Triplet-triplet Annihilation Photon Upconversion Research Articles

Exploring Sensitized Photon Upconversion - From Past to Present.

The conversion of low energy photons into high energy photons via triplet-triplet annihilation (TTA) photon upconversion (UC) has become a promising avenue for furthering a wide range of optoelectronic applications. Through the decades of research, many combinations of triplet sensitizer species and annihilator molecules have been investigated unlocking the entire visible spectrum upon proper pairings of sensitizer and annihilator identities. Here, we reflect upon the seminal works which lay the foundation for TTA-UC originating from solution-based methods and highlight the recent advances made within the solid state primarily focusing on perovskite-based triplet generation.

Electronic Couplings for Triplet-Triplet Annihilation Upconversion in Crystal Rubrene.

Triplet-triplet annihilation photon upconversion (TTA-UC) is a process able to repackage two low-frequency photons into light of higher energy. This transformation is typically orchestrated by the electronic degrees of freedom within organic compounds possessing suitable singlet and triplet energies and electronic couplings. In this work, we propose a computational protocol for the assessment of electronic couplings crucial to TTA-UC in molecular materials and apply it to the study of crystal rubrene. Our methodology integrates sophisticated yet computationally affordable approaches to quantify couplings in singlet and triplet energy transfer, the binding of triplet pairs, and the fusion to the singlet exciton. Of particular significance is the role played by charge-transfer states along the b-axis of rubrene crystal, acting as both partial quenchers of singlet energy transfer and mediators of triplet fusion. Our calculations identify the π-stacking direction as holding notable triplet energy transfer couplings, consistent with the experimentally observed anisotropic exciton diffusion. Finally, we have characterized the impact of thermally induced structural distortions, revealing their key role in the viability of triplet fusion and singlet fission. We posit that our approaches are transferable to a broad spectrum of organic molecular materials, offering a feasible means to quantify electronic couplings.

Triplet-Mediator Ligand-Protected Metal Nanocluster Sensitizers for Photon Upconversion.

Triplet-triplet annihilation photon upconversion (TTA-UC) is attracting a great deal of attention as a viable approach to exploit unutilized wavelengths of light in solar-driven devices. Recently, ligand-protected metal nanoclusters have emerged as a compelling platform for serving as triplet sensitizers for TTA-UC. In this study, we developed an atomically precise, triplet-mediator ligand (TL)-protected metal nanocluster, Au2Cu6(S-Adm)6[P(DPA)3]2 (Au2Cu6DPA; S-Adm = 1-adamanthanethiolate, DPA = 9,10-diphenylanthracene). In Au2Cu6DPA, the excitation of the Au2Cu6 core rapidly generates a metal-to-ligand charge transfer state, followed by the formation of the long-lived triplet state (approximately 150 μs) at a DPA site in the TL. By combining Au2Cu6DPA with a DPA annihilator, we achieved a red-to-blue upconversion quantum yield (ΦUCg) of 20.7 ± 0.4% (50% max.) with a low threshold excitation intensity of 36 mW cm-2 at 640 nm. This quantum yield almost reaches the maximum limit achievable using a DPA annihilator and establishes a record-setting value, outperforming previously reported nanocrystal and nanocluster sensitizers. Furthermore, strong upconversion emission based on a pseudo-first-order TTA process was observed under 1 sun illumination, indicating that the Au2Cu6DPA sensitizer holds promise for applications in solar-energy-based systems.

Tuning the triplet population of arylselanyl-BODIPY photosensitizers through substituents engineering for triplet-triplet annihilation photon upconversion with perylene

Organic triplet-triplet annihilation photon upconversion (TTA-UC) systems have attracted considerable attention owing to their promising applicability in solar energy harvesting, optoelectronic devices, photocatalysts, and bio-imaging. In this study, a series of BODIPYs prepared by incorporating substituted/ unsubstituted arylselenium groups, 1 (R = H), 2 (R = OMe), and 3 (R = F), were evaluated as triplet photosensitizers for TTA-UC. Direct Se-C bond formation on the BODIPY core provided a facile intersystem crossing (ISC) channel from the excited singlet state to the metastable triplet state, being the most effective in 2, as inferred from the singlet oxygen generation experiments, possibly because of the n-electron arising from the OMe group. The UC behavior of systems comprising the sensitizers and perylene as the acceptor in deaerated toluene was investigated using a 524 nm-wavelength laser to detect upconverted emission at 449 nm; thus, the UC yield decreased in the order of 21% for 3 > 16% for 2 > 12% for 1. This trend is consistent with the Stern-Volmer constants calculated from the quenched triplet state lifetimes of the sensitizers as a function of the concentration of the perylene quencher. This suggests that the UC efficiency was mainly governed by the intermolecular triplet-triplet energy transfer (TTET) process between arylselanyl-BODIPY photosensitizers and the perylene acceptor. This result was rationalized by the efficient population of the long-lived triplet excited state of the sensitizer, which is advantageous for diffusion-controlled TTA-UC behavior.

Diarylethene Isomerization by Using Triplet-Triplet Annihilation Photon Upconversion.

Green-to-blue triplet-triplet annihilation photon upconversion with the well-studied upconversion pair 9,10-diphenylanthracene (DPA)/platinum octaethylporphyrin (PtOEP) was used to reversibly drive the photoisomerization of diarylethene (DAE) photoswitches by using visible light. By carefully selecting the kinetic and spectral properties of the molecular system as well as the experimental geometry, a single green light source can be used to selectively trigger both the ring-opening and the ring-closing reactions, whilst also inducing fluorescence from the colored closed isomer that can be used as a readout to monitor the isomerization process in situ. The upconversion solution and the DAE solution are kept physically separated, allowing them to be characterized both concomitantly and individually without further separation processes. The ring-closing reaction using upconverted photons was quantified and compared to the efficiency of direct isomerization with ultraviolet light.

Photochemically deoxygenating micelles for protecting TTA-UC against oxygen quenching.

Pluronic F127, P123 and cross-linked F127 diacrylate micelles are photochemically deoxygenating nanocapsules in which oxygen could be removed by photochemical reaction with a surfactant and efficient triplet-triplet annihilation photon upconversion (TTA-UC) can be achieved in air. The efficiency of TTA-UC under air is comparable to that under deoxygenated conditions.

Entropy-Powered Endothermic Energy Transfer from CsPbBr3 Nanocrystals for Photon Upconversion.

Colloidal semiconductor nanocrystals as triplet photosensitizers are characterized by a negligible intersystem crossing energy loss as compared to that of traditional molecular sensitizers. This property in principle allows for a large apparent anti-Stokes shift in sensitized triplet-triplet annihilation photon upconversion (TTA-UC) for a variety of applications. In previous systems, however, this advantage is largely erased by the energy loss associated with energy transfer from nanocrystals to surface-anchored triplet transmitter molecules. Here we report visible-to-ultraviolet TTA-UC from 473 to 355 nm, corresponding to an apparent anti-Stokes shift of 0.87 eV, with a quantum efficiency that reaches 4.5% (normalized at 100%). The system consists of CsPbBr3 nanocrystal sensitizers, phenanthrene transmitters, and diphenyloxazole annihilators. Time-resolved spectroscopy reveals that triplet energy transfer from CsPbBr3 nanocrystals to phenanthrene can be endothermic yet efficient thanks to a sizable entropic gain. This study exemplifies how entropic effects can be harnessed to enhance or control a plethora of applications with nanocrystals as photosensitizers.

Triplet-triplet annihilation photon-upconversion in hydrophilic media with biorelevant cholesteryl triplet energy acceptors

We report two new biorelevant cholesteryl-based triplet energy acceptors, derivatives of DPA or 9,10-diphenylanthracene (C–DPA and C2–DPA). Using two different triplet sensitizers: QDN (ET ≈ 1.67 eV in PEG200) and PdTPP (ET ≈ 1.78 eV in PEG200), we were able to achieve both endothermic (with QDN) and exothermic (with PdTPP) triplet sensitization of DPA, C–DPA and C2–DPA in hydrophilic PEG200 media. While the maximum rate of triplet energy transfer (TET) was achieved with PdTPP and DPA (kTET = 4.7 × 107 M−1 s−1), for the cholesteryl-based acceptors, we found that the kinetic of the TET process was dependent upon the concentration of the acceptor. For PdTPP/C–DPA pair, the rate of the dynamic triplet energy quenching was kTET = 1.9 × 107 M−1 s−1; however, at higher concentrations of the quencher, the system reached a stationary state due to formation of self-assembled sub-domains of C–DPA that likely slowed the TET process. It was also found that this aggregation of C–DPA in PEG200 led to a 3.5 folds increase in the Ith compared to 133 mW cm2 for DPA. Subsequently, we estimated the ΦUC for these donor/acceptor pairs: QDN/DPA, PdTPP/DPA, and PdTPP/C–DPA. With respect to the estimated threshold intensity (Ith), we found that the quantum yields of TTA-UC were 2 ≤ QYUC≤12%.

Steering Nanohelix and Upconverted Circularly Polarized Luminescence by Using Completely Achiral Components.

Enormous attention has been paid to upconverted circularly polarized luminescence (UC-CPL). However, so far, chiral species are still needed in UC-CPL materials, either through the covalent or noncovalent bond. Here, we report a general supramolecular coassembly approach for the fabrication of UC-CPL systems from completely achiral components. We have found that an achiral C3-symmetric molecule could form a chiral nanohelix through symmetry breaking, which could serve as a general helical platform to endow achiral guests with induced chirality and CPL activity. Two different photon upconversion systems, namely, triplet-triplet annihilation photon upconversion (TTA-UC) donor/acceptor pairs and inorganic lanthanide upconversion nanoparticles (UCNPs), are selected. When these two systems coassembled with the chiral nanohelix made from an achiral C3-symmetric molecule, hybrid nanohelix structures formed and UC-CPL activity was induced. Through such an approach, we demonstrated that the fabrication of the UC-CPL materials does not require any chiral molecules. Moreover, we have shown that the polarization of UC-CPL can be tuned by the helicity of the nanohelix, which could be controlled through the seeded vortex. Our work provides a general approach for designing tunable UC-CPL materials from completely achiral motifs, which largely expands the research scope of the CPL materials.

Controlling the triplet states and their application in external stimuli-responsive triplet–triplet-annihilation photon upconversion: from the perspective of excited state photochemistry

The property of organic light-responsive materials is determined by their electronic excited states to a large extent, for instance, the radiative decay rate constants, redox potentials, and lifetimes. Tuning the excited state properties with external stimuli will lead to versatile functional materials; a representative example is the fluorescence molecular probes, in which the singlet excited states are controlled by the external stimuli, i.e., by interaction with the analytes. In comparison, controlling the triplet excited state with external stimuli has been rarely reported, although it is also crucial for the development of novel materials for targeted photodynamic therapy (PDT) reagents and phosphorescent molecular probes. The reported results show that the principles used in singlet excited state tuning are unable to be simply applied to the triplet excited state. In this review article, we summarized the recent results on controlling the triplet excited states by the external stimuli (chemical or light), and the application of the triplet state tuning in the chemical/light controllable triplet-triplet-annihilation upconversion (TTA UC). We discussed the methods for the control of the triplet states, as well as singlet excited state, for the purpose of controlling the TTA UC. Both successful and unsuccessful methods are discussed. This information is helpful for understanding the photophysical processes in which the triplet excited state is involved, and the development of novel external stimuli-responsive triplet photosensitizers.

Covalent incorporation of diphenylanthracene in oxotriphenylhexanoate organogels as a quasi-solid photon upconversion matrix.

Triplet-triplet annihilation photon upconversion (TTA-UC) in solid state assemblies are desirable since they can be easily incorporated into devices such as solar cells, thus utilizing more of the solar spectrum. Realizing this is, however, a significant challenge that must circumvent the need for molecular diffusion, poor exciton migration, and detrimental back energy transfer among other hurdles. Here, we show that the above-mentioned issues can be overcome using the versatile and easily synthesized oxotriphenylhexanoate (OTHO) gelator that allows covalent incorporation of chromophores (or other functional units) at well-defined positions. To study the self-assembly properties as well as its use as a TTA-UC platform, we combine the benchmark couple platinum octaethylporphyrin as a sensitizer and 9,10-diphenylanthracene (DPA) as an annihilator, where DPA is covalently linked to the OTHO gelator at different positions. We show that TTA-UC can be achieved in the chromophore-decorated gels and that the position of attachment affects the photophysical properties as well as triplet energy transfer and triplet-triplet annihilation. This study not only provides proof-of-principle for the covalent approach but also highlights the need for a detailed mechanistic insight into the photophysical processes underpinning solid state TTA-UC.

Photon Upconversion in TTA-Inducing Ionic Liquids: Pinpointing the Role of IL Nanostructured Media Using MD Simulations.

The use of task-specific chromophoric ionic liquids as energy transfer media in triplet-triplet annihilation photon upconversion (TTA-UC) processes has produced several examples of systems with signifficantly enhanced performances. In this work, we use molecular dynamics simulations to probe the relation between the nanostructure of chromophoric ionic liquids and their ability to achieve high TTA-UC quantum yields. The existing atomistic and systematic force fields commonly used to model different ionic liquids are extended to include substituted anthracene moieties, thus allowing the modeling of several chromophoric ionic liquids. The simulation results show that the polar network of the ionic liquids can orient the anthracene moieties within the nonpolar domains preventing direct contacts between them but allowing orientations at the optimal distance for triplet energy migration.

Water-Dispersible Triplet-Triplet Annihilation Photon Upconversion Particle: Molecules Integrated in Hydrophobized Two-Dimensional Interlayer Space of Montmorillonite and Their Application for Photocatalysis in the Aqueous Phase.

Green incident light (λ = ∼500 nm) is converted to blue light (λ = 400-450 nm) in air using bulky alkylammonium (DMDOA+), 9,10-diphenylanthracene (DPA), and Ru(dmb)32+ (dmb = 4,4'-dimethyl-2,2'-bipyridine) intercalated in a layered clay compound called "montmorillonite" [MMT-DMDOA+-DPA-Ru(dmb)32+]. The two-dimensional interstitial space has an interlayer spacing of a few nanometers. Emitter DPA is present in this interlayer spacing, having an intermolecular distance of approximately 3.0 nm at a high concentration. Sensitizer Ru(dmb)32+ is relatively dilute, having an intermolecular distance of 47 nm. The emission decay measurements and quantitative evaluation of the emission intensity demonstrate that blue light emission is induced by sequential processes, which consist of a triplet-triplet (T-T) energy transfer reaction from Ru(dmb)32+ to DPA and T-T annihilation of DPA molecules. From thermogravimetry and Fourier transform infrared spectra measurements, we observe that the cointercalated alkylammonium acts as a waterproof agent to prevent quenching of the molecules in the excited triplet states by H2O. Finally, we demonstrate a photocatalytic decomposition of Rhodamine B dissolved in H2O-containing MMT-DMDOA+-DPA-Ru(dmb)32+ and Pt-deposited WO3 photocatalyst, where wavelength of incident light (λ > 440 nm) is longer than the absorption edge of WO3 photocatalyst. The mechanism of photocatalytic decomposition is the following: (i) the incident long wavelength light is upconverted to 400-450 nm light by MMT-DMDOA+-DPA-Ru(dmb)32+, and then, (ii) WO3 photocatalyst is excited by the generated 400-450 nm light, and finally, (iii) Rhodamine B is decomposed on the Pt cocatalyst induced by the holes in a valence band of WO3.

Annihilation Versus Excimer Formation by the Triplet Pair in Triplet-Triplet Annihilation Photon Upconversion.

The triplet pair is the key functional unit in triplet–triplet annihilation photon upconversion. The same molecular properties that stabilize the triplet pair also allow dimers to form on the singlet energy surface, creating an unwanted energy relaxation pathway. Here we show that excimer formation most likely is a consequence of a triplet dimer formed before the annihilation event. Polarity-dependent studies were performed to elucidate how to promote wanted emission pathways over excimer formation. Furthermore, we show that the yield of triplet–triplet annihilation is increased in higher-viscosity solvents. The results will bring new insights in how to increase the upconversion efficiency and how to avoid energy-loss channels.

Dual Upconverted and Downconverted Circularly Polarized Luminescence in Donor-Acceptor Assemblies.

Through mimicking both the chiral and energy transfer in an artificial self-assembled system, not only was chiral transfer realized but also a dual upconverted and downconverted energy transfer system was created that emit circularly polarized luminescence. The individual chiral π-gelator can self-assemble into a nanofiber exhibiting supramolecular chirality and circularly polarized luminescence (CPL). In the presence of an achiral sensitizer PdII octaethylporphyrin derivative, both chirality transfer from chiral gelator to achiral sensitizer and triplet-triplet energy transfer from excited sensitizer to chiral gelator could be realized. Upconverted CPL could be observed through a triplet-triplet annihilation photon upconversion (TTA-UC), while downconverted CPL could be obtained from chirality-transfer-induced emission of the achiral sensitizer. The interplay between chiral energy acceptor and achiral sensitizer promoted the communication of chiral and excited energy information.

The Janus-faced chromophore: a donor-acceptor dyad with dual performance in photon up-conversion.

An electron donor-acceptor dyad based on BODIPY (acceptor) and anthracene (donor) plays either the role of sensitizer or emitter in triplet-triplet annihilation photon up-conversion (TTA-UC). This Janus-like behavior was achieved via altering the relative ordering of charge-transfer and local excited state energies in the dyad through the polarity of TTA-UC media.

Molecular Road Map to Tuning Ground State Absorption and Excited State Dynamics of Long-Wavelength Absorbers.

Realizing chromophores that simultaneously possess substantial near-infrared (NIR) absorptivity and long-lived, high-yield triplet excited states is vital for many optoelectronic applications, such as optical power limiting and triplet-triplet annihilation photon upconversion (TTA-UC). However, the energy gap law ensures such chromophores are rare, and molecular engineering of absorbers having such properties has proven challenging. Here, we present a versatile methodology to tackle this design issue by exploiting the ethyne-bridged (polypyridyl)metal(II) (M; M = Ru, Os)-(porphinato)metal(II) (PM'; M' = Zn, Pt, Pd) molecular architecture (M-(PM')n-M), wherein high-oscillator-strength NIR absorptivity up to 850 nm, near-unity intersystem crossing (ISC) quantum yields (ΦISC), and triplet excited-state (T1) lifetimes on the microseconds time scale are simultaneously realized. By varying the extent to which the atomic coefficients of heavy metal d orbitals contribute to the one-electron excitation configurations describing the initially prepared singlet and triplet excited-state wave functions, we (i) show that the relative magnitudes of fluorescence (k0F), S1 → S0 nonradiative decay (knr), S1 → T1 ISC (kISC), and T1 → S0 relaxation (kT1→S0) rate constants can be finely tuned in M-(PM')n-M compounds and (ii) demonstrate designs in which the kISC magnitude dominates singlet manifold relaxation dynamics but does not give rise to T1 → S0 conversion dynamics that short-circuit a microseconds time scale triplet lifetime. Notably, the NIR spectral domain absorptivities of M-(PM')n-M chromophores far exceed those of classic coordination complexes and organic materials possessing similarly high yields of triplet-state formation: in contrast to these benchmark materials, this work demonstrates that these M-(PM')n-M systems realize near unit ΦISC at extraordinarily modest S1-T1 energy gaps (∼0.25 eV). This study underscores the photophysical diversity of the M-(PM')n-M platform and presents a new library of long-wavelength absorbers that efficiently populate long-lived T1 states.

Photon upconversion with directed emission.

Photon upconversion has the potential to increase the efficiency of single bandgap solar cells beyond the Shockley Queisser limit. Efficient light management is an important point in this context. Here we demonstrate that the direction of upconverted emission can be controlled in a reversible way, by embedding anthracene derivatives together with palladium porphyrin in a liquid crystalline matrix. The system is employed in a triplet-triplet annihilation photon upconversion scheme demonstrating controlled switching of directional anti Stokes emission. Using this approach an emission ratio of 0.37 between the axial and longitudinal emission directions and a directivity of 1.52 is achieved, reasonably close to the theoretical maximal value of 2 obtained from a perfectly oriented sample. The system can be switched for multiple cycles without any visible degradation and the speed of switching is only limited by the intrinsic rate of alignment of the liquid crystalline matrix.

Hyperbranched unsaturated polyphosphates as a protective matrix for long-term photon upconversion in air.

The energy stored in the triplet states of organic molecules, capable of energy transfer via an emissive process (phosphorescence) or a nonemissive process (triplet-triplet transfer), is actively dissipated in the presence of molecular oxygen. The reason is that photoexcited singlet oxygen is highly reactive, so the photoactive molecules in the system are quickly oxidized. Oxidation leads to further loss of efficiency and various undesirable side effects. In this work we have developed a structurally diverse library of hyperbranched unsaturated poly(phosphoester)s that allow efficient scavenging of singlet oxygen, but do not react with molecular oxygen in the ground state, i.e., triplet state. The triplet-triplet annihilation photon upconversion was chosen as a highly oxygen-sensitive process as proof for a long-term protection against singlet oxygen quenching, with comparable efficiencies of the photon upconversion under ambient conditions as in an oxygen-free environment in several unsaturated polyphosphates. The experimental results are further correlated to NMR spectroscopy and theoretical calculations evidencing the importance of the phosphate center. These results open a technological window toward efficient solar cells but also for sustainable solar upconversion devices, harvesting a broad-band sunlight excitation spectrum.

All Organic Nanofibers As Ultralight Versatile Support for Triplet-Triplet Annihilation Upconversion.

We present a method for the fabrication of ultralight upconverting mats consisting of rigid polymer nanofibers. The mats are prepared by simultaneously electrospinning an aqueous solution of a polymer with pronounced oxygen-barrier properties and functional nanocapsules containing a sensitizer/emitter couple optimized for triplet-triplet annihilation photon upconversion. The optical functionality of the nanocapsules is preserved during the electrospinning process. The nanofibers demonstrate efficient upconversion fluorescence centered at λmax = 550 nm under low intensity excitation with a continuous wave laser (λ = 635 nm, power = 5 mW). The pronounced oxygen-barrier property of the polymer matrix may efficiently prevent the oxygen penetration so upconversion fluorescence is registered in ambient atmosphere. The demonstrated method can be used for the production of upconverting ultralight porous coatings for sensors or upconverting membranes with freely variable thickness for solar cells.