopy using a recently reported TADF molecule, DMACPDO, as a representative. By introducing an explicit model to describe the corresponding singlet-triplet coupling system, elusive intersystem crossing and reverse intersystem crossing rates can be extracted by fitting the kinetics of the observed fluorescence. The ΔES-T value can then be determined. Moreover, our modeling accurately explained the opposite trend in fluorescence intensity of DMACPDO with solvent polarity under air-saturated and deoxygenated conditions. Additionally, the validity of this approach has been demonstrated in another well-known TADF molecule, 4CzIPN. We demonstrate how this approach of determining ΔES-T sheds light on a deeper understanding of energy-loss mechanisms involved in related photoconversion processes.

Efficient Triplet-Triplet Annihilation Upconversion in Solution and Hydrogel Enabled by an S-T Absorption Os(II) Complex Dyad with an Elongated Triplet Lifetime.

A new Os(II) complex dyad featuring direct singlet-to-triplet (S-T) absorption and intramolecular triplet energy transfer (ITET) with lifetime up to 7.0 µs was designed to enhance triplet energy transfer efficiency during triplet-triplet annihilation upconversion (TTA-UC). By pairing with 9,10-bis(phenylethynyl)anthracene (BPEA) as a triplet acceptor, intense upconverted green emission in deaerated solution was observed with unprecedented TTA-UC emission efficiency up to 26.3% (with a theoretical maximum efficiency of 100%) under photoexcitation in the first biological transparency window (650-900 nm). Meanwhile, a 7.1% TTA-UC emission efficiency was acquired in an air-saturated hydrogel containing the photosensitizer and a newly designed hydrophilic BPEA derivative. This ITET mechanism would inspire further development of a highly efficient TTA-UC system for biological fields and renewable energy production.

Triplet-triplet annihilation upconversion with reversible emission-tunability induced by chemical-stimuli: a remote modulator for photocontrol isomerization.

Triplet-triplet annihilation upconversion (TTA-UC) has been widely studied, but a color-tunable TTA-UC system triggered by chemical stimuli has not yet been proposed. Herein, reversible acid/base switching of the TTA-UC emission wavelength is achieved for the first time by a simple platform, composed of a direct singlet-triplet (S0-T1) absorption photosensitizer, and proton-responsive 9,10-di(pyridin-4-yl)anthracene (DPyA) as an acceptor. The photosensitizer-acceptor pair exhibits efficient UC emission (quantum yield up to 3.3%, and anti-Stokes shift up to 0.92 eV) with remarkable contrast upon base/acid treatment (Δλem,max = 82 nm, 0.46 eV). In a proof-of-concept study, the color-adjustable TTA-UC emission was applied as a remote modulator to photo-control reversible chemical reactions for the first time. This platform enriches the portfolio of color-switchable TTA-UC, and the mechanism would inspire further development of smart UC systems and extend the application field of upconversion.

Solvent effects on triplet-triplet annihilation upconversion kinetics of perylene with a Bodipy-phenyl-C60 photosensitizer.

The solvent effect usually plays an important role in triplet-triplet annihilation (TTA) upconversion processes. In this work, we have studied the TTA upconversion kinetics of perylene with Bodipy-phenyl-C60 as the triplet photosensitizer in five solvents, 1,4-dioxane, dichlorobenzene, chlorobenzene, toluene, and tetrahydrofuran (THF). Although no significant solvent effect was observed in steady-state absorption and fluorescence emission spectra, the overall TTA upconversion quantum yields showed a profound dependence on solvent properties, i.e. 4.9% in 1,4-dioxane, 7.1% in dichlorobenzene, 6.7% in chlorobenzene, 4.6% in toluene, and 2.2% in THF (the maximum of 50%). Each elementary reaction step involved in the overall process was analyzed by applying femtosecond and nanosecond time-resolved transient absorption spectroscopy, revealing that the fluorescence emission of perylene was more significantly affected by the solvents in contrast to the other steps. Moreover, an extra intramolecular energy-transfer pathway of Bodipy-phenyl-C60 was found via the formation of charge-separated states in dichlorobenzene, chlorobenzene, and THF solvents, once being excited. These conclusions provide valuable clues to choose the most favorable solvent for the higher TTA upconversion efficiency in related applications.

Dinuclear ZnII Complexes Exhibiting Thermally Activated Delayed Fluorescence and Luminescence Polymorphism.

ZnII complexes exhibiting strong emission in the solid state remain scarce, and most of them exhibit only prompt fluorescence. Herein the synthesis, structures, and photoluminescence properties of two ZnII complexes containing new donor-acceptor ligands is reported. The new ZnII complexes have dinuclear structures in which each metal ion adopts a distorted square-pyramidal geometry. The ZnII complexes show strong emission in the solid state with quantum yields up to 50 %. Variable-temperature transient photoluminescence studies revealed an emission mechanism involving prompt and thermally activated delayed fluorescence (TADF). DFT calculations showed well-separated HOMO and LUMO in the ground state and small excited singlet-triplet energy splitting, accounting for the TADF. The complexes also exhibit different emission colors in the as-synthesized powder state and in single crystals, that is, they exhibit luminescence polymorphism. The single-crystal emission is responsive to mechanical grinding and was characterized by powder XRD.

Near-infrared to violet triplet-triplet annihilation fluorescence upconversion of Os(ii) complexes by strong spin-forbidden transition.

Three Os(ii) complexes were synthesized with ligands 2,2'-dipyridyl (dipy), 1,10-phenanthroline monohydrate (phen), and 4,7-diphenyl-1,10-phenanthroline (diphen), and applied as triplet photosensitizers for triplet-triplet annihilation (TTA) fluorescence upconversion. The strong spin-orbital coupling made direct spin-forbidden transition of S0-T1 feasible. Lifetimes of the lowest triplet state of these complexes were determined to be 107 ns, 373 ns, and 386 ns for Os-dipy, Os-phen, and Os-diphen, respectively, using nanosecond transient absorption spectra. From steady-state phosphorescence emission spectra, energies of the triplet states were derived to be 1.75 eV, 1.80 eV, and 1.74 eV for Os-dipy, Os-phen, and Os-diphen, respectively. Using these photosensitizers, strong upconverted fluorescence of the triplet acceptors, 9,10-diphenylanthracene (DPA), perylene, and 9,10-bis(phenethynyl) anthracene (BPEA), was observed in the visible to violet range. In particular, fluorescence emission with the largest anti-Stokes shift of 1.14 eV was observed for the Os-phen/DPA system, and the upconverted quantum yield was determined as 5.9% in deoxygenated dichloroethane. Additionally, upconversion was determined in air using mixtures of dichloroethane and DMSO solvents, and the maximal quantum yield was measured to be 4.5% for Os-phen/DPA.

Application of a bodipy-C70 dyad in triplet-triplet annihilation upconversion of perylene as a metal-free photosensitizer.

A bodipy-C70 dyad was synthesized and applied in triplet-triplet annihilation (TTA) upconversion of perylene as a novel metal-free organic photosensitizer. The photophysical processes were investigated by the methods of steady-state UV-Vis absorption and fluorescence spectroscopy, nanosecond time-resolved transient absorption spectroscopy, cyclic voltammetry, and density functional theory calculations. The bodipy-C70 dyad showed an increased molar extinction coefficient up to 82 300 mol-1 cm-1 at 518 nm compared with the C70 monomer. With photo-excitation of the bodipy moiety at 532 nm, the intramolecular singlet-singlet energy transfer between bodipy and C70 units was efficient with a quantum yield of nearly 100%, and the lowest triplet state of the dyad was subsequently populated via ISC of the C70 moiety, with a lifetime of ca. 80 µs in toluene. Electrochemical investigation suggested that the intramolecular electron transfer of the excited dyad was thermodynamically prohibited in toluene due to the positive ΔGCS for charge-separation. With the presence of perylene in solution as the triplet energy acceptor and emitter, the TTA upconverted fluorescence was observed with a maximum quantum yield of 10.3%. The overall upconversion capability of 4417 M-1 cm-1 exceeded that of C70 approximately two-fold. Moreover, the bodipy-C70 dyad also exhibited an enhanced optical stability under intense irradiation. All data indicated that the dyad was another ideal photosensitizer for TTA upconversion of perylene in the fullerene derivative family.

Photochemical Reaction Between 1,2-Naphthoquinone and Adenine in Binary Water-Acetonitrile Solutions.

The photochemical reaction between 1,2-naphthoquinone (NQ) and adenine was investigated using nanosecond time-resolved laser flash photolysis. With photolysis at 355 nm, the lowest triplet state T1 of NQ was produced via intersystem crossing from its singlet excited state. The triplet-triplet absorption of the state contributes three bands of transient spectra at 374, 596 and 650 nm, respectively, in pure acetonitrile and binary water-acetonitrile solutions. In the presence of adenine, the observation of A·+ (at 363 nm) and NQ+H· radical (at 343 and 485 nm) indicates a multistep mechanism of electron transfer process followed by a proton transfer between 3 NQ* and adenine. By fitting with the Stern-Volmer relationship, the quenching rate constant kq of 3 NQ* by adenine in binary water-acetonitrile solutions (4/1, volume ratio, v/v) is determined as 1.66 × 109  m-1  s-1 . Additionally, no spectral evidence confirms the existence of electron transfer between 3 NQ* with thymine, cytosine and uracil.

Triplet-triplet annihilation upconversion kinetics of C60-Bodipy dyads as organic triplet photosensitizers.

Three new triplet photosensitizers consisting of a bodipy derivative and C60 moieties were synthesized for triplet-triplet annihilation upconversion of perylene. With the extension of the π-conjugated structure of the bodipy derivative, the three photosensitizers exhibited different absorption wavelengths, e.g. 517 nm for B-2, 532 nm for B-4, and 557 nm for B-6. The steady-state and transient absorption, steady-state fluorescence, and upconverted fluorescence emission were investigated to reveal step-by-step the dynamic processes of the above systems. The quantum yields of intramolecular energy transfer, intersystem crossing, and triplet-triplet energy transfer were measured. From the upconverted fluorescence emission spectra, the overall quantum yield of the triplet-triplet annihilation upconversion, ΦUC, was determined to be 5.80% for B-2, 7.95% for B-4, and 4.99% for B-6.

Solvent effects on the triplet-triplet annihilation upconversion of diiodo-Bodipy and perylene.

Solvent effects play a very important role in photochemical reactions and energy transfer processes in solution; however, these effects are rarely mentioned in the triplet-triplet annihilation (TTA) upconversion fluorescence experiments. In a typical TTA upconversion system of a photosensitizer of diiodo-Bodipy (I2-Bodipy) and a triplet acceptor of perylene, five common inert solvents, hexane, heptane, toluene, 1,4-dioxane, and dimethyl sulfoxide (DMSO), were used to investigate the solvent effects on the overall quantum yield of upconversion fluorescence. Femtosecond and nanosecond time-resolved transient difference absorption spectra were obtained to study the efficiencies of intersystem crossing (ISC) and triplet-triplet energy transfer (TTET). From the obtained upconversion fluorescence emission spectra, the overall TTA upconversion fluorescence quantum yield was derived. Among the five solvents, the upconversion quantum yield in dioxane is the highest at 19.16%, more than twice that that in toluene (8.75%). For the solvents hexane, heptane, toluene, and dioxane, the yields generally follow the sequences of polarity and viscosity. However, a very low upconversion quantum yield (1.51%) was observed in DMSO although the TTET process and fluorescence quantum yield of perylene in DMSO were almost as efficient as in dioxane. Based on density functional theory calculations, a reasonable explanation for these solvent effects was proposed.