Intermediate Triplet State Research Articles

Understanding of complex spin up-conversion processes in charge-transfer-type organic molecules

Despite significant progress made over the past decade in thermally activated delayed fluorescence (TADF) molecules as a material paradigm for enhancing the performance of organic light-emitting diodes, the underlying spin-flip mechanism in these charge-transfer (CT)-type molecular systems remains an enigma, even since its initial report in 2012. While the initial and final electronic states involved in spin-flip between the lowest singlet and lowest triplet excited states are well understood, the exact dynamic processes and the role of intermediate high-lying triplet (T) states are still not fully comprehended. In this context, we propose a comprehensive model to describe the spin-flip processes applicable for a typical CT-type molecule, revealing the origin of the high-lying T state in a partial molecular framework in CT-type molecules. This work provides experimental and theoretical insights into the understanding of intersystem crossing for CT-type molecules, facilitating more precise control over spin-flip rates and thus advancing toward developing the next-generation platform for purely organic luminescent candidates.

Benchmarking DFT Functionals for Excited-State Calculations of Donor–Acceptor TADF Emitters: Insights on the Key Parameters Determining Reverse Inter-System Crossing

The importance of intermediate triplet states and the nature of excited states has gained interest in recent years for the thermally activated delayed fluorescence (TADF) mechanism. It is widely accepted that simple conversion between charge transfer (CT) triplet and singlet excited states is too crude, and a more complex route involving higher-lying locally excited triplet excited states has to be invoked to witness the magnitude of the rate of reverse inter-system crossing (RISC) rates. The increased complexity has challenged the reliability of computational methods to accurately predict the relative energy between excited states as well as their nature. Here, we compare the results of widely used density functional theory (DFT) functionals, CAM-B3LYP, LC-ωPBE, LC-ω*PBE, LC-ω*HPBE, B3LYP, PBE0, and M06-2X, against a wavefunction-based reference method, Spin-Component Scaling second-order approximate Coupled Cluster (SCS-CC2), in 14 known TADF emitters possessing a diversity of chemical structures. Overall, the use of the Tamm-Dancoff Approximation (TDA) together with CAM-B3LYP, M06-2X, and the two ω-tuned range-separated functionals LC-ω*PBE and LC-ω*HPBE demonstrated the best agreement with SCS-CC2 calculations in predicting the absolute energy of the singlet S1, and triplet T1 and T2 excited states and their energy differences. However, consistently across the series and irrespective of the functional or the use of TDA, the nature of T1 and T2 is not as accurately captured as compared to S1. We also investigated the impact of the optimization of S1 and T1 excited states on ΔEST and the nature of these states for three different functionals (PBE0, CAM-B3LYP, and M06-2X). We observed large changes in ΔEST using CAM-B3LYP and PBE0 functionals associated with a large stabilization of T1 with CAM-B3LYP and a large stabilization of S1 with PBE0, while ΔEST is much less affected considering the M06-2X functional. The nature of the S1 state barely evolves after geometry optimization essentially because this state is CT by nature for the three functionals tested. However, the prediction of the T1 nature is more problematic since these functionals for some compounds interpret the nature of T1 very differently. SCS-CC2 calculations on top of the TDA-DFT optimized geometries lead to a large variation in terms of ΔEST and the excited-state nature depending on the chosen functionals, further stressing the large dependence of the excited-state features on the excited-state geometries. The presented work highlights that despite good agreement of energies, the description of the exact nature of the triplet states should be undertaken with caution.

Electroluminescence from a phthalocyanine monolayer encapsulated in a van der Waals tunnel diode

Monolayers of free base phthalocyanine (H2Pc) are grown on monolayer and few-layer exfoliated flakes of hexagonal boron nitride (hBN) which are subsequently integrated into a van der Waals tunnel diode. This heterostructure consists of two thin hBN flakes between which the H2Pc monolayer is sandwiched and also incorporates upper and lower few-layer graphene contacts. When a voltage is applied between the contacts, a tunnel current flows and the embedded molecules can be excited resulting in the emission of photons with wavelengths which are close to the peaks observed in photoluminescence. We also observe electroluminescence at voltages where the energy gained by a tunnelling electron is lower than the energy of the emitted photon implying a multi-electron excitation pathway which we attribute to the formation of an intermediate triplet state. Our results provide insights into the differences in excitation and relaxation of molecules in supramolecular monolayers and bulk crystals and we discuss how the alignment of the energy levels of the molecules and contact layers determine the emission process.

Efficient Reverse Intersystem Crossing in Carbene-Copper-Amide TADF Emitters via an Intermediate Triplet State.

The mechanism behind reverse intersystem crossing (rISC) in metal-based TADF emitters is still under debate. Thermal rISC necessitates small singlet/triplet energy gaps as realized in donor-acceptor systems with charge-transfer excited states. However, their associated spin-orbit couplings are too small to account for effective rISC. Here, we report the first nonadiabatic dynamics simulation of the rISC process in a carbene-copper(I)-carbazolyl TADF emitter. Efficient rISC on a picosecond time scale is demonstrated for an initial triplet minimum geometry that exhibits a perpendicular orientation of the ligands. The dynamics involves an intermediate higher-lying triplet state of metal-to-ligand charge transfer character (3 MLCT), which enables large spin-orbit couplings with the lowest singlet charge transfer state. The mechanism is completed in the S1 state, where the complex can return to a co-planar coordination geometry that presents high fluorescence efficiency.

An Oligomer Approach for Blue Thermally Activated Delayed Fluorescent Emitters Based on Twisted Donor-Acceptor Units.

The development of efficient blue donor-acceptor thermally activated delayed fluorescence (TADF) emitters remains a challenge. To enhance the efficiency of TADF-related processes of the emitter, we targeted a molecular design that would introduce a large number of intermediate triplet states between the lowest energy excited triplet (T1) and singlet (S1) excited states. Here, we introduce an oligomer approach using repetitive donor-acceptor units to gradually increase the number of quasi-degenerate states. In our design, benzonitrile (BN) moieties were selected as acceptors that are connected together via the amine donors, acting as bridges to adjacent BN acceptors. To preserve the photoluminescence emission wavelength across the series, we employed a design based on an ortho substitution pattern of the donors about the BN acceptor that induces a highly twisted conformation of the emitters, limiting the conjugation. Via a systematic photophysical study, we show that increasing the oligomer size allows for enhancement of the intersystem crossing and reverse intersystem crossing rates. We attribute the increasing intersystem crossing rate to the increasing number of intermediate triplet states along the series, confirmed by the time-dependent density functional theory. Overall, we report an approach to enhance the efficiency of TADF-related processes without changing the blue photoluminescence color.

General theory of light propagation and triplet generation for studies of spin dynamics and triplet dynamic nuclear polarisation

A general theory is presented describing the photo-excitation dynamics of transient, paramagnetic triplet states of aromatic molecules including their absorption properties in a molecular host crystal when irradiated by a pulsed laser beam. It is applied to the system of a pentacene doped naphthalene single crystal, where the photo-excitation of pentacene results in a highly non-equilibrium population of intermediate electronic triplet states. These paramagnetic states can be addressed to align the proton spins of the naphthalene host at moderate experimental conditions using dynamic nuclear polarisation (DNP). The photo-excitation profile and the resulting triplet state distribution, which is determined by the material and the laser parameters, leads to a corresponding proton polarisation profile. Measurements of the resulting polarisation inhomogeneity by spatially resolved neutron transmission confirm the theory. The theoretical model then allows the extraction of crucial parameters that enable quantitative investigations of the dynamics of spin systems. For applications of triplet DNP with pentacene-doped naphthalene crystals, polarisation maximum, homogeneity and build-up rate are key factors, and the theory allows the identification of optimal experimental parameters depending on the priorities placed on these factors.

Tailoring intersystem crossing of perylenediimide through chalcogen-substitution at bay-position: A theoretical perspective.

Molecular-scale design strategies for promoting intersystem crossing (ISC) in small organic molecules are ubiquitous in developing efficient metal-free triplet photosensitizers with high triplet quantum yield (ΦT). Air-stable and highly fluorescent perylenediimide (PDI) in its pristine form displays very small ISC compared to the fluorescence due to the large singlet-triplet gap (ΔES-T) and negligibly small spin-orbit coupling (SOC) between the lowest singlet (S1) and triplet state (T1). However, its ΦT can be tuned by different chemical and mechanical means that are capable of either directly lowering the ΔES-T and increasing SOC or introducing intermediate low-lying triplet states (Tn, n = 2, 3, …) between S1 and T1. To this end, herein, a few chalcogen (X = O, S, Se) bay-substituted PDIs (PDI-X2) are computationally modeled aiming at introducing geometrical-strain at the PDI core and also mixing nπ* orbital character to ππ* in the lowest singlet and triplet excited states, which altogether may reduce ΔES-T and also improve the SOC. Our quantum-chemical calculations based on optimally tuned range-separated hybrid reveal the presence of intermediate triplet states (Tn, n = 2, 3) in between S1 and T1 for all three PDI-X2 studied in dichloromethane. More importantly, PDI-X2 shows a significantly improved ISC rate than the pristine PDI due to the combined effects stemming from the smaller ΔES-T and the larger SOC. The calculated ISC rates follow the order as PDI-O2 < PDI-S2 < PDI-Se2. These research findings will be helpful in designing PDI based triplet photosensitizers for biomedical, sensing, and photonic applications.

Molecular structure analysis of 4-fluoro phenyl(4-methyl piperidin-1-yl) methanone and a comparative study of its optical, antimicrobial and antioxidant activities with 4-chloro phenyl (4-methyl piperidin-1-yl) methanone

A new fluoro derivative of 4-methyl piperidine (FPMPM) was synthesized by Scholten-Baumann condensation reaction, and the crystal structure was elucidated using single-crystal X-ray diffraction intensities. The molecules are arranged in monoclinic P21/n symmetry allowing for a dihedral angle of 36.76 (8)° observed between the mean plane of the benzene ring and the mean plane of the piperidine chair. Essentially projected non-bonded interactions were corroborated through Hirshfeld surface analysis. Predominant H…H and long-ranged halogen interactions packed with weak dispersion forces suggest the sizeable hydrophobic surface area. The chloro analogue (CPMPM) of FPMPM was compared for its FT-IR and FT-Raman spectra displaying their characteristic vibration modes of the functional groups. The bandgaps of 2.82 and 3.97 eV in FPMPM and CPMPM divulged by the Tauc's plots of UV–vis spectral data are concomitant with the optical band gaps disclosed by photoluminescence spectra. A longer delayed fluorescence lifetime of 31.5(8) and 33.1(1) ns with relatively high contribution confirmed the intermediate triplet state in the materials. The fast, prompt fluorescence decay of 3.72 (2) and 2.85 (1) ns in FPMPM and CPMPM with 54 (1) and 69 (1) % percent fractional contribution are promising shreds of evidence for the materials to act as an optical imaging fluorophore and an imminent scintillating material at moderate temperatures. Relatively moderate values of nonlinear susceptibility (3.44 and 3.85) × 10−6 (e. s. u.) and positive nonlinear absorption coefficient with z-scan measurements supported thermal concave lensing behavior and reverse saturable absorption in both the materials. Thermogravimetry coupled with Differential Scanning Calorimetry (DSC) declares the moderately low melting point (70.4 and 107 °C) for the material, FPMPM, and CPMPM, respectively. The F substituent in FPMPM possesses high hydrophobicity and lipophilicity, mitigating antibacterial activity, while moderate H…F and C-H…π interactions allow for susceptible antimicrobial activities. CPMPM exhibits robust antifungal activity against Trichoderma with reference to amphotericin-B. The antioxidant scavenging property is reflected by relatively high proton reactivity sites in FPMPM and hence relatively low % DPPH activity in CPMPM.

Space-Confined Donor-Acceptor Strategy Enables Fast Spin-Flip of Multiple Resonance Emitters for Suppressing Efficiency Roll-Off.

Multi-resonance boron-nitrogen-containing thermally activated delayed fluorescence (MR-TADF) emitters have experienced great success in assembling narrowband organic light-emitting diodes (OLEDs). However, the slow reverse intersystem crossing rate (kRISC ) of MR-emitters (103 -105 s-1 ) that will lead to severe device efficiency roll-off has received extensive attention and remains a challenging issue. Herein, we put forward a "space-confined donor-acceptor (SCDA)" strategy to accelerate RISC process. The introduction of SCDA units onto the MR-skeleton induces intermediate triplet states, which leads to a multichannel RISC process and thus increases kRISC . As illustrated examples, efficient MR-emitters have been developed with a sub-microsecond delayed lifetime and a high kRISC of 2.13×106 s-1 , which enables to assemble high-performance OLEDs with a maximum external quantum efficiency (EQEmax ) as high as 32.5 % and an alleviated efficiency roll-off (EQE1000 : 22.9 %).

Space‐Confined Donor‐Acceptor Strategy Enables Fast Spin‐Flip of Multiple Resonance Emitters for Suppressing Efficiency Roll‐Off

AbstractMulti‐resonance boron‐nitrogen‐containing thermally activated delayed fluorescence (MR‐TADF) emitters have experienced great success in assembling narrowband organic light‐emitting diodes (OLEDs). However, the slow reverse intersystem crossing rate (kRISC) of MR‐emitters (103–105 s−1) that will lead to severe device efficiency roll‐off has received extensive attention and remains a challenging issue. Herein, we put forward a “space‐confined donor‐acceptor (SCDA)” strategy to accelerate RISC process. The introduction of SCDA units onto the MR‐skeleton induces intermediate triplet states, which leads to a multichannel RISC process and thus increaseskRISC. As illustrated examples, efficient MR‐emitters have been developed with a sub‐microsecond delayed lifetime and a highkRISCof 2.13×106 s−1, which enables to assemble high‐performance OLEDs with a maximum external quantum efficiency (EQEmax) as high as 32.5 % and an alleviated efficiency roll‐off (EQE1000: 22.9 %).

Regiochemistry of Donor Dendrons Controls the Performance of Thermally Activated Delayed Fluorescence Dendrimer Emitters for High Efficiency Solution-Processed Organic Light-Emitting Diodes.

The potential of dendrimers exhibiting thermally activated delayed fluorescence (TADF) as emitters in solution‐processed organic light‐emitting diodes (OLEDs) has to date not yet been realized. This in part is due to a poor understanding of the structure–property relationship in dendrimers where reports of detailed photophysical characterization and mechanism studies are lacking. In this report, using absorption and solvatochromic photoluminescence studies in solution, the origin and character of the lowest excited electronic states in dendrimers with multiple dendritic electron‐donating moieties connected to a central electron‐withdrawing core via a para‐ or a meta‐phenylene bridge is probed. Characterization of host‐free OLEDs reveals the superiority of meta‐linked dendrimers as compared to the already reported para‐analogue. Comparative temperature‐dependent time‐resolved solid‐state photoluminescence measurements and quantum chemical studies explore the effect of the substitution mode on the TADF properties and the reverse intersystem crossing (RISC) mechanism, respectively. For TADF dendrimers with similarly small ∆E ST, it is observed that RISC can be enhanced by the regiochemistry of the donor dendrons due to control of the reorganization energies, which is a heretofore unexploited strategy that is distinct from the involvement of intermediate triplet states through a nonadiabatic (vibronic) coupling with the lowest singlet charge transfer state.

The role of the intermediate triplet state in iron-catalyzed multi-state C-H activation.

Efficient activation and functionalization of the C-H bond under mild conditions are of a great interest in chemical synthesis. We investigate the previously proposed spin-accelerated activation of the C(sp2)-H bond by a Fe(II)-based catalyst to clarify the role of the intermediate triplet state in the reaction mechanism. High-level electronic structure calculations on a small model of a catalytic system utilizing the coupled cluster with the single, double, and perturbative triple excitations [CCSD(T)] are used to select the density functional for the full-size model. Our analysis indicates that the previously proposed two-state quintet-singlet reaction pathway is unlikely to be efficient due to a very weak spin-orbit coupling between these two spin states. We propose a more favorable multi-state quintet-triplet-singlet reaction pathway and discuss the importance of the intermediate triplet state. This triplet state facilitates a spin-accelerated reaction mechanism by strongly coupling to both quintet and singlet states. Our calculations show that the C-H bond activation through the proposed quintet-triplet-singlet reaction pathway is more thermodynamically favorable than the single-state quintet and two-state singlet-quintet mechanisms.

Modulating the intersystem crossing mechanism of anthracene carboxyimide-based photosensitizers via structural adjustments and application as a potent photodynamic therapeutic reagent.

Herein, a series of compact anthracene carboxyimide (ACI) based donor-acceptor dyads were prepared by substituting bulky aryl moieties with various electron-donating ability to study the triplet-excited state properties. The ISC mechanism and triplet yield of the dyads were successfully tuned via structural manipulation. Efficient ISC (ΦΔ ≈ 99%) and long-lived triplet state (τT ≈ 122 μs) was observed for the orthogonal anthracene-labeled ACI derivative compared to the Ph-ACI and NP-ACI dyads, which showed fast triplet state decay (τT ≈ 7.7 μs). Femtosecond transient absorption study demonstrated the ultrafast charge separation (CS) and efficient charge recombination (CR) in the orthogonal dyads and ISC occurring via spin-orbit charge transfer (SOCT) mechanism (AN-ACI: τCS = 355 fs, τCR = 2.41 ns; PY-ACI: τCS = 321 fs, τCR = 1.61 ns), while in Ph-ACI and NP-ACI dyads triplet populate following the normal ISC channel (nπ* → ππ* transition), no CS was observed. We found that the attachment of suitable aryl donor moiety (AN- or PY-) to the ACI core can ensure the insertion of the intermediate triplet state, resulting in a small energy gap among charge separated state (CSS) and triplet state, which leads to efficient ISC in these derivatives. The SOCT-ISC-based AN-ACI dyad was confirmed to be a potent photodynamic therapeutic reagent; an ultra-low IC50 value (0.27 nM) that was nearly 214 times lower than that of the commercial Rose Bengal photosensitizer (57.8 nM) was observed.

BODIPY‐Based Photodynamic Agents for Exclusively Generating Superoxide Radical over Singlet Oxygen

AbstractDeveloping Type‐I photosensitizers is considered as an efficient approach to overcome the deficiency of traditional photodynamic therapy (PDT) for hypoxic tumors. However, it remains a challenge to design photosensitizers for generating reactive oxygen species by the Type‐I process. Herein, we report a series of α,β‐linked BODIPY dimers and a trimer that exclusively generate superoxide radical (O2−.) by the Type‐I process upon light irradiation. The triplet formation originates from an effective excited‐state relaxation from the initially populated singlet (S1) to triplet (T1) states via an intermediate triplet (T2) state. The low reduction potential and ultralong lifetime of the T1 state facilitate the efficient generation of O2−. by inter‐molecular charge transfer to molecular oxygen. The energy gap of T1‐S0 is smaller than that between 3O2 and 1O2 thereby precluding the generation of singlet oxygen by the Type‐II process. The trimer exhibits superior PDT performance under the hypoxic environment.

BODIPY-Based Photodynamic Agents for Exclusively Generating Superoxide Radical over Singlet Oxygen.

Developing Type-I photosensitizers is considered as an efficient approach to overcome the deficiency of traditional photodynamic therapy (PDT) for hypoxic tumors. However, it remains a challenge to design photosensitizers for generating reactive oxygen species by the Type-I process. Herein, we report a series of α,β-linked BODIPY dimers and a trimer that exclusively generate superoxide radical (O2-. ) by the Type-I process upon light irradiation. The triplet formation originates from an effective excited-state relaxation from the initially populated singlet (S1 ) to triplet (T1 ) states via an intermediate triplet (T2 ) state. The low reduction potential and ultralong lifetime of the T1 state facilitate the efficient generation of O2-. by inter-molecular charge transfer to molecular oxygen. The energy gap of T1 -S0 is smaller than that between 3 O2 and 1 O2 thereby precluding the generation of singlet oxygen by the Type-II process. The trimer exhibits superior PDT performance under the hypoxic environment.

Electron spin resonance resolves intermediate triplet states in delayed fluorescence

Molecular organic fluorophores are currently used in organic light-emitting diodes, though non-emissive triplet excitons generated in devices incorporating conventional fluorophores limit the efficiency. This limit can be overcome in materials that have intramolecular charge-transfer excitonic states and associated small singlet-triplet energy separations; triplets can then be converted to emissive singlet excitons resulting in efficient delayed fluorescence. However, the mechanistic details of the spin interconversion have not yet been fully resolved. We report transient electron spin resonance studies that allow direct probing of the spin conversion in a series of delayed fluorescence fluorophores with varying energy gaps between local excitation and charge-transfer triplet states. The observation of distinct triplet signals, unusual in transient electron spin resonance, suggests that multiple triplet states mediate the photophysics for efficient light emission in delayed fluorescence emitters. We reveal that as the energy separation between local excitation and charge-transfer triplet states decreases, spin interconversion changes from a direct, singlet-triplet mechanism to an indirect mechanism involving intermediate states.

Nonradiative Triplet Loss Suppressed in Organic Photovoltaic Blends with Fluoridated Nonfullerene Acceptors

In organic photovoltaic (OPV) blends, photogenerated excitons dissociate into charge-separated electrons and holes at donor/acceptor interfaces. The bimolecular recombination of spin-uncorrelated electrons and holes may cause nonradiative loss by forming the low-lying triplet excited states (T1) via the intermediate charge-transfer triplet states. Here, we show that such a spin-related loss channel can be suppressed in the OPV blends with fluorinated nonfullerene acceptors (NFAs). By combining ultrafast optical spectroscopy and triplet sensitization measurements, the T1 states at the acceptors have been observed to generate from the charge-separated electrons and holes in the OPV blends with a same polymer donor and two sets of NFAs with and without fluorination. The triplet formation is largely suppressed and the lifetime of charge carrier is markedly prolonged in the blends with fluorinated NFAs. The fluorination effect on the charge dynamics can be ascribed to the modified energy alignment between the triplet excited states of charge-transfer and locally excited characters as supported by quantum chemical computation. Our findings explain the mechanism responsible for the improved photocurrent generation in the OPV blends with fluorinated NFAs, suggesting that manipulating the energy landscape of triplet excited states is a promising strategy for further optimizing OPV devices.

Planar and Rigid Pyrazine‐Based TADF Emitter for Deep Blue Bright Organic Light‐Emitting Diodes

AbstractTwo blue thermally activated delayed fluorescence (TADF) emitters bearing di‐tert‐butyl carbazoles as the electron donor groups and pyrazine (DTCz‐Pz) or dipyrazine (DTCz‐Pz) as the electron acceptor are presented. The DFT calculations predict DTCz‐Pz and DTCz‐DPz to possess high S1 energies (3.19 eV and 3.08 eV, respectively), and relatively large ΔEST values (0.52 eV and 0.56 eV, respectively). The closely layered intermediate triplet states between S1 and T1, predicted by DFT calculations, are expected to facilitate the reverse intersystem crossing (RISC) and improve spin‐vibronic coupling efficiency between the excited states, even the relatively larger ΔESTs. The ΔESTs for DTCz‐Pz and DTCz‐DPz are 0.27 eV and 0.38 eV, and both molecules show high photoluminescence quantum yields (65 %, and 70 %, respectively). The decay lifetimes show temperature dependence in a PPT host, which is consistent with the fact that both molecules are TADF emitters in PPT. The OLEDs based on DTCz‐Pz exhibit deep blue emission with λEL of 460 nm and CIE of (0.15, 0.16). The maximum external quantum efficiency (EQEmax) reaches 11.6 %, with a maximum luminance (Lmax) of up to 6892 cd m−2, while the device based on DTCz‐DPz exhibits sky blue emission with λEL of 484 nm and CIE of (0.15, 0.30), an EQEmax of 7.2 %, and Lmax of 8802 cd m−2.

Deposition of the Spin Crossover FeII -Pyrazolylborate Complex on Au(111) Surface at the Molecular Level.

The interaction at the molecular level of the spin-crossover (SCO) FeII ((3,5-(CH3 )2 Pz)3 BH)2 complex with the Au(111) surface is analyzed by means of rPBE periodic calculations. Our results show that the adsorption on the metallic surface enhances the transition energy, increasing the relative stability of the low spin (LS) state. The interaction indeed is spin-dependent, stronger for the low spin than the high spin (HS) state. The different strength of the Fe ligand field at low and high temperature manifests on the nature, spatial extension and relative energy of the states close to the Fermi level, with a larger metal-ligand hybridization in the LS state. This feature is of relevance for the differential adsorption of the LS and HS molecules, the spin-dependent conductance, and for the differences found in the corresponding STM images, correctly reproduced from the density of states provided by the rPBE calculations. It is expected that this spin dependence will be a general feature of the SCO molecule-substrate interaction, since it is rooted in the different ligand field of Fe site at low and high temperatures, a common hallmark of the FeII SCO complexes. Finally, the states involved in the LIESST phenomenon has been identified through NEVPT2 calculations on a model reaction path. A tentative pathway for the photoinduced LS→HS transition is proposed, that does not involve the intermediate triplet states, and nicely reproduces both the blue laser wavelength required for the activation, and the wavelength of the reverse HS → LS transition.

Long Persistent Luminescence Enabled by Dissociation of Triplet Intermediate States in an Organic Guest/Host System.

Organic guest/host systems with long persistent luminescence benefiting from the formation of a long-lived charge-separated state have recently been demonstrated. However, the photogeneration mechanism of such key charge-separated states remains elusive. Here, we report the identification of intermediate triplet states with mixed local excitation and charge-transfer character that connect the initial photoexcited singlet states and the long-lived charge-separated states. Using time-resolved optical spectroscopy, we observe the intersystem crossing from photoexcited singlet charge-transfer states to triplet intermediate states on a time scale of ∼52 ns. Temperature-dependent measurements reveal that the long-lived triplet intermediate states ensure a relatively high efficiency of diffusion-driven charge separation to form the charge-separated state responsible for LPL emission. The findings in this work provide a rationale for the development of new LPL materials that may also improve our understanding of the mechanism of photon-to-charge conversion in many organic optoelectronic devices.