Exciton, Excimer, Exciplex: Study of Triplet State Harvesting in Organic Molecules for Organic Light-Emitting Diode Applications

Triplet state harvesting is an important issue in the area of organic electronics, including organic light emitting diode (OLED) technology that has already entered the global market. In the aim to achieve efficient light-emitting diodes the photophysical properties of OLED emitters need to be understood in great detail. This work is devoted to triplet state harvesting in OLEDs. In this work a set of triplet-harvesting systems comprising exciton, excimer or exciplex emitters are characterized and used to fabricate prototype devices. The first system is based on metal-free emitters, using acridone or phenothiazine, which show thermally activated delayed fluorescence (TADF) or room-temperature phosphorescence (RTP). The competition between the rate of deactivation pathways affecting the triplet state and the reverse intersystem crossing (RISC) rate determine whether these molecules emit through TADF or RTP. The second system explores the effects of different substitution patterns on the properties of excitonic tetradentate ONNO Pt(II) complexes, and their performance in OLEDs, revealing a complicated host-to-guest energy transfer mechanism in doped films. The third work in this thesis explores the properties of newly synthesized Pt(II) metal complexes that have been found to efficiently form photoluminescent excimers and have strong potential to be used in solution-processed OLED devices. The photophysical characterisation of these complexes doped in film has revealed co-existence of excimer and aggregate emissions. Finally, the last two works in this thesis are focused on small molecule and polymer-based exciplex blends that exhibit efficient TADF emissions and can be used to fabricate solution-processed or vacuum-deposited OLEDs. The photophysics of these exciplex systems is characterised in-depth and undoubtedly demonstrates that local triplet states are not involved in the RISC process in this blends, which is in clear contrast with most exciton small molecule TADF systems. Furthermore, in this work a clear rationale for the observation of emission decaying in power law regimes is obtained for the first time.

Recent advances in highly-efficient near infrared OLED emitters

Near infrared (NIR) light (700–1400 nm) can be used in numerous biological/medical as well as technological applications. In this work we review the most recent examples of highly efficient NIR organic light-emitting diode (OLED) emitters among the most relevant types of luminophores: platinum(II), iridium(III), and osmium(II) complexes, unimolecular thermally activated delayed fluorescence (TADF) emitters and exciplexes, fluorescent dyes, and the emerging group of stable luminescent radicals. We dive into the structural design principles of emitters with improved NIR efficiency. In our discussion we consider unimolecular emission as well as that arising from aggregated luminophores, as the latter often leads to a longer wavelength NIR. Our analysis of numerous emitters from various groups concludes, without a doubt, that platinum(II) complexes present superior efficiency in nearly all wavelengths from 700 to 1000 nm. We report on an apparent NIR boundary line, which appears to be a current limitation for NIR OLED efficiency. Presently, virtually only platinum(II) complexes exceed the efficiency limit set out by this boundary. So far efficient OLEDs, i.e. >1% external quantum efficiency, emitting significantly beyond 1000 nm have not yet been reported

Recent advances in highly-efficient near infrared OLED emitters

dos Santos P.L., Stachelek P., Takeda Y., et al. Recent advances in highly-efficient near infrared OLED emitters. Materials Chemistry Frontiers 8, 1731 (2024); https://doi.org/10.1039/D3QM01067H.Near infrared (NIR) light (700-1400 nm) can be used in numerous biological/medical as well as technological applications. In this work we review the most recent examples of highly efficient NIR organic light-emitting diode (OLED) emitters among the most relevant types of luminophores: platinum(ii), iridium(iii), and osmium(ii) complexes, unimolecular thermally activated delayed fluorescence (TADF) emitters and exciplexes, fluorescent dyes, and the emerging group of stable luminescent radicals. We dive into the structural design principles of emitters with improved NIR efficiency. In our discussion we consider unimolecular emission as well as that arising from aggregated luminophores, as the latter often leads to a longer wavelength NIR. Our analysis of numerous emitters from various groups concludes, without a doubt, that platinum(ii) complexes present superior efficiency in nearly all wavelengths from 700 to 1000 nm. We report on an apparent NIR boundary line, which appears to be a current limitation for NIR OLED efficiency. Presently, virtually only platinum(ii) complexes exceed the efficiency limit set out by this boundary. So far efficient OLEDs, i.e. >1% external quantum efficiency, emitting significantly beyond 1000 nm have not yet been reported

Near-infrared electroluminescence beyond 940 nm in Pt(N^C^N)X complexes: influencing aggregation with the ancillary ligand X

We present a study of aggregate excited states formed by complexes of the type Pt(N^C^N)X, where N^C^N represents a tridentate cyclometallating ligand, and X = SCN or I. These materials display near-infrared (NIR) photoluminescence in film and electroluminescence in NIR OLEDs with λmaxEL = 720–944 nm. We demonstrate that the use of X = SCN or I modulates aggregate formation compared to the parent complexes where X = Cl. While the identity of the monodentate ligand affects the energy of Pt–Pt excimers in solution in only a subtle way, it strongly influences aggregation in film. Detailed calculations on aggregates of different sizes support the experimental conclusions from steady-state and time-resolved luminescence studies at variable temperatures. The use of X = I appears to limit aggregation to the formation of dimers, while X = SCN promotes the formation of larger aggregates, such as tetramers and pentamers, leading in turn to NIR photo- and electroluminescence > 850 nm. A possible explanation for the contrasting influence of the monodentate ligands is the lesser steric hindrance associated with the SCN group compared to the bulkier I ligand. By exploiting the propensity of the SCN complexes to form extended aggregates, we have prepared an NIR-emitting OLED that shows very long wavelength electroluminescence, with λmaxEL = 944 nm and a maximum EQE = 0.3 ± 0.1%. Such data appear to be unprecedented for a device relying on a Pt(II) complex aggregate as the emitter

Unusual Excimer/Dimer Behavior of a Highly Soluble C,N Platinum(II) Complex with a Spiro-Fluorene Motif.

In this work, we introduce a spiro-fluorene unit into a phenylpyridine (CN)-type ligand as a simple way to deplanarize the structure and increase the solubility of the final platinum(II)···complex. Using a spiro-fluorene unit, orthogonal to the main coordination plane of the complex, reduces intermolecular interactions, leading to increased solubility but without significantly affecting the ability of the complex to form Pt···Pt dimers and excimers. This approach is highly important in the design of platinum(II) complexes, which often suffer from low solubility due to their mainly planar structure, and offers an alternative to the use of bulky alkyl groups. The nonplanar structure is also beneficial for vacuum-deposition techniques as it lowers the sublimation temperature. Importantly, there are no sp hybridized carbon atoms in the cyclometalating ligand that contain hydrogens, the undesired feature that is associated with the low stability of the materials in OLEDs. The complex displays high solubility in toluene, ∼10 mg mL , at room temperature, which allows producing solution-processed OLEDs in a wide range of doping concentrations, 5-100%, and EQE up to 5.9%, with a maximum luminance of 7400 cd m . Concurrently, we have also produced vacuum-deposited OLEDs, which display luminance up to 32 500 cd m and a maximum EQE of 11.8%

Intermolecular Interactions in Molecular Crystals and Their Effect on Thermally Activated Delayed Fluorescence of Helicene-Based Emitters

Here, we discuss the influence of the crystal structure on the photophysical properties of two new TADF emitters containing a non-planar helical moiety. The presence of solvent in the crystal lattice of a diaza[5]helicene-based compound alters molecular packing significantly and suppresses aggregation. This results in more intense TADF emission and an increase in PLQY. Solution-processed OLED devices gave a maximum external quantum efficiency of 7.1%

9-Borafluoren-9-yl and diphenylboron tetracoordinate complexes of 8-quinolinolato ligands with heavy-atoms substituents: synthesis, fluorescence and application in OLED devices

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 (Φf) ranging from 0.02 to 0.15 and prompt fluorescence (PF) lifetimes (τf) 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. 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) (λEL = 502 nm) with maximum external quantum efficiency (EQEmax) of 2.5% and maximum luminance (Lmax) of 2200 cd m-2

Exceptionally Fast Radiative Decay of a Dinuclear Platinum Complex Through Thermally Activated Delayed Fluorescence

A novel dinuclear platinum(II) complex featuring a ditopic, bis-tetradentate ligand has been prepared. The ligand offers each metal ion a planar O^N^C^N coordination environment, with the two metal ions bound to the nitrogen atoms of a bridging pyrimidine unit. The complex is brightly luminescent in the red region of the spectrum with a photoluminescence quantum yield of 83% in deoxygenated methylcyclohexane solution at ambient temperature, and shows a remarkably short excited state lifetime of 2.1 μs. These properties are the result of an unusually high radiative rate constant of around 4 × 105 s–1, a value which is comparable to that of the very best performing Ir(III) complexes. This unusual behaviour is the result of efficient thermally activated reverse intersystem crossing, promoted by a small singlet–triplet energy difference of only 69 ± 3 meV. The complex was incorporated into solution-processed OLEDs achieving EQEmax = 7.4 %. We believe this to be the first fully evidenced report of a Pt(II) complex showing thermally activated delayed fluorescence (TADF) at room temperature, and indeed of a Pt(II)-based delayed fluorescence emitter to be incorporated into an OLED

Rigidly linked dinuclear platinum( ii ) complexes showing intense, excimer-like, near-infrared luminescence

Many luminescent platinum(ii) complexes undergo face-to-face interactions between neighbouring molecules, leading to bimolecular excited states that may emit at lower energy (dimers and/or excimers). Detailed photophysical studies are reported on dinuclear complexes, in which two NCN-coordinated Pt(ii) units are covalently linked by a xanthene such that intramolecular formation of such dimeric or excimeric states is possible. These complexes display strong excimer-like photoluminescence at low concentrations where their monometallic analogues do not. However, a striking difference emerges between complexes where the Pt(NCN) units are directly connected to the xanthene through the tridentate ligand (denoted Class a) and a new class of compounds reported here (Class b) in which the attachment is through a monodentate acetylide ligand. The former require a substantial geometrical rearrangement to move the metal centres of the Pt(NCN) units to a distance short enough to form excimer-like states. The latter require only a small deformation. Consequently, Class a compounds display negligible excimer-like emission in solid films, as the rigid environment hinders the requisite geometric rearrangement. Class b complexes, in contrast, display strong excimer-like emission in film, even at very low loadings. The new dinuclear molecular architecture may thus offer new opportunities in the quest for efficient NIR-emitting devices

Delayed Fluorescence by Triplet–Triplet Annihilation from Columnar Liquid Crystal Films

Delayed fluorescence (DF) by triplet–triplet annihilation (TTA) is observed in solutions of a benzoperylene-imidoester mesogen that shows a hexagonal columnar mesophase at room temperature in the neat state. A similar benzoperylene-imide with a slightly smaller HOMO–LUMO gap, that also is hexagonal columnar liquid crystalline at room temperature, does not show DF in solution, and mixtures of the two mesogens show no DF in solution either, because of collisional quenching of the excited triplet states on the imidoester by the imide. In contrast, DF by TTA from the imide but not from the imidoester is observed in condensed films of such mixtures, even though neat films of either single material are not displaying DF. In contrast to the DF from the monomeric imidoester in solution, DF of the imide occurs from dimeric aggregates in the blend films, assisted by the imidoester. Thus, the close contact of intimately stacked molecules of the two different species in the columnar mesophase leads to a unique mesophase-assisted aggregate DF. This constitutes the first observation of DF by TTA from the columnar liquid crystalline state. If the imide is dispersed in films of polybromostyrene, which provides an external heavy-atom effect facilitating triplet formation, DF is also observed. Organic light-emitting diodes (OLEDs) devices incorporating these liquid crystal molecules demonstrated high external quantum efficiency (EQE). On the basis of the literature and to the best of our knowledge, the EQE reported is the highest among nondoped solution-processed OLED devices using a columnar liquid crystal molecule as the emitting layer