Triplet-triplet Annihilation Upconversion Research Articles

Harnessing Heavy-Atom Effects in Multiple Resonance Thermally Activated Delayed Fluorescence (MR-TADF) Sensitizers: Unlocking High-Performance Visible-to-Ultraviolet (Vis-to-UV) Triplet Fusion Upconversion.

Ultraviolet (UV) light plays a crucial role in various applications, but currently, the efficiency of generating artificial UV light is low. The visible-to-ultraviolet (Vis-to-UV) system based on the triplet-triplet annihilation upconversion (TTA-UC) mechanism can be a viable solution. Metal-free multiple resonance thermally activated delayed fluorescence (MR-TADF) materials are ideal photosensitizers (PSs) apart from the drawback of high photoluminescence quantum yields (PLQYs). Herein, we systematically investigated the impact of the heavy-atom effect (HAE) on the MR-TADF sensitizers. BNCzBr was then synthesized by incorporating a bromine atom into the skeleton of the precursor BNCz. Impressively, the internal HAE (iHAE) leads to a significantly decreased PLQY and a remarkably increased intersystem crossing quantum yield (ΦISC). Consequently, a higher upconversion quantum efficiency of 12.5% was realized. While the external HAE (eHAE) harms the UC performance. This work guides the further development of MR-TADF sensitizers for high-performance Vis-to-UV TTA-UC systems.

Iron(III) Carbene Complexes with Tunable Excited State Energies for Photoredox and Upconversion.

Substituting precious elements in luminophores and photocatalysts by abundant first-row transition metals remains a significant challenge, and iron continues to be particularly attractive owing to its high natural abundance and low cost. Most iron complexes known to date face severe limitations due to undesirably efficient deactivation of luminescent and photoredox-active excited states. Two new iron(III) complexes with structurally simple chelate ligands enable straightforward tuning of ground and excited state properties, contrasting recent examples, in which chemical modification had a minor impact. Crude samples feature two luminescence bands strongly reminiscent of a recent iron(III) complex, in which this observation was attributed to dual luminescence, but in our case, there is clear-cut evidence that the higher-energy luminescence stems from an impurity and only the red photoluminescence from a doublet ligand-to-metal charge transfer (2LMCT) excited state is genuine. Photoinduced oxidative and reductive electron transfer reactions with methyl viologen and 10-methylphenothiazine occur with nearly diffusion-limited kinetics. Photocatalytic reactions not previously reported for this compound class, in particular the C-H arylation of diazonium salts and the aerobic hydroxylation of boronic acids, were achieved with low-energy red light excitation. Doublet-triplet energy transfer (DTET) from the luminescent 2LMCT state to an anthracene annihilator permits the proof of principle for triplet-triplet annihilation upconversion based on a molecular iron photosensitizer. These findings are relevant for the development of iron complexes featuring photophysical and photochemical properties competitive with noble-metal-based compounds.

Enhancing Triplet–Triplet Annihilation Upconversion Performance Through Anthracene–Carbazole Interactions for Organic Optoelectronic Applications

Three carbazole‐substituted anthracene 2CbzAn, 26CbzAn, and 246CbzAn have been developed. The introduction of these carbazole substituents could generate more triplet states with energy levels close to 2× E(T1) that could successfully facilitate the triplet‐triplet annihilation upconversion (TTA‐UC) process to achieve high upconversion quantum yield (UCQY). This observation aligns with the Adachi theory about TTA‐UC mechanisms. In organic light‐emitting diode (OLED) device investigation, in a non‐doped state show an external quantum efficiency (EQEmax) of 5.82% with exceptional pure‐blue emission (CIEy of 0.101), and the DPaNIF doped DMPPP/26CbzAn bilayer structure reaches an impressive EQEmax of 11.12%.

Ferromagnetically Coupled Chromium(III) Dimer Shows Luminescence and Sensitizes Photon Upconversion.

There has been much progress on mononuclear chromium(III) complexes featuring luminescence and photoredox activity, but dinuclear chromium(III) complexes have remained underexplored in these contexts until now. We identified a tridentate chelate ligand able to accommodate both meridional and facial coordination of chromium(III), to either access a mono- or a dinuclear chromium(III) complex depending on reaction conditions. This chelate ligand causes tetragonally distorted primary coordination spheres around chromium(III) in both complexes, entailing comparatively short excited-state lifetimes in the range of 400 to 800 ns in solution at room temperature and making photoluminescence essentially oxygen insensitive. The two chromium(III) ions in the dimer experience ferromagnetic exchange interactions that result in a high spin (S=3) ground state with a coupling constant of +9.3 cm-1. Photoinduced energy transfer from the luminescent ferromagnetically coupled dimer to an anthracene derivative results in sensitized triplet-triplet annihilation upconversion. Based on these proof-of-principle studies, dinuclear chromium(III) complexes seem attractive for the development of fundamentally new types of photophysics and photochemistry enabled by magnetic exchange interactions.

Multi‐Resonance Thermally Activated Delayed Fluorescence Molecules for Triplet‐Triplet Annihilation Upconversion

Triplet‐triplet annihilation upconversion (TTA‐UC) has made significant progress in recent years in several key applications, including solar energy harvesting, photocatalysis, stereoscopic 3D printing, and disease therapeutics. In TTA‐UC research, photosensitizers serve the vital function of harvesting low‐energy photons. The photophysical characteristics of photosensitizers, including absorbance, triplet state quantum yield, triplet state energy level, triplet state lifetime, etc., determine the performance of TTA‐UC. Thus, the study of photosensitizers has been a key aspect of TTA‐UC. In recent years, multi‐resonance thermally activated delayed fluorescence (MR‐TADF) molecules have received extensive attention due to their excellent photophysical properties and electroluminescent device performance. MR‐TADF molecules not only present a narrow energy gap between the singlet and triplet excited states, but also have stronger absorption and better wavelength regulation than conventional TADF molecules. Nowadays, the preliminary attempts in TTA‐UC using MR‐TADF molecules as photosensitizers have resulted in the development of green to ultraviolet, blue to ultraviolet, and even near‐infrared to blue emission. This concept will summarize the research progress of MR‐TADF molecules as photosensitizers in TTA‐UC, analyzing the challenges and giving possible solutions. Finally, we prospect the future development of MR‐TADF molecules as photosensitizers, including the molecular design as well as the possible application areas.

Triplet-triplet annihilation photon upconversion-mediated photochemical reactions.

Photon upconversion is a method for harnessing high-energy excited states from low-energy photons. Such photons, particularly in the red and near-infrared wavelength ranges, can penetrate tissue deeply and undergo less competitive absorption in coloured reaction media, enhancing the efficiency of large-scale reactions and in vivo phototherapy. Among various upconversion methodologies, the organic-based triplet-triplet annihilation upconversion (TTA-UC) stands out - demonstrating high upconversion efficiencies, requiring low excitation power densities and featuring tunable absorption and emission wavelengths. These factors contribute to improved photochemical reactions for fields such as photoredox catalysis, photoactivation, 3D printing and immunotherapy. In this Review, we explore concepts and design principles of organic TTA-UC-mediated photochemical reactions, highlighting notable advancements in the field, as well as identify challenges and propose potential solutions. This Review sheds light on the potential of organic TTA-UC to advance beyond the traditional photochemical reactions and paves the way for research in various fields and clinical applications.

Molecular near-infrared triplet-triplet annihilation upconversion with eigen oxygen immunity

Molecular triplet-triplet annihilation upconversion often experiences drastic luminescence quenching in the presence of oxygen molecules, posing a significant constraint on practical use in aerated conditions. We present an oxygen-immune near-infrared triplet-triplet annihilation upconversion system utilizing non-organometallic cyanine sensitizers (λex = 808 nm) and chemically synthesized benzo[4,5]thieno[2,3-b][1,2,5]thiadiazolo[3,4-g]quinoxaline dyes with a defined dimer structure as annihilators (λem = 650 nm). This system exhibits ultrastable upconversion under continuous laser irradiance (>480 mins) or extended storage (>7 days) in aerated solutions. Mechanistic investigations reveal rapid triplet-triplet energy transfer from sensitizer to annihilators, accompanied by remarkably low triplet oxygen quenching efficiencies (ηO2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\eta }_{{{{\\mbox{O}}}}_{2}}$$\\end{document} < 13% for the sensitizer, <3.7% for the annihilator), endowing the bicomponent triplet-triplet annihilation system with inherent oxygen immunity. Our findings unlock the direct and potent utilization of triplet-triplet annihilation upconversion systems in real-world applications, demonstrated by the extended and sensitive nanosensing of peroxynitrite radicals in the liver under in vivo nitrosative stress.

Porphyrin-Sensitizers and Anthracene-Annihilators Built in Isostructural Frameworks for Investigating Triplet-Triplet Annihilation Upconversion.

In this study, four isostructural pillar-layered frameworks were constructed using a porphyrin layer and an anthracene pillar, which served as the sensitizer and annihilator, respectively, in the triplet-triplet annihilation upconversion (TTA-UC) system. Framework 1 demonstrated the highest upconversion quantum yield of 1.01%. Additionally, 1 and 2 also exhibited down-conversion fluorescence resulting from the porphyrin component. A twist intramolecular charge transfer (TICT) state was observed in the bianthracene chromophore of 2, resulting in transient rotation of two anthracene rings and red-shifted emission. Both computational studies and experiments confirmed the transition from a locally excited state to a TICT state upon the inclusion of polar guest molecules into the framework.

New Type Annihilator of π-Expanded Diketopyrrolopyrrole for Robust Photostable NIR-Excitable Triplet-Triplet Annihilation Upconversion.

Near-infrared light excitable triplet-triplet annihilation upconversion (NIR TTA-UC) materials have attracted interest in a variety of emerging applications such as photoredox catalysis, optogenetics, and stereoscopic 3D printing. Currently, the practical application of NIR TTA-UC materials requires substantial improvement in photostability. Here, we found that the new annihilator of π-expanded diketopyrrolopyrrole (π-DPP) cannot activate oxygen to generate superoxide anion via photoinduced electron transfer, and its electron-deficient characteristics prevent the singlet oxygen-mediated [2 + 2] cycloaddition reaction; thus, π-DPP exhibited superior resistance to photobleaching. In conjunction with the NIR photosensitizer PdTNP, the upconversion efficiency of π-DPP is as high as 8.9%, which is eight times of the previously reported PdPc/Furan-DPP. Importantly, after polystyrene film encapsulation, less than 10% photobleaching was observed for this PdTNP/π-DPP-based NIR TTA-UC material after four hours of intensive NIR light exposure. These findings provide a type of annihilator with extraordinary photostability, facilitating the development of NIR TTA-UC materials for practical photonics.

Expanding the Anti-Stokes Shift of TTA-UC to 1.04 eV by Chemical Tuning of BODIPY-Based Organic Photosensitizers.

A series of BODIPY-derivatives B-1 ∼ B-5 were synthesized as metal-free photosensitizers in triplet-triplet annihilation (TTA) upconversion (UC) with the purpose of finely tuning the excited state properties to reduce the energy loss during intersystem crossing (ISC), and hence to expand the anti-Stokes shift of TTA-UC. It was revealed that B-5 showed a ΔEST of as small as 0.28 eV, thus, providing a large anti-Stokes shift of 1.04 eV in TTA-UC with organic sensitizers. A deep red-blue upconversion emission with UC quantum yields of up to 10.7% (out of a 50% maximum) was observed.

Triplet Upconversion under Ambient Conditions Enables Digital Light Processing 3D Printing.

The rapid photochemical conversion of materials from liquid to solid (i.e., curing) has enabled the fabrication of modern plastics used in microelectronics, dentistry, and medicine. However, industrialized photocurables remain restricted to unimolecular bond homolysis reactions (Type I photoinitiations) that are driven by high-energy UV light. This narrow mechanistic scope both challenges the production of high-resolution objects and restricts the materials that can be produced using emergent manufacturing technologies (e.g., 3D printing). Herein we develop a photosystem based on triplet-triplet annihilation upconversion (TTA-UC) that efficiently drives a Type I photocuring process using green light at low power density (<10 mW/cm2) and in the presence of ambient oxygen. This system also exhibits a superlinear dependence of its cure depth on the light exposure intensity, which enhances spatial resolution. This enables for the first-time integration of TTA-UC in an inexpensive, rapid, and high-resolution manufacturing process, digital light processing (DLP) 3D printing. Moreover, relative to traditional Type I and Type II (photoredox) strategies, the present TTA-UC photoinitiation method results in improved cure depth confinement and resin shelf stability. This report provides a user-friendly avenue to utilize TTA-UC in ambient photochemical processes and paves the way toward fabrication of next-generation plastics with improved geometric precision and functionality.

Ultraviolet Circularly Polarized Luminescence in Chiral Perovskite Nanoplatelet-Molecular Hybrids: Direct Binding Versus Efficient Triplet Energy Transfer.

The development of ultraviolet circularly polarized light (UVCPL) sources has the potential to benefit plenty of practical applications but remains a challenge due to limitations in available material systems and a limited understanding of the excited state chirality transfer. Herein, by constructing hybrid structures of the chiral perovskite CsPbBr3 nanoplatelets and organic molecules, excited state chirality transfer is achieved, either via direct binding or triplet energy transfer, leading to efficient UVCPL emission. The underlying photophysical mechanisms of these two scenarios are clarified by comprehensive optical studies. Intriguingly, UVCPL realized via the triple energy transfer, followed by the triplet-triplet annihilation upconversion processes, demonstrates a 50-fold enhanced dissymmetry factor glum . Furthermore, stereoselective photopolymerization of diacetylene monomer is demonstrated by using such efficient UVCPL. This study provides both novel insights and a practical approach for realizing UVCPL, which can also be extended to other material systems and spectral regions, such as visible and near-infrared.

Triplet properties and intersystem crossing mechanism of PtAg28 nanocluster sensitizers achieving low threshold and efficient photon upconversion.

Ligand-protected metal nanoclusters have emerged as a promising platform for providing sensitizers for triplet-triplet annihilation upconversion (TTA-UC). Herein, we report [PtAg28(BDT)12]4- (PtAg28; BDT = 1,3-benzenedithiolate) as a sensitizer enabling TTA-UC at low excitation intensities. PtAg28 exhibits a long-lived triplet state (approximately 7 μs) generated with a 100% intersystem crossing (ISC) quantum yield. The mechanism driving this efficient ISC was unveiled with the aid of theoretical calculations. Specifically, the S1-T1 ISC reveals a small spin-orbit coupling (SOC) matrix element, attributed to their similar electron configuration. In contrast, the T2 state, which is energetically close to S1, features a hole distribution derived from the Py superatomic orbital of the icosahedral Pt@Ag12 core. This distribution enables direct SOC based on the orbital angular momentum change from the S1 state with a Pz-derived hole distribution. Consequently, the efficient ISC was rationalized by the S1 → T2 → T1 pathway. The T1 state possesses a metal core-to-surface metal charge transfer character, facilitating triplet energy transfer and conferring superior sensitization ability. Leveraging these characteristics, the combination of PtAg28 sensitizer with a 9,10-diphenylanthracene annihilator/emitter attained an extremely low UC threshold of 0.81 mW cm-2 at 532 nm excitation, along with efficient green-to-blue TTA-UC with an internal quantum yield (ΦUCg) of 12.2% (50% maximum). This results in a pseudo-first-order TTA process with strong UC emission under 1-sun conditions.

Crystalline hydrogen-bonded organic framework for air-tolerant triplet-triplet annihilation upconversion.

A hydrogen-bonded organic framework (HOF) consisting of a 9,10-diphenylanthracene carboxylic derivative, DPACOOH, was developed for solid state triplet-triplet annihilation upconversion (TTA-UC). The HOF sample shows a 70% increase in upconversion quantum yield and a lower threshold value of 126.0 mW cm-2 compared to those of the disordered powder sample, due to a 43% longer triplet diffusion length in HOF than that in the powder sample.

Study on the energy level limitations of triplet-triplet annihilation upconversion with anthracene-isomerized dimers as annihilators

Study on the energy level limitations of triplet-triplet annihilation upconversion with anthracene-isomerized dimers as annihilators

Ambient solid-state triplet-triplet annihilation upconversion in ureasil organic-inorganic hybrid hosts.

Triplet-triplet-annihilation upconversion (TTA-UC) has attracted significant attention as an approach to harvest low energy solar photons that cannot be captured by conventional photovoltaic devices. However, device integration requires the design of solid-state TTA-UC materials that combine high upconversion efficiency with long term stability. Herein, we report an efficient solid-state TTA-UC system based on organic-inorganic hybrid polymers known as ureasils as hosts for the archetypal sensitiser/emitter pair of palladium(ii) octaethylporphyrin and diphenylanthracene. The role of the ureasil structure on the TTA-UC performance was probed by varying the branching and molecular weight of the organic precursor to tune the structural, mechanical, and thermal properties. Solid-state green-to-blue UC quantum yields of up to 1.86% were observed under ambient conditions. Notably, depending on the ureasil structure, UC emission could be retained for >70 days without any special treatment, including deoxygenation. Detailed analysis of the structure-function trends revealed that while a low glass transition temperature is required to promote TTA-UC molecular collisions, a higher inorganic content is the primary factor that determines the UC efficiency and stability, due to the inherent oxygen barrier provided by the silica nanodomains.

Coulomb interactions for mediator-enhanced sensitized triplet-triplet annihilation upconversion in solution.

Sensitized triplet-triplet annihilation upconversion offers an attractive possibility to replace a high-energy photon by two photons with lower energy through the combination of a light-harvesting triplet sensitizer and an annihilator for the formation of a fluorescent singlet state. Typically, high annihilator concentrations are required to achieve an efficient initial energy transfer and as a direct consequence the most highly energetic emission is often not detectable due to intrinsic reabsorption by the annihilator itself. Herein, we demonstrate that the addition of a charge-adapted mediator drastically improves the energy transfer efficiency at low annihilator concentrations via an energy transfer cascade. Inspired by molecular dyads and recent developments in nanocrystal-sensitized upconversion, our system exploits a concept to minimize intrinsic filter effects, while boosting the upconversion quantum yield in solution. A sensitizer-annihilator combination consisting of a ruthenium-based complex and 9,10-diphenylanthracene (DPA) is explored as model system and a sulfonated pyrene serves as mediator. The impact of opposite charges between sensitizer and mediator - to induce coulombic attraction and subsequently result in accelerated energy transfer rate constants - is analyzed in detail by different spectroscopic methods. Ion pairing and the resulting static energy transfer in both directions is a minor process, resulting in an improved overall performance. Finally, the more intense upconverted emission in the presence of the mediator is used to drive two catalytic photoreactions in a two-chamber setup, illustrating the advantages of our approach, in particular for photoreactions requiring oxygen that would interfere with the upconversion system.

Enhancing Triplet-Triplet Annihilation Upconversion of Pyrene Derivatives for Photoredox Catalysis via Molecular Engineering.

Triplet-triplet annihilation upconversion (TTA-UC) has the potential to enhance photoredox catalysis yield. It includes a sensitizer and an annihilator. Efficient and stable annihilators are essential for photoredox catalysis, yet only a few examples are reported. Herein, we designed four novel pyrene annihilators (1, 2, 3 and 4) via introducing aryl-alkynyl groups onto pyrene to systematically modulate their singlet and triplet energies. Coupled with platinum octaethylporphyrin (PtOEP), the TTA-UC efficiency is enhanced gradually as the number of aryl-alkynyl group increases. When combining 4 with palladium tetraphenyl-tetrabenzoporphyrin (PdTPTBP), we achieved the highest red-to-green upconversion efficiency (22.4±0.3 %) (out of a 50 % maximum) so far. Then, this pair was used to activate photooxidation of aryl boronic acid under red light (630 nm), which achieved a great improved reaction yield compared to that activated by green light directly. The results not only provide a design strategy for efficient annihilators, but also show the advantage of applying TTA-UC into improving the photoredox catalysis yield.

Developments and Challenges Involving Triplet Transfer across Organic/Inorganic Heterojunctions for Singlet Fission and Photon Upconversion.

In this Perspective, we provide an overview of recent advances in harvesting triplets for photovoltaic and photon upconversion applications from two angles. In singlet fission-sensitized solar cells, the triplets are harvested through a low band gap semiconductor such as Si. Recent literature has shown how a thin interlayer or orientation of the singlet fission molecule can successfully lead to triplet transfer. On the other hand, the integration of transition metal dichalcogenides (TMDCs) with suitable organic molecules has shown triplet-triplet annihilation upconversion (TTA-UC) of near-infrared photons. We consider the theoretical aspect of the triplet transfer process between a TMDC and organic semiconductors. We discuss possible bottlenecks that can limit the harvesting of energy from triplets and perspectives to overcome these.

Uncovering the Mechanisms of Triplet-Triplet Annihilation Upconversion Enhancement via Plasmonic Nanocavity Tuning.

The nonlinear conversion of photons from lower to higher energy is important for a wide range of applications, from quantum communications and optoelectronics to solar energy conversion and medicine. Triplet-triplet annihilation upconversion (TTA UC), which utilizes an absorber/emitter molecular pair, is a promising tool for upconversion applications requiring low intensity light such as photovoltaics, photocatalysis, and bioimaging. Despite demonstrations of efficient TTA UC in solution, practical applications have proven difficult, as thin films retard the necessary energy transfer steps and result in low emission yields. In this work, TTA UC emission from a thin film is greatly enhanced through integration into plasmonic nanogap cavities consisting of a silver mirror, a nanometer-scale polymer spacer containing a TTA molecular pair, and colloidally synthesized silver nanocubes. Mechanistic studies performed by varying the nanocube side length (45-150 nm) to tune the nanogap cavity resonance paired with simulations reveal absorption rate enhancement to be the primary operative mechanism in overall TTA UC emission enhancement. This absorption enhancement decreases the TTA UC threshold intensity by an order of magnitude and allows TTA UC emission to be excited with light up to 120 nm redder than the usable wavelength range for the control samples. Further, combined nanogap cavities composed of two distinct nanocube sizes result in surfaces which simultaneously enhance the absorption rate and emission rate. These dual-size nanogap cavities result in 45-fold TTA UC emission enhancement. In total, these studies present TTA UC emission enhancement, illustrate how the usable portion of the spectrum can be expanded for a given sensitizer-emitter pair, and develop both mechanistic understanding and design rules for TTA UC emission enhancement by plasmonic nanostructures.