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Photon interconversion promises to alleviate thermalization losses for high energy photons and facilitates utilization of sub-bandgap photons - effectively enabling the optimal use of the entire solar spectrum. However, for solid-state device applications, the impact of intermolecular interactions on the energetic landscape underlying singlet fission and triplet-triplet annihilation upconversion cannot be neglected. In the following, the implications of molecular arrangement, intermolecular coupling strength and molecular orientation on the respective processes of solid-state singlet fission and triplet-triplet annihilation are discussed., (Copyright 2024 Lea Nienhaus. License: This work is licensed under a Creative Commons Attribution 4.0 International License.)

Photon upconversion (UC) from red or near-infrared (NIR) light to blue light is promising for in vivo optogenetics. However, the examples of in vivo optogenetics have been limited to lanthanide inorganic UC nanoparticles, and there have been no examples of optogenetics without using heavy metals. Here the first example of in vivo optogenetics using biocompatible heavy metal-free TTA-UC nanoemulsions is shown. A new organic TADF sensitizer, a boron difluoride curcuminoid derivative modified with a bromo group, can promote intersystem crossing to the excited triplet state, significantly improving TTA-UC efficiency. The TTA-UC nanoparticles formed from biocompatible surfactants and methyl oleate acquire water dispersibility and remarkable oxygen tolerance. By combining with genome engineering technology using the blue light-responding photoactivatable Cre-recombinase (PA-Cre), TTA-UC nanoparticles promote Cre-reporter EGFP expression in neurons in vitro and in vivo. The results open new opportunities toward deep-tissue control of neural activities based on heavy metal-free fully organic UC systems., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Within this work, we review the metal coordination effect on the photophysics of metal dipyrrinato complexes. Dipyrrinato complexes are promising candidates in the search for alternative transition metal photosensitizers for application in photodynamic therapy (PDT). These complexes can be activated by irradiation with light of a specific wavelength, after which, cytotoxic reactive oxygen species (ROS) are generated. The metal coordination allows for the use of the heavy atom effect, which can enhance the triplet generation necessary for generation of ROS. Additionally, the flexibility of these complexes for metal ions, substitutions and ligands allows the possibility to tune their photophysical properties. A general overview of the mechanism of photodynamic therapy and the properties of the triplet photosensitizers is given, followed by further details of dipyrrinato complexes described in the literature that show relevance as photosensitizers for PDT. In particular, the photophysical properties of Re(I), Ru(II), Rh(III), Ir(III), Zn(II), Pd(II), Pt(II), Ni(II), Cu(II), Ga(III), In(III) and Al(III) dipyrrinato complexes are discussed. The potential for future development in the field of (dipyrrinato)metal complexes is addressed, and several new research topics are suggested throughout this work. We propose that significant advances could be made for heteroleptic bis(dipyrrinato)zinc(II) and homoleptic bis(dipyrrinato)palladium(II) complexes and their application as photosensitizers for PDT. [ABSTRACT FROM AUTHOR]

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With the increase of user demand, higher brightness become a trend for the information display products, which makes efficiency roll‐off issue even more concerning in organic light‐emitting diodes (OLED). Here, we fabricated a set of red phosphorescent OLED structure for investigating the origin of roll‐off. By replacing different kinds of red dopant materials (RD‐1 and RD‐2) and red host materials, we found the main reason affecting efficiency roll‐off is dopant materials in emitting layer. Three key factors, including triplet‐triplet annihilation (TTA), triplet‐polaron quenching (TPQ), as well as the width of recombination zone were investigated. Firstly, the transient photoluminescence (PL) and electroluminescence (EL) results illustrated a longer excited state lifetime for RD‐2. Consequently, we demonstrated a relatively serious TPQ phenomenon in the unipolar device with RD‐2, which revealed a higher interaction probability between photon‐induced exciton and polaron. Finally, the OLED with RD‐2 showed apparently higher SCLC (space charge limited current) hole mobility in the hole‐only device. According to the recombination zone profiles and capacitance results, we proposed that a higher hole‐type space charge concentration in the device based on RD‐2 contributed to a higher polaron and triplet concentration in EML. Combined with a longer exciton diffusion length, a higher rate of TPQ was induced and resulted in relatively serious roll‐off phenomenon. [ABSTRACT FROM AUTHOR]

[Display omitted] • Bis(8-carbazol-N-yl)fluorene- and benzonitrile-modified anthracene/chrysene (FAnCN and FCsCN) as solution-processable TTA emitters were developed. • FAnCN and FCsCN present stable deep blue emissions, high-quality solution-cast thin films, shallow HOMO levels, and decent hole mobilities. • FAnCN and FCsCN were effectively employed as non-doped emissive layers in solution-processed TTA OLEDs. • FCsCN-based TTA OLED shows stable deep blue electroluminescent emission with a high EQE of 6.84%. Triplet-triplet annihilation (TTA) emitters can effectively utilize non-radiative triplet excitons through the interaction of low triplet energy excitons to produce high energy singlet excitons, but they are mostly restricted by their multilayered device structure fabricated using layer-by-layer thermal vacuum evaporation. It is a great challenge to develop, for the first time, efficient solution-processed non-doped TTA organic light-emitting diodes (OLEDs). In this study, two solution-processable blue emissive TTA molecules (FAnCN and FCsCN) bearing (anthracen-9-yl)benzonitrile (AnCN) and (chrysen-6-yl)benzonitrile (CsCN) as TTA emissive cores modified with 9,9′-bis(8-(carbazole-N-yl)octyl)fluorene (F) are designed and synthesized, respectively. The experimental and theoretical studies reveal that both molecules exhibit deep blue emissions, amorphous morphology with good thermal stability, high-quality solution-cast thin films, decent hole mobility, high-lying HOMO levels (∼-5.45 eV), and suitable lowest singlet (S 1)/triplet (T 1) excited states (2T 1 > S 1) for TTA process. FAnCN and FCsCN are successfully employed as solution-processed non-doped emissive layers (EML) in simple structured TTA OLEDs. These devices show intense blue emissions, low turn-on voltages (∼3.6 V), excellent electroluminescent (EL) performances (EQE max = 5.47–6.84 % and LE max = 5.66–5.83 cd/A), and TTA characteristics. Especially, FCsCN -based TTA OLED emits deep blue EL emission peaked at 435 nm with a high EQE max of 6.84 %. This work not only presents a new strategic design for the preparation of solution-processable TTA emitter, but also further ratifies that the TTA mechanism can also be applicable in solution-processed OLEDs. [ABSTRACT FROM AUTHOR]

The effect of triplet-triplet annihilation (TTA) on the room-temperature phosphorescence (RTP) in metal-organic frameworks (MOFs) is studied in benchmark RTP MOFs based on Zn metal centers and isophthalic or terephthalic acid linkers (ZnIPA and ZnTPA). The ratio of RTP to singlet fluorescence is observed to decrease with increasing excitation power density. Explicitly, in ZnIPA the ratio of the RTP to fluorescence is 0.58 at 1.04 mW cm−2, but only 0.42 at (the still modest) 52.6 mW cm−2. The decrease in ratio is due to the reduction of RTP efficiency at higher excitation due to TTA. The density of triplet states increases at higher excitation power densities, allowing triplets to diffuse far enough during their long lifetime to meet another triplet and annihilate. On the other hand, the shorter-lived singlet species can never meet an annihilate. Therefore, the singlet fluorescence scales linearly with excitation power density whereas the RTP scales sub-linearly. Equivalently, the efficiency of fluorescence is unaffected by excitation power density but the efficiency of RTP is significantly reduced at higher excitation power density due to TTA. Interestingly, in time-resolved measurements, the fraction of fast decay increases but the lifetime of long tail of the RTP remains unaffected by excitation power density. This may be due to the confinement of triplets to individual grains, leading decay to be faster until there is only one triplet per grain left. Subsequently, the remaining “lone triplets” decay with the unchanging rate expressed by the long tail. These results increase the understanding of RTP in MOFs by explicitly showing the importance of TTA in determining the (excitation power density dependent) efficiency of RTP. Also, for applications in optical sensing, these results suggest that a method based on long tail lifetime of the RTP is preferable to a ratiometric approach as the former will not be affected by variation in excitation power density whereas the latter will be.

This work describes the synthesis and characterisation of new tetrahedral boron complexes, incorporating bromine- or iodine-substituted 8-quinolinolato chelate chromophores connected to 9-borafluoren-9-yl or diphenylboron orthogonal fragments. The molecular features and photophysical properties of these complexes are analysed in both solution and solid state. Steady-state photophysical studies reveal photoluminescence quantum yields (Φ f) ranging from 0.02 to 0.15 and prompt fluorescence (PF) lifetimes (τ f) between 2 and 16 ns. Time-resolved photophysical experiments show the presence of delayed fluorescence (DF) and phosphorescence at both 77 K and room temperature. The DF intensity increases with a rise in temperature. This variation is ascribed to an enhancement in the intersystem crossing (ISC) process promoted by the bromine or iodine heavy-atom effect. Investigations into the dependence of DF intensity relative to the excitation dose indicate emissions stemming either from Triplet-Triplet Annihilation (TTA), Thermally Activated Delayed Fluorescence (TADF), or a combination of these competing mechanisms. The effect is related to the size and number of heavy-atom substituents in each boron complex. A study of the DF emission intensity as a function of the excitation dose reveals that diiodo-substituted 8-quinolinolato boron complexes, whether rigid or flexible, display TADF emission. Rigid 5,7-dibromo- and 5-chloro-7-iodo-substituted 8-quinolinolato complexes exhibit a combined TADF-TTA mechanism, whereas the other complexes predominantly demonstrate pure TTA emission. DFT and TDDFT calculations showed that the ground state structures reproduced the experimental geometries and only small increases in bond lengths were observed in the excited state geometries. The low energy absorption bands displayed mainly intra-ligand π→π* (8-quinolinato) character. The fluorescence emission energies were well reproduced, while the singlet-triplet energy gaps were relatively high and spin-orbit coupling was relevant for complexes with heavy-atoms. Ultimately, organic light-emitting diodes (OLEDs) are fabricated using the most luminescent boron complexes. The best OLED is obtained when using complex 3a , which displays green electroluminescence (EL) (λ EL = 502 nm) with maximum external quantum efficiency (EQE max) of 2.5% and maximum luminance (L max) of 2200 cd m−2. • New boron complexes with Br- or I-substituted 8-quinolinolato ligands were prepared. • DFT/TDDFT calculations revealed 8-quinolinolato intra-ligand electronic transitions. • The new boron complexes exhibited Delayed Fluorescence (DF). • The DF arises from either TTA, TADF or mixed TTA-TADF processes. • Selected boron complexes were tested as dopants in OLED devices. [ABSTRACT FROM AUTHOR]

Sensitized triplet‐triplet annihilation upconversion (sTTA‐UC) mainly relies on precious metal complexes thanks to their high intersystem crossing (ISC) efficiencies, excited state energies, and lifetimes, while complexes of abundant first‐row transition metals are only rarely utilized and with often moderate UC quantum yields. [Cr(bpmp)2]3+ (bpmp=2,6‐bis(2‐pyridylmethyl)pyridine) containing earth‐abundant chromium possesses an absorption band suitable for green light excitation, a doublet excited state energy matching the triplet energy of 9,10‐diphenyl anthracene (DPA), a close to millisecond excited state lifetime, and high photostability. Combined ISC and doublet‐triplet energy transfer from excited [Cr(bpmp)2]3+ to DPA gives 3DPA with close‐to‐unity quantum yield. TTA of 3DPA furnishes green‐to‐blue UC with a quantum yield of 12.0 % (close to the theoretical maximum). Sterically less‐hindered anthracenes undergo a [4+4] cycloaddition with [Cr(bpmp)2]3+ and green light. [ABSTRACT FROM AUTHOR]

The article analyzes the potential for photon upconversion to enhance photovoltaic efficiencies. It is noted that photovoltaic (PV) cells experience a number of loss mechanisms which limit efficiency thereby increasing operating costs to make up for the losses. Some of the strategies include multiple exciton generation multi-junction cells and spectral converters.

Triplet–triplet annihilation photon upconversion (TTA-UC) is a process in which low-energy light is transformed into light of higher energy. During the last two decades, it has gained increasing attention due to its potential in, e.g., biological applications and solar energy conversion. The highest efficiencies for TTA-UC systems have been achieved in liquid solution, owing to that several of the intermediate steps require close contact between the interacting species, something that is more easily achieved in diffusion-controlled environments. There is a good understanding of the kinetics dictating the performance in liquid TTA-UC systems, but so far, the community lacks cohesiveness in terms of how several important parameters are best determined experimentally. In this perspective, we discuss and present a "best practice" for the determination of several critical parameters in TTA-UC, namely triplet excited state energies, rate constants for triplet–triplet annihilation ( k TTA ), triplet excited-state lifetimes ( τ T ), and excitation threshold intensity ( I th ). Finally, we introduce a newly developed method by which k TTA , τ T , and I th may be determined simultaneously using the same set of time-resolved emission measurements. The experiment can be performed with a simple experimental setup, be ran under mild excitation conditions, and entirely circumvents the need for more challenging nanosecond transient absorption measurements, a technique that previously has been required to extract k TTA . Our hope is that the discussions and methodologies presented herein will aid the photon upconversion community in performing more efficient and manageable experiments while maintaining—and sometimes increasing—the accuracy and validity of the extracted parameters. [ABSTRACT FROM AUTHOR]

Photon upconversion (UC) based on triplet–triplet annihilation (TTA) is considered one of the most attractive methodologies for switching wavelengths from lower to higher energy. This two-photon process, which requires the involvement of a bimolecular system, has been widely used in numerous fields such as bioimaging, solar cells, displays, drug delivery, and so on. In the last years, we have witnessed the harnessing of this concept by the organic community who have developed new strategies for synthetic purposes. Interestingly, the generation of high-energetic species by this phenomenon has provided the opportunity not only to photoredox activate compounds with high-energy demanding bonds, expanding the reactivity window that lies outside the energy window of the initial irradiation wavelength, but also to sensitized conventional photocatalysts through energy transfer processes even employing infrared irradiation. Herein, an overview of the principal examples found in literature is described where TTA–UC systems are found to be suitable photosensitizers for several chemical transformations. [ABSTRACT FROM AUTHOR]

Realization of efficient photon upconversion (UC) mediated by triplet–triplet annihilation (TTA) in a solid state is a great challenge, even though order of magnitude higher efficiencies are routinely reported in a solution/liquid state. To address this issue in a typical emitter/sensitizer UC system, a combined approach is introduced based on 1) thorough emitter purification for reduced exciton quenching and 2) UC film fabrication via melt‐processing for attaining large emitter concentrations with suppressed aggregation. Emitter purification via vacuum sublimation is shown to reduce the number of both singlet and triplet quenchers as confirmed by fluorescence and UC quantum yield measurements along with the respective transient measurements performed on nanosecond and millisecond time domains. Application of this approach to the benchmark TTA‐UC system DPA/PtOEP is demonstrated to yield a record‐high UC efficiency (=8 ± 1%, out of maximum 50%) achieved at 40 wt% of DPA homogeneously dispersed in the PMMA host. Importantly, such high efficiency is accomplished in large‐area amorphous films, the most preferred for practical applications, and featuring low UC threshold (=5 mW cm−2) that is close to the solar irradiance. The presented approach describes the guidelines for boosting UC efficiency in the solid state, and generally, is applicable to any conventional TTA‐UC system. [ABSTRACT FROM AUTHOR]

Highly efficient blue top emission organic light‐emitting diode with a remarkable blue index (BI) of 305 was demonstrated. This was achieved step by step through a combination of customized high reflectivity Ag anode, CPL with high refractivity, electron/hole transporting materials with high injection and transportation capabilities, and carefully engineered device configurations. [ABSTRACT FROM AUTHOR]

The photon upconversion based on triplet–triplet annihilation (TTA) is a mechanism that converts the absorbed low-energy electromagnetic radiation into higher energy photons also at extremely low excitation intensities, but its use in actual technologies is still hindered by the limited availability of efficient annihilator moieties. We present here the results obtained by the synthesis and application of two new fluorinated chromophores based on phenazine and acridine structures, respectively. Both compounds show upconverted emission demonstrating their ability as TTA annihilator. More interesting, the acridine-based chromophore shows an excellent TTA yield that overcomes the one of some of best model systems. By correlating the experimental data and the quantum mechanical modeling of the investigated compound, we propose an alternative efficient pathway for the generation of the upconverted emissive states involving the peculiar high-energy triplet levels of the dye, thus suggesting a new development strategy for TTA annihilators based on the fine tuning of their high-energy excited states properties. [ABSTRACT FROM AUTHOR]

Triplet-triplet annihilation upconversion (TTA-UC) nanoparticles (NPs) have emerged as imaging probes and therapeutic probes in recent years due to their excellent optical properties. In contrast to lanthanide ion-doped inorganic materials, highly efficient TTA-UC can be generated by low excitation power density, which makes it suitable for clinical applications. In the present study, we used biodegradable poly(lactic-co-glycolic acid) (PLGA)-NPs as a delivery vehicle for TTA-UC based on the heavy metal porphyrin Platinum(II) octaethylporphyrin (PtOEP) and the polycyclic aromatic hydrocarbon 9,10-diphenylanthracene (DPA) as a photosensitizer/emitter pair. TTA-UC-PLGA-NPs were successfully synthesized according to an oil-in-water emulsion and solvent evaporation method. After physicochemical characterization, UC-efficacy of TTA-UC-PLGA-NPs was assessed in vitro and ex vivo. TTA-UC could be detected in the tumour area 96 h after in vivo administration of TTA-UC-PLGA-NPs, confirming the integrity and suitability of PLGA-NPs as a TTA-UC in vivo delivery system. Thus, this study provides proof-of-concept that the advantageous properties of PLGA can be combined with the unique optical properties of TTA-UC for the development of advanced nanocarriers for simultaneous in vivo molecular imaging and drug delivery. [ABSTRACT FROM AUTHOR]

ABSTRACT: Two phenylene based geometrical/isomeric triplet ortho- and para–dyads (o–3 and p–3, respectively) were synthesized and fully characterized using advanced photophysical tools and computations. In dyad o–3, the through-space donor-acceptor interactions led to simultaneous triplet energy transfer and charge transfer with identical kinetics. On the other hand, in the dyad p–3, it was found that the phenylene spacer favors a fast triplet energy delocalization over the charge transfer process. Furthermore, analysis of the results from the present investigation indicates that the deactivation of the photo-excited species (o–3)* occurs through both the intrinsic channel viz. S0←S1 and charge recombination. In the case of dyad p–3, the results indicate that the primary deactivation pathway is self-quenching or triplet-triplet annihilation involving the acceptor unit(s).

Triplet–triplet annihilation (TTA) up‐conversion is an effective way to utilize triplet excitons in organic light‐emitting diodes (OLEDs). However, the parameters characterizing the triplet excitons and relevant TTA process in OLEDs under working conditions have not been quantified. Here, an in situ method is established to map these parameters for further ascertaining their impact on device efficiency. The physical parameters, including triplet recombination rate, TTA rate, typical current JTTA, and saturated ratio, can be in situ quantified by transient electroluminescence technique. The expression of JTTA shows that minimizing the triplet quenching and maximizing the TTA rate are effective ways to lower JTTA. While highly efficient devices require a lower JTTA. Guided by these criteria, the device efficiency is promoted by weakening the triplet quenching via blending two materials. These investigations establish an in situ method to quantify the physical parameters that allow identifying the useful TTA materials and optimizing the design of device structures. [ABSTRACT FROM AUTHOR]

High‐performance deep‐blue fluorescent materials matching the required Commission Internationale de l'Eclairage y coordinate value (CIEy) of < 0.08 are much‐needed in organic light‐emitting diodes (OLEDs) for realizing the perfect application of full‐color displays. However, deep‐blue fluorophors commonly show unsatisfactory performance due to the intrinsic large bandgap characteristic. Here, the deep‐blue nondoped OLED with the good CIE coordinates of (0.15, 0.07) and external quantum efficiency (EQE) of ≈9% is achieved based on a multifunctional and efficient anthracene‐based fluorophor (2M‐ph‐3CzAnBzt). Using it as a host, the sky‐blue fluorescent OLED realizes the maximum EQE of 9.50%, and keeps as high as 9.27% and 8.56% at 1000 and 5000 cd m−2. More surprisingly, high‐performance hybrid white OLEDs (WOLEDs) with good color stability and low roll‐off are achieved by using it as the blue emitter. Two‐color WOLED shows the forward‐viewing efficiencies of 20.46%, and 76.80 lm W−1. The three‐color WOLED emitting a candlelight with the color rendering index of ≥ 82 realizes the maximum EQE of 21.49% and remains 20.80% at 1000 cd m−2. Such superior electroluminescence performance achieved in these OLEDs ranks among the highest values based on deep‐blue fluorophors with CIEy < 0.08. [ABSTRACT FROM AUTHOR]

Organic small molecules that exhibit second-scale phosphorescence at room temperature are of interest for potential applications in sensing, anticounterfeiting, and bioimaging. However, such materials systems are uncommon-requiring millisecond to second-scale triplet lifetimes, efficient intersystem crossing, and slow rates of nonradiative recombination. Here, a simple and scalable approach is demonstrated to activate long-lived phosphorescence in a wide variety of molecules by suspending them in rigid polymer hosts and annealing them above the polymer's glass transition temperature. This process produces submicron aggregates of the chromophore, which suppresses intramolecular motion that leads to nonradiative recombination and minimizes triplet-triplet annihilation that quenches phosphorescence in larger aggregates. In some cases, evidence of excimer-mediated intersystem crossing that enhances triplet generation in aggregated chromophores is found. In short, this approach circumvents the current design rules for long-lived phosphors, which will streamline their discovery and development., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Photon upconversion (UC) and down‐conversion (DC) are the technology that can increase solar utilization efficiencies.UC and DC are the major key factors for designing and developing efficient organic solar cells. In this mini‐review, we have focused on the recent progress on the ionic liquids (ILs) as novel sustainable media or building blocks for the fabrication of up and down‐converted materials in which energy is migrated through Dexter type of energy transfer by triplet‐triplet annihilation (TTA) and Förster resonance energy transfer (FRET) mechanism to overcome the problems for the use of these phenomena for solar utilization efficiencies associated with conventional solvents. We have surveyed most of the important, recent, and exemplary articles and tried to provide the latest information to help researchers to grab updated knowledge in this field. Finally, we critically assess the potentiality of these sustainable media‐based up and down‐converters to fulfill the requirements for solar utilization efficiencies conceptually. [ABSTRACT FROM AUTHOR]

Achieving continuous‐wave (CW) lasing in organic semiconductors is known to be a difficult task because long‐lived triplets quench radiative singlets via singlet–triplet annihilation (STA). To avoid STA and operate organic lasers in CW or long‐pulse photoexcitation, the triplets need to be removed from an organic laser gain medium. However, this triplet removal leads to a loss of excitons. In addition to removing the detrimental triplets, here it is reported a triplet recycling process, which includes triplet scavenging and successive triplet upconversion via triplet–triplet annihilation (TTA) to regenerate emissive singlet excitons in a laser medium. An anthracene derivative of 9‐(1‐naphthalenyl)‐10‐(4‐(2‐naphthalenyl)phenyl)anthracene (NaNaP‐A) and a laser dye of 4,4′‐bis[4‐(diphenylamino)styryl]biphenyl (BDAVBi) are used as the triplet recycling sensitizer and the emitting laser dye, respectively. In this laser system, NaNaP‐A can efficiently scavenge the triplets formed on BDAVBi because the triplet level is deeper for NaNaP‐A than for BDAVBi, and then NaNaP‐A successively recycles the triplets into the BDAVBi's singlet state via TTA. The TTA compensates and overcomes the STA in this laser system. Hence, these laser devices can be operated with long pulse widths of up to 10 ms. This unique triplet recycling behavior is confirmed by transient photoluminescence (PL) and electroluminescence (EL) studies. [ABSTRACT FROM AUTHOR]

Developing high‐performance visible‐to‐UV photon upconversion systems based on triplet–triplet annihilation photon upconversion (TTA‐UC) is highly desired, as it provides a potential approach for UV light‐induced photosynthesis and photocatalysis. However, the quantum yield and spectral range of visible‐to‐UV TTA‐UC based on nanocrystals (NCs) are still far from satisfactory. Here, three different sized CdS NCs are systematically investigated with triplet energy transfer to four mediators and four annihilators, thus substantially expanding the available materials for visible‐to‐UV TTA‐UC. By improving the quality of CdS NCs, introducing the mediator via a direct mixing fashion, and matching the energy levels, a high TTA‐UC quantum yield of 10.4% (out of a 50% maximum) is achieved in one case, which represents a record performance in TTA‐UC based on NCs without doping. In another case, TTA‐UC photons approaching 4 eV are observed, which is on par with the highest energies observed in optimized organic systems. Importantly, the in‐depth investigation reveals that the direct mixing approach to introduce the mediator is a key factor that leads to close to unity efficiencies of triplet energy transfer, which ultimately governs the performance of NC‐based TTA‐UC systems. These findings provide guidelines for the design of high‐performance TTA‐UC systems toward solar energy harvesting. [ABSTRACT FROM AUTHOR]

The efficiency roll‐off in organic light‐emitting diodes (OLEDs) based on thermally activated delayed fluorescence (TADF) is attributed to either singlet–triplet or triplet–triplet annihilation (TTA) as well as triplet–charge annihilation. The origin of the efficiency roll‐off on a TADF OLED consisting of a host‐less single‐layer emitter is studied. Varying the charge‐carrier concentration at constant exciton density or the exciton density at constant charge‐carrier density with temperature unambiguously shows that the dominant contribution to the roll‐off originates from TTA. Using an analytical model, also the TTA rate constant can be obtained. These results show that single‐layer TADF OLEDs are suited not only to determine the roll‐off mechanism, but also to provide its rate constant directly from OLED efficiency measurements. [ABSTRACT FROM AUTHOR]

Photon interconversion generally describes processes which change the wavelength of the emitted light upon irradiation, with a gain in photon energy (upconversion), or a splitting of the incident photon energy to create multiple photons (downconversion). The focus of this progress report is placed on halide perovskite materials and their role in upconversion by triplet–triplet annihilation and downconversion via singlet fission in organic semiconductors, and a short perspective is given into quantum cutting and lanthanide‐based upconversion applications. The current advances are highlighted regarding halide perovskites and perovskite‐inspired materials with varying framework and material dimensionalities, as relating to photon interconversion processes. The majority of the literature is based on 3D perovskites, which leaves room for growth for perovskite materials with varying dimensionalities. Gaps in the current field are emphasized, leading to a bright outlook on future possibilities of coupling perovskites to photon interconversion mechanisms, which can open the door for future breakthroughs in this field. [ABSTRACT FROM AUTHOR]

Novel electron donor–acceptor–donor (D‐A‐D) compounds comprising dibenzo[a,j]phenazine as the central acceptor core and two 7‐membered diarylamines (iminodibenzyl and iminostilbene) as the donors have been designed and synthesized. Investigation of their physicochemical properties revealed the impact of C2 insertion into well‐known carbazole electron donors on the properties of previously reported twisted dibenzo[a,j]phenazine‐core D‐A‐D triads. Slight structural modification caused a drastic change in conformational preference, allowing unique photophysical behavior of dual emission derived from room‐temperature phosphorescence and triplet–triplet annihilation. Furthermore, electrochemical analysis suggested sigma‐dimer formation and electrochemical polymerization on the electrode. Quantum chemical calculations also rationalized the experimental results. [ABSTRACT FROM AUTHOR]

Triplet–triplet annihilation (TTA) mechanism utilizing the conversion of low triplet energy excitons to generate singlet excitons has been successfully employed in realizing highly efficient fluorescent organic light‐emitting diodes (OLEDs). Herein, new anthracene‐based TTA molecules (TPNACN and TPBACN) are developed as deep‐blue emitters for high‐efficiency non‐doped TTA‐OLEDs. Their structural, physical, and photophysical properties are experimentally and theoretically investigated. These compounds in solid‐state exhibit different photophysical properties due to a discrepancy in the molecular packing. Particularly, in the crystal of TPNACN, anthracene moieties are arranged with dimeric π–π stacking, and the material shows a strong excimer emission in the deep‐blue region with ΦPL close to the ideal theoretical value. The non‐doped TTA‐OLED based on TPNACN attains a high maximum external quantum efficiency of 7.89% (6.63 cd A−1) with a low turn‐on voltage of 2.6 V, and displays deep‐blue emission with CIE coordinates of (0.146, 0.101). These results prove that a separated dimeric π‐stacked molecular alignment of anthracene enhances not only the fluorescence efficiency in the solid state but also the ratio of singlet exciton harvested by the TTA process in the device, bringing about excellent device electroluminescent properties. This can be a new tactic to designing new emissive materials for efficient OLED devices. [ABSTRACT FROM AUTHOR]

The ability to optically induce biological responses in 3D has been dwarfed by the physical limitations of visible light penetration to trigger photochemical processes. However, many biological systems are relatively transparent to low‐energy light, which does not provide sufficient energy to induce photochemistry in 3D. To overcome this challenge, hydrogels that are capable of converting red or near‐IR (NIR) light into blue light within the cell‐laden 3D scaffolds are developed. The upconverted light can then excite optically active proteins in cells to trigger a photochemical response. The hydrogels operate by triplet–triplet annihilation upconversion. As proof‐of‐principle, it is found that the hydrogels trigger an optogenetic response by red/NIR irradiation of HeLa cells that have been engineered to express the blue‐light sensitive protein Cry2olig. While it is remarkable to photoinduce the clustering of Cry2olig with blanket NIR irradiation in 3D, it is also demonstrated how the hydrogels trigger clustering within a single cell with great specificity and spatiotemporal control. In principle, these hydrogels may allow for photochemical control of cell function within 3D scaffolds, which can lead to a wealth of fundamental studies and biochemical applications. [ABSTRACT FROM AUTHOR]

Abstract Anionic 9,10-diphenylanthracene chromophores electrostatically bound to cationic, chiral bilayer membranes show ordered self-assembly in water. The integrity of the chromophore-accumulated aqueous bilayer membranes is ensured by multiple hydrogen-bond networks introduced in the bilayer, which allowed adaptive accommodation of the guest chromophores at the inner surface of the bilayer while maintaining their cohesive interactions. The regular chromophore alignment in the aqueous assembly is confirmed by differential scanning calorimetry, circular dichroism, and circularly polarized luminescence spectra. Excitonic migration of triplet energy occurs among the chromophores densely organized at the inner surface of the bilayer, which lead to triplet–triplet annihilation-based photon upconversion (TTA-UC). This acceptor-bilayer self-assemblies show a notably long triplet lifetime of 8.0 ms, which allows TTA-UC at sufficiently low excitation light intensity. These results demonstrate the usefulness of the simple electrostatic accumulation approach for TTA-UC chromophores where the suitable molecular design of the TTA-UC chromophore-integrated bilayer membranes plays a key role.

Photon frequency conversion using optical materials is a common strategy for light generation and utilization. Materials capable of visible‐to‐ultraviolet (UV) light conversion have attracted particular attention due to their potential applications in nonlinear optics, biophotonics, as well as environmental sciences. There are four main mechanisms of visible‐to‐UV light conversion processes, including second‐harmonic generation, two‐photon absorption, lanthanide‐based upconversion, and triplet–triplet annihilation. Herein, recent developments in visible‐to‐UV light conversion materials are collectively reviewed and the emerging applications are presented. The prospects and challenges for further development in this field are also highlighted.

NIR light‐induced polymerization has attracted more and more attention in the photopolymerization field due to the possibility to use safer and more penetrating wavelengths, reducing the hazardousness. Here, a novel perspective for the free radical polymerization of acrylate‐based monomers based on triplet–triplet annihilation upconversion (TTA‐UC) is proposed, avoiding the introduction of heavy metals, usually required in the TTA processes. Thermal imaging experiments and Fourier transform infrared spectroscopy are respectively used to record the temperature during NIR irradiation and measure the reactive function conversion. The competition between the TTA‐UC and the NIR photothermal activation is investigated to compare the relative efficiency of both NIR processes. In view of the results obtained by the different methods, the photothermal effect seems to get the upper hand over the photoactivation of the system. [ABSTRACT FROM AUTHOR]

The development of near UV‐emitting materials will be presented. A novel ladder‐like multiresonant thermally activated delayed fluorescence (TADF) compound was studied in the solid state. The compound shows narrow near UV‐emission centered at 395 nm of optical excitation and at 410 nm in an OLED; however, the efficiency remains low. Photophysical studies reveal the presence of aggregate or excimer‐like species that seem to provide an additional loss channel. [ABSTRACT FROM AUTHOR]

Triplet-triplet annihilation upconversion (TTA-UC) nanoparticles (NPs) have emerged as imaging probes and therapeutic probes in recent years due to their excellent optical properties. In contrast to lanthanide ion-doped inorganic materials, highly efficient TTA-UC can be generated by low excitation power density, which makes it suitable for clinical applications. In the present study, we used biodegradable poly(lactic-co-glycolic acid) (PLGA)-NPs as a delivery vehicle for TTA-UC based on the heavy metal porphyrin Platinum(II) octaethylporphyrin (PtOEP) and the polycyclic aromatic hydrocarbon 9,10-diphenylanthracene (DPA) as a photosensitizer/emitter pair. TTA-UC-PLGA-NPs were successfully synthesized according to an oil-in-water emulsion and solvent evaporation method. After physicochemical characterization, UC-efficacy of TTA-UC-PLGA-NPs was assessed in vitro and ex vivo. TTA-UC could be detected in the tumour area 96 h after in vivo administration of TTA-UC-PLGA-NPs, confirming the integrity and suitability of PLGA-NPs as a TTA-UC in vivo delivery system. Thus, this study provides proof-of-concept that the advantageous properties of PLGA can be combined with the unique optical properties of TTA-UC for the development of advanced nanocarriers for simultaneous in vivo molecular imaging and drug delivery.

Efficiency and operation lifetime of blue triplet‐triplet annihilation organic light emitting diodes (TTA‐OLEDs) were enhanced by 16% and 297%, respectively, by employing double emitting layer structure. Blue OLED with maximum external quantum efficiency of 9.4% and half‐lifetime of 96,620 hours at initial luminance of 1,000 cd/m2 was achieved. [ABSTRACT FROM AUTHOR]

A series of bottom‐emitting Blue OLEDs with an optimal efficiency and lifetime are successfully fabricated by introducing different electrical material combinations. Distinct EQE‐Current density performance are analyzed and validated by the transient EL response, which reveal the Triplet‐Triplet Annihilation (TTA) impact differently. Overall, an efficiency‐lifetime‐trade‐off have been obtained, with 60% Lifetime promotion, 3% EQE decline and 6% voltage rise. The investigation of mechanism and experimental validation provide a method in long‐lifetime and high‐efficiency device design. [ABSTRACT FROM AUTHOR]

Scintillating materials emit light when exposed to ionizing radiation or particles and are used for the detection of nuclear threats, medical imaging, high-energy physics, and other usages. For some of these applications, it is vital to distinguish neutrons and charged particles from γ-rays. This is achievable by pulse shape discrimination (PSD), a time-gated technique, which exploits that the scintillation kinetics can depend on the nature of the incident radiation. However, it proves difficult to realize efficient PSD with plastic scintillators, which have several advantages over liquid or crystalline scintillating materials, including mechanical robustness and shapeability. It is shown here that sensitive and rapid PSD is possible with nanostructured polymer scintillators that consist of a solid polymer matrix and liquid nanodomains in which an organic dye capable of triplet-triplet annihilation (TTA) is dissolved. The liquid nature of the nanodomains renders TTA highly efficient so that delayed fluorescence can occur at low energy density. The nanostructured polymer scintillators allow discriminating α particles, neutrons, and γ-rays with a time response that is better than that of commercial scintillators. Exploiting that the liquid nanodomains can facilitate energy transfer processes otherwise difficult to realize in solid polymers, an auxiliary triplet sensitizer is incorporated. This approach further increases the scintillator's sensitivity toward α particles and neutrons and other high-energy processes where localized interactions are involved., (© 2024 Wiley‐VCH GmbH.)

While many studies have been done on triplet–triplet annihilation‐based photon upconversion (TTA‐UC) to produce visible light with high efficiency, the efficient TTA‐UC from visible to UV light, despite its importance for a variety of solar and indoor applications, remains a challenging task. Here, we report the highest visible‐to‐UV TTA‐UC efficiency of 20.5 % based on the discovery of an excellent UV emitter, 1,4‐bis((triisopropylsilyl)ethynyl)naphthalene (TIPS‐Nph). TIPS‐Nph is an acceptor with desirable features of high fluorescence quantum yield and high singlet generation efficiency by TTA. TIPS‐Nph has a low enough triplet energy level to be sensitized by Ir(C6)2(acac), a superior donor that does not quench UV emission. The combination of TIPS‐Nph and Ir(C6)2(acac) realizes the efficient UV light production even with weak light sources such as an AM 1.5 solar simulator and room LEDs. [ABSTRACT FROM AUTHOR]

Perovskite solar cells have emerged as the next‐generation high‐efficiency solar cell, but their absorption is mostly limited to the visible (vis) range. One possible solution is to integrate near‐infrared (NIR)‐to‐vis photon upconversion (UC). Herein, we show the first example of endowing perovskite solar cells with NIR sensitivity by using solid films showing NIR‐to‐vis UC based on triplet‐triplet annihilation (TTA). A high TTA‐UC efficiency of 4.1±0.3 % at an excitation intensity of 125 W/cm2 is achieved by sensitizing a rubrene (acceptor) triplet with an osmium (Os) complex donor having singlet‐to‐triplet (S−T) absorption in the NIR range, and by increasing the fluorescence quantum yield through energy harvesting to a highly fluorescent collector. In particular, our spectroscopic studies indicate that the upconverted acceptor singlet energy is almost selectively transferred to the collector rather than being quenched by the donor. By attaching the TTA‐UC film behind a semi‐transparent perovskite solar cell, a photocurrent generation is observed under excitation at 938 nm. [ABSTRACT FROM AUTHOR]

Device fabrication methods for applications in upconversion processes using perovskite thin films have suffered from reproducibility and scalability issues, which prevent the upscaling of this technology. In this contribution, we developed a perovskite‐based upconversion device approach where the triplet annihilator is added in situ to the antisolvent and investigated the effect of the device fabrication procedure on the properties of our device. By comparing the properties of a device based on our new fabrication approach with the existing bilayer procedure, we seek to shed light on the underlying optoelectronic processes influenced by the different fabrication methods, while further advancing possible device architectures for upconversion devices. Device characterization by optical methods, X‐ray diffraction and atomic force microscopy revealed that the in situ fabricated devices match the performance or even outcompete our previously developed bilayer devices while significantly simplifying the device fabrication. In particular, we find that the developed one‐step fabrication technique enables intercalation of the upconverting layer into the perovskite film prior to annealing, resulting in a larger interface thus, more efficient charge extraction. [ABSTRACT FROM AUTHOR]

Recent studies have demonstrated that in thermally activated delayed fluorescence (TADF) materials, efficient reverse intersystem crossing occurs from nonradiative triplet exited states to radiative singlet excited states due to a small singlet–triplet energy gap. This reverse intersystem crossing significantly influences exciton annihilation processes and external quantum efficiency roll‐off in TADF based organic light‐emitting diodes (OLEDs). In this work, a comprehensive exciton quenching model is developed for a TADF system to determine singlet–singlet, singlet–triplet, and triplet–triplet annihilation rate constants. A well‐known TADF molecule, 3‐(9,9‐dimethylacridin‐10(9H)‐yl)‐9H‐xanthen‐9‐one (ACRXTN), is studied under intensity‐dependent optical and electrical pulse excitation. The model shows singlet–singlet annihilation dominates under optically excited decays, whereas singlet–triplet annihilation and triplet–triplet annihilation have strong contribution in electroluminescence decays under electrical pulse excitation. Furthermore, the efficiency roll‐off characteristics of ACRXTN OLEDs at steady state is investigated through simulation. Finally, singlet and triplet diffusion length are calculated from annihilation rate constants. [ABSTRACT FROM AUTHOR]

Photolysis reactions are widely utilized to release desired molecules under the control of light irradiation in the fields of photochemistry, biology, and drug delivery. In biological and medical applications, it is highly desired to increase the excitation wavelength for activating photolysis reactions, since the long-wavelength light (red or near-infrared light) has deep tissue penetration depth and low photocytotoxicity. Here, we briefly summarize current strategies of achieving long-wavelength light-excitable photolysis. We highlight our recently developed strategy of one-photon upconversion-like photolysis. Compared with the multiphoton upconversion-based photolysis, the one-photon strategy has a simpler energy transfer process and a higher -energy utilization efficiency, providing a new path of activating photolysis reactions with increased excitation wavelength and photolysis quantum yield. [ABSTRACT FROM AUTHOR]

The addition of stimuli‐responsiveness to anti‐Stokes emission provides a unique platform for biosensing and chemosensing. Particularly, stimuli‐responsive photon upconversion based on triplet–triplet annihilation (TTA‐UC) is promising due to its occurrence at low excitation intensity with high efficiency. This Minireview summarizes the recent developments of TTA‐UC switching by external stimuli such as temperature, oxygen, chemicals, light, electric field, and mechanical force. For the systematic understanding of the underlying general mechanisms, the switching mechanisms are categorized into four types: 1) aggregation‐induced UC; 2) assembly‐induced air‐stable UC; 3) diffusion‐controlled UC; and 4) energy‐transfer‐controlled UC. The development of stimuli‐responsive smart TTA‐UC systems would enable sensing with unprecedented sensitivity and selectivity, and expand the scope of TTA‐UC photochemistry by combination with supramolecular chemistry, materials chemistry, mechanochemistry, and biochemistry. [ABSTRACT FROM AUTHOR]