Local Triplet Excited State Research Articles

Efficient Blue Photo- and Electroluminescence from CF3-Decorated Cu(I) Complexes.

Luminescent organometallic complexes of earth-abundant copper(I) have long been studied in organic light-emitting diodes (OLED). Particularly, Cu(I)-based carbene-metal-amide (CMA) complexes have recently emerged as promising organometallic emitters. However, blue-emitting Cu(I) CMA complexes have been rarely reported. Here we constructed two blue-emitting Cu(I) CMA emitters, MAC*-Cu-CF3Cz and MAC*-Cu-2CF3Cz, by introducing one or two CF3 substitutes into carbazole ligands. Both complexes exhibited high thermal stability and blue emission colors. Moreover, two complexes exhibited different emission origins rooting from different donor ligands: a distinct thermally activated delayed fluorescence (TADF) from ligand-to-ligand charge transfer excited states for MAC*-Cu-CF3Cz or a dominant phosphorescence nature from local triplet excited state of the carbazole ligand for MAC*-Cu-2CF3Cz. Inspiringly, MAC*-Cu-CF3Cz had high photoluminescence quantum yields of up to 94 % and short emission lifetimes of down to 1.2 μs in doped films, accompanied by relatively high radiative rates in the 105 s-1 order. The resultant vacuum-deposited OLEDs based on MAC*-Cu-CF3Cz delivered pure-blue electroluminescence at 462 nm together with a high external quantum efficiency of 13.0 %.

Ultrafast and Multichannel Generation of the Triplet State in DNA-Intercalated Gilvocarcin V for an Enhanced Photoaddition Reaction.

Gilvocarcin V (GV) is a natural antibiotic exhibiting excellent antitumor activities and remarkably low toxicity in near-ultraviolet or visible light-dependent treatment. Notwithstanding, the [2 + 2] cycloaddition reaction between GV and thymine has been proven to be the key for its function in photodynamic therapy, and crucial mechanistic details about such a reaction are poorly understood. In this study, the electronic relaxation pathways and photoaddition reaction are characterized by femto- to nanosecond time-resolved spectroscopy combined with quantum chemical calculation. Our results reveal that ultrafast intersystem crossing (<3 ps) leads to the population of a local triplet excited state in DNA-intercalated GV. Such a state can further induce the formation of a biradical state, which is identified as the important reactive precursor for photoaddition between GV and thymine. The overall photoaddition quantum efficiency is determined to be 11.57 ± 1.0%. These results are essential to the elucidation of the DNA photoaddition mechanism of C-aryl glycoside-based artificial photocytotoxic agents and could help further development of those medicines.

Exploring the Early Time Behavior of the Excited States of an Archetype Thermally Activated Delayed Fluorescence Molecule.

Optical pump-probe techniques allow for an in-depth study of dark excited states. Here, we utilize them to map and gain insights into the excited states involved in the thermally activated delayed fluorescence (TADF) mechanism of a benchmark TADF emitter DMAC-TRZ. The results identify different electronic excited states involved in the key TADF transitions and their nature by combining pump-probe and photoluminescence measurements. The photoinduced absorption signals are highly dependent on polarity, affecting the transition oscillator strength but not their relative energy positions. In methylcyclohexane, a strong and vibronically structured local triplet excited state absorption (3LE → 3LEn) is observed, which is quenched in higher polarity solvents as 3CT becomes the lowest triplet state. Furthermore, ultrafast transient absorption (fsTA) confirms the presence of two stable conformers of DMAC-TRZ: (1) quasi-axial (QA) interconverting within 20 ps into (2) quasi-equatorial (QE) in the excited state. Moreover, fsTA highlights how sensitive excited state couplings are to the environment and the molecular conformation.

Impact of π-Expanded Boron-Carbonyl Hybrid Acceptors on TADF Properties: Controlling Local Triplet Excited States and Unusual Emission Tuning

Three donor-acceptor-type thermally activated delayed fluorescence (TADF) emitters (PXZBAO (1), PXZBTO (2), and PXZBPO (3)) comprising a phenoxazine (PXZ) donor and differently π-expanded boron-carbonyl (BCO) hybrid acceptor units are proposed. The emitters exhibit red (1) to orange (3) emissions with an increase in the π-expansion in the BCO acceptors. The control of the strength of local aromaticity for the BCO unit and the corresponding LUMO level is attributed to inducing the unusual emission color shifts. The photoluminescence quantum yield and delayed fluorescence lifetime of the emitters are also adjusted by the π-expansion. Notably, although 1 possesses a 3nπ* state in the acceptor unit as a local triplet excited state (3LE, T2), the T2 states of 2 and 3 mainly comprise a 3ππ* state in the acceptor. Consequently, all of the emitters exhibit strong spin-orbit coupling between their T2 and excited singlet (S1) states, leading to a fast reverse intersystem crossing with rate constants of ∼106 s-1. By employing the emitters as dopants, we realize efficient red-to-orange TADF-OLEDs. Maximum external quantum efficiencies of 17.7% for the yellowish-orange (3), 15.5% for the orange (2), and 13.9% for the red (1) devices are achieved, and the values are very close to the theoretical limit predicted from the optical simulation.

Efficient TADF from carbon−carbon bonded donor−acceptor molecules based on boron-carbonyl hybrid acceptor

We present a new type of thermally activated delayed fluorescence (TADF) emitters, namely, PCzBCO and BuPCzBCO, composed of the donor (D) and acceptor (A) units linked by a C–C bond. The two emitters have N-aryl carbazole as a donor and a planarized boron-carbonyl (BCO) unit as an acceptor. The crystal structure of BuPCzBCO reveals a moderate twist between the D and A units with a dihedral angle of 49.2°. Although both emitters exhibit the prompt fluorescence only in solution, they exhibit distinct TADF characteristics in the rigid state, with the high photoluminescence quantum yields of 81% and 93% in an mCBP host, respectively. Importantly, fast reverse intersystem crossing (RISC) with the rate constants of ∼106 s−1 is obtained in their host films. Along with the small singlet−triplet energy gap below 50 meV, theoretical studies demonstrate that RISC is facilitated by the strong spin-orbit coupling between the charge-transfer singlet excited state (1CT, S1) and the BCO-centered, local triplet excited state (3LE, T2) with a 3nπ* character. With the PCzBCO and BuPCzBCO molecules as emitters, efficient greenish blue TADF-OLEDs with similar maximum external quantum efficiency of 16.2% are realized. These findings highlight the potential of C–C bonded D−A molecules as efficient TADF emitters.

Naphthalimide-phenothiazine dyads: effect of conformational flexibility and matching of the energy of the charge-transfer state and the localized triplet excited state on the thermally activated delayed fluorescence.

In order to investigate the joint influence of the conformation flexibility and the matching of the energies of the charge-transfer (CT) and the localized triplet excited (3LE) states on the thermally activated delayed fluorescence (TADF) in electron donor–acceptor molecules, a series of compact electron donor–acceptor dyads and a triad were prepared, with naphthalimide (NI) as electron acceptor and phenothiazine (PTZ) as electron donor. The NI and PTZ moieties are either directly connected at the 3-position of NI and the N-position of the PTZ moiety via a C–N single bond, or they are linked through a phenyl group. The tuning of the energy order of the CT and LE states is achieved by oxidation of the PTZ unit into the corresponding sulfoxide, whereas conformation restriction is imposed by introducing ortho-methyl substituents on the phenyl linker, so that the coupling magnitude between the CT and the 3LE states can be controlled. The singlet oxygen quantum yield (ΦΔ) of NI-PTZ is moderate in n-hexane (HEX, ΦΔ = 19%). TADF was observed for the dyads, the biexponential luminescence lifetime are 16.0 ns (99.9%)/14.4 μs (0.1%) for the dyad and 7.2 ns (99.6%)/2.0 μs (0.4%) for the triad. Triplet state was observed in the nanosecond transient absorption spectra with lifetimes in the 4–48 μs range. Computational investigations show that the orthogonal electron donor–acceptor molecular structure is beneficial for TADF. These calculations indicate small energetic difference between the 3LE and 3CT states, which are helpful for interpreting the ns-TA spectra and the origins of TADF in NI-PTZ, which is ultimately due to the small energetic difference between the 3LE and 3CT states. Conversely, NI-PTZ-O, which has a higher CT state and bears a much more stabilized 3LE state, does not show TADF.

Facile access to high-performance reverse intersystem crossing OLED materials through an unsymmetrical D-A-D’ molecular scaffold

Organic light-emitting diode (OLED) materials based on a reverse intersystem crossing (RISC) triplet harvesting mechanism have attracted tremendous attention. Currently, many research efforts have been devoted to the construction of D-A or D-A-D RISC-OLED materials whose charge-transfer-featured singlet excited states (1CTD-A) are very close to the local triplet excited states of their D or/and A moieties (3LED or/and 3LEA), so that a small singlet–triplet energy splitting and a large spin–orbit coupling matrix element can be acquired concurrently. However, the chief technical difficulty lies in the accurate prediction and delicate tuning of the 1CTD–A energy levels of these compounds. Herein, by using PCz-TXO2 as an example, we demonstrated that high-performance RISC-OLED materials can be readily achieved by integrating an appropriate D’ subunit into a traditional D-A fluorophore that lacks RISC property, i.e., constructing a D–A–D’ triad whose 1CTD-A is close to its 3LED’. In comparison with its D-A or D-A-D counterpart of P-TXO2 or DP-TXO2 showing satisfactory photoluminescence efficiency, pure blue gamut but poor RISC, the presence of a carbazole-based D’ subunit has negligible influence on the transition feature of its lowest singlet excited state (S1), but triggers significantly enhanced RISC property. Consequently, PCz-TXO2 shows pure blue electroluminescence (EL) inherited from DP-TXO2 [CIE1931: (0.160, 0.089) vs. (0.154, 0.102)], but significantly enhanced external quantum efficiency (EQEmax: 9.5% vs. 6.1%) and exciton utilization efficiency (EUEmax: 93% vs. 42%). Our results present a new method to facilely access RISC materials and can greatly extend the design rationales for high-performance OLED materials.

Blue TADF Emitters Based on B-Heterotriangulene Acceptors for Highly Efficient OLEDs with Reduced Efficiency Roll-Off.

The design of robust boron acceptors plays a key role in the development of boron-based thermally activated delayed fluorescence (TADF) emitters for the realization of efficient and stable blue organic light-emitting diodes (OLEDs). Herein, we report a set of donor (D)-acceptor (A)-type blue TADF compounds (1-3) comprising triply bridged triarylboryl acceptors, the so-called B-heterotriangulenes, which differ depending on the identity of one of the bridging groups: methylene (1), dimethylmethylene (2), or oxo (3). The X-ray crystal structures of 2 and 3 reveal a highly twisted D-A connectivity and a completely planar geometry for the B-heterotriangulene rings. All compounds exhibit blue emissions with the unitary photoluminescence quantum yields and small singlet-triplet energy splitting (<0.1 eV) in their doped host films. The compounds exhibit a fast reverse intersystem crossing rate (kRISC ≈ 106 s-1) with short-lived delayed fluorescence (τd ≈ 2 μs), which is found to be promoted by the strong spin-orbit coupling between the local triplet excited state (3LE, T2) and singlet (S1) states. Using compounds 1-3 as the emitters, highly efficient blue TADF-OLEDs are realized. The devices based on the emitters with B-heterotriangulenes exhibit better performances than the device incorporating a singly bridged reference emitter over the whole luminance range. Notably, the device based on the fully dimethylmethylene-bridged emitter (2) achieves the highest maximum external quantum efficiency (EQE) of 28.2% and the lowest efficiency roll-off, maintaining a high EQE value of 21.2% at 1000 cd/m2.

Managing local triplet excited states of boron-based TADF emitters for fast spin-flip process: Toward highly efficient TADF-OLEDs with low efficiency roll-off

Improving the rate of a spin-flip process from a triplet to a singlet excited state, which is known as reverse intersystem crossing (RISC), is a challenging issue in realizing efficient and stable organic light-emitting diodes based on thermally activated delayed fluorescence (TADF-OLEDs). Herein, we report two donor−acceptor-type TADF emitters (TMCzBCO and DMACBCO) employing a boron-carbonyl (BCO) hybrid acceptor unit. The emitters possess a 3nπ* state of the BCO unit as an intermediate local triplet excited state (3LE, T2), leading to the large spin–orbit coupling between the T2 and excited singlet (S1) states with significantly low activation barriers <10 meV. Thus, a fast RISC with rate constants (kRISC) exceeding 106 s−1, as well as short exciton lifetimes (~1 μs), are realized. Using the TADF emitters, high-performance TADF-OLEDs with maximum external quantum efficiencies of 24.7% for the green (TMCzBCO) and 28.4% for the yellow (DMACBCO) are presented. Remarkably, the devices sufficiently maintain high efficiency at high luminance, exceeding 20% at 5,000 cd m−2 and 18% at 10,000 cd m−2. These results indicate the crucial role of the 3nπ* state of BCO in the improvement of the RISC rate and shortening of the exciton lifetime, enhancing the optoelectrical performance of TADF-OLEDs.

Pyrido[3,4‐d]pyrimidine as an Acceptor of Thermally Activated Delayed Fluorescent Emitters: Time‐dependent Density Functional Theory Study

Pyrido[3,4‐d]pyrimidine (PyPm) was designed as a new acceptor of thermally activated delayed fluorescent (TADF) emitters and the potential of the new acceptor moiety for TADF properties was investigated. Time‐dependent density functional theory calculation was performed to estimate TADF characteristics by comparing five isomers of PyPm‐based TADF emitters. Geometries of the emitters were affected by the presence of hydrogen bonding depending on the substitution position of the phenyl linker in the donor‐phenyl linker‐acceptor type backbone structure, which also influenced the molecular orbital distributions. The nature of the triplet excited state was also dependent on the substitution position of the phenyl linker and donor moiety in the molecular structure, and the substitution at 5 position of the PyPm provided small singlet‐triplet energy gap and hybridized local and charge transfer triplet excited state for efficient reverse intersystem crossing. From the computational calculation results, it can be expected that PyPm would effectively work as an acceptor of TADF emitters.

Long-Lived Local Triplet Excited State and Charge Transfer State of 4,4'-Dimethoxy Triphenylamine-BODIPY Compact Electron Donor/Acceptor Dyads.

The spin-orbit charge transfer intersystem crossing (SOCT-ISC) and the formation of a long-lived charge transfer (CT) state were studied with a series of 4,4'-dimethoxy triphenylamine-BODIPY compact electron donor/acceptor dyads. Different torsion freedoms were applied in the dyads to tune the electronic coupling between the donor and acceptor, and a red-shifted CT absorption band was observed for one dyad. The dyads show solvent polarity-dependent singlet oxygen photosensitizing ability (quantum yields 3%-79%). Nanosecond transient absorption spectra of the dyad in nonpolar solvent confirm the formation of triplet states. The intrinsic triplet state lifetime is up to 383 μs (in fluid solution), which is much longer than that accessed with the heavy atom effect (276 μs). Intermolecular triplet photosensitizing of the dyads in a polar solvent produces a long-lived 3CT state (lifetime, τCT = 8.0 μs supported by the electron spin density surface analysis). The triplet state lifetime of the dyads doped in a Clear Flex 50 polymer film is exceptionally long (7.6-11.4 ms), and formation of a long-lived CT state (37 μs) was observed. Triplet-triplet annihilation upconversion was performed with the electron donor/acceptor dyads used as the triplet photosensitizer and perylene used as the triplet acceptor; the upconversion quantum yield is up to 15.8%.

Influence of energy gap between charge-transfer and locally excited states on organic long persistence luminescence

Organic long-persistent luminescence (LPL) is an organic luminescence system that slowly releases stored exciton energy as light. Organic LPL materials have several advantages over inorganic LPL materials in terms of functionality, flexibility, transparency, and solution-processability. However, the molecular selection strategies for the organic LPL system still remain unclear. Here we report that the energy gap between the lowest localized triplet excited state and the lowest singlet charge-transfer excited state in the exciplex system significantly controls the LPL performance. Changes in the LPL duration and spectra properties are systematically investigated for three donor materials having a different energy gap. When the energy level of the lowest localized triplet excited state is much lower than that of the charge-transfer excited state, the system exhibits a short LPL duration and clear two distinct emission features originating from exciplex fluorescence and donor phosphorescence.

Triggering Thermally Activated Delayed Fluorescence by Managing the Heteroatom in Donor Scaffolds: Intriguing Photophysical and Electroluminescence Properties.

Establishment of the structure-property relationships of thermally activated delayed fluorescence (TADF) materials has become a significant quest for the scientific community. Herein, two new donors, 10H-benzofuro[3,2-b]indole (BFI) and 10H-benzo[4,5]thieno[3,2-b]indole (BTI), have been developed and integrated with a aryltriazine acceptor to design the green TADF emitters benzofuro[3,2-b]indol-10-yl)-5-(4,6-diphenyl-1,3,5-triazin-2-yl)benzonitrile (BFICNTrz) and 2-(10H-benzo[4,5]thieno[3,2-b]indol-10-yl)-5-(4,6-diphenyl-1,3,5-triazin-2-yl)benzonitrile (BTICNTrz), respectively. The physicochemical and electroluminescence properties of the compounds were tuned by exchanging the heteroatom in the donor scaffold. Intriguingly, the electronegativity of the heteroatom and the ionization potential of the donor unit played vital roles in control of the singlet-triplet energy splitting and TADF mechanism of the compounds. Both compounds showed similar singlet excited states that originated from the charge transfer (CT) states (1 CT), whereas the triplet excited states were tuned by the heteroatom in the donor unit. The origin of phosphorescence in the BTICNTrz emitter was CT emission from the triplet state (3 CT), whereas that in the BFICNTrz emitter stemmed from the local triplet excited state (3 LE). Consequently, BTICNTrz showed a small singlet-triplet energy splitting of 0.08 eV, compared with 0.26 eV for BFICNTrz. Thus, BTICNTrz showed efficient delayed fluorescence with a high quantum yield and a short delayed exciton lifetime, whereas BFICNTrz displayed weak delayed fluorescence with a relatively long lifetime. Furthermore, a BTICNTrz-based device exhibited a maximum external quantum efficiency (EQE) of 15.2 % and reduced efficiency roll-off (12 %) compared with its BFICNTrz-based counterpart, which showed a maximum EQE of 6.4 % and severe efficiency roll-off (55 %) at a practical brightness range of 1000 cd m-2 . These results demonstrate that the choice of subunit plays a vital role in the design of efficient TADF emitters.

Design of Efficient Exciplex Emitters by Decreasing the Energy Gap Between the Local Excited Triplet (3LE) State of the Acceptor and the Charge Transfer (CT) States of the Exciplex.

A series of thermally activated delayed fluorescence (TADF) exciplex based on the TX-TerPy were constructed. The electronic coupling between the triplet local excited states (3LE) of the donors and acceptor and the charge transfer states had a great influence on the triplet exciton harvesting and ΦPL. Herein, based on this strategy, three donor molecules TAPC, TCTA, and m-MTDATA were selected. The local triplet excited state (3LE) of the three donors are 2.93, 2.72 and 2.52 eV in pure films. And the 3LE of TX-TerPy is 2.69 eV in polystyrene film. The energy gap between the singlet charge transfer (1CT) states of TAPC:TX-TerPy (7:1), TCTA:TX-TerPy (7:1) and the 3LE of TX-TerPy are 0.30 eV and 0.20 eV. Finally, the ΦPL of TAPC:TX-TerPy (7:1) and TCTA:TX-TerPy (7:1) are 65.2 and 69.6%. When we changed the doping concentration of the exciplex from 15% to 50%, the ratio of the triplet decreased, and ΦPL decreased by half, perhaps due to the increased energy gap between 1CT and 3LE. Therefore, optimizing the 1CT, 3CT, and 3LE facilitated the efficient exciplex TADF molecules.

Ruthenium(II) Tris(2,2′-bipyridyl) Complex Incorporated in UiO-67 as Photoredox Catalyst

Ruthenium(II) bis(2,2′-bipyridine) (2,2′-bipyridyl-5,5′-dicarboxylic acid), Rudcbpy, attached to the UiO-67(Zr) metal organic framework (MOF), generates upon visible light excitation the localized triplet excited state of the ruthenium(II) bipyridyl complex that decays partly to a very long-lived (millisecond time scale) photoinduced charge-separated state following a similar behavior as that of analogous ruthenium(II) tris(bipyridyl) complex dissolved in water, except that the lifetime of the soluble complex excited state is orders of magnitude shorter. The occurrence of photoinduced charge separation on the Rudcbpy-UiO-67(Zr) MOF has been proven visually by using methyl viologen as electron acceptor. Rudcbpy-UiO-67(Zr) behaves as a heterogeneous, reusable, photoredox catalyst promoting debromination of α-bromoketones with excellent selectivity at high conversions. Characterization data show that Rudcbpy-UiO-67(Zr) is stable under the photocatalytic reaction conditions.

Synthesis and photophysical properties of ruthenium(ii) polyimine complexes decorated with flavin

A bipyridine ruthenium(ii) complex (Ru-1) with a flavin moiety connected to one of the bipyridine ligands via an acetylene bond was designed and synthesized, and its photophysical properties were investigated. Compared with the tris(bipyridine) Ru(ii) complex (Ru-0), which has an extinction coefficient ε = 1.36 × 104 M-1 cm-1 at 453 nm, the introduction of the flavin moiety endows Ru-1 with strong absorption in the visible range (ε = 2.34 × 104 M-1 cm-1 at 456 nm). Furthermore, Ru-1 exhibits phosphorescence (λem = 643 nm, ΦP = 1%, τP = 1.32 μs at 293 K and 4.53 μs at 77 K). We propose that the emission of Ru-1 originates from the low lying triplet excited state of 3IL according to the time-resolved transient difference absorption spectra, the calculated T1 spin density and the T1 thermo-vibration modes localized on the flavin-decorated bipyridine ligand. This is the first time that the phosphorescence of flavin was observed within Ru(ii) complexes. Consequently, Ru-1 was used for triplet-triplet annihilation upconversion, showing a reasonable quantum yield of 0.7% with respect to the phosphorescence quantum yield of 1%. These findings pave the way for the rational design of phosphorescence transition metal complexes. Also, further approaches that may improve the performance of flavin-decorated Ru(ii) bipyridine complexes are proposed.

Singlet–Triplet Splitting Energy Management via Acceptor Substitution: Complanation Molecular Design for Deep‐Blue Thermally Activated Delayed Fluorescence Emitters and Organic Light‐Emitting Diodes Application

A barely reached balance between weak intramolecular‐charge‐transfer (ICT) and small singlet–triplet splitting energy (ΔEST) for reverse intersystem crossing from non‐emissive triplet state to radiative singlet state impedes the realization of deep‐blue thermally activated delayed fluorescence (TADF) materials. By discarding the twisted‐ICT framework for a flattened molecular backbone and introducing a strong acceptor possessing n–π* transition character, hypsochromic color, a large radiative rate (kF), and small ΔEST are achieved simultaneously. Six molecules with a 9,9‐dimethyl‐10‐phenyl‐9,10‐dihydroacridine (i‐DMAc) donor are synthesized and investigated. Coinciding with time‐dependent density functional theory, the reduced dihedral angles between donor (D) and acceptor (A) weaken ICT from dispersed charge density and enable a large kF from increased frontier molecular orbitals overlap. Despite the separated highest occupied (HOMO) and lowest unoccupied molecular orbital (LUMO) population, the intercalation of phenyl bridges between D–A increases kF but significantly lowers the local triplet excited state, indicating small HOMO and LUMO overlap is not a sufficient, but necessary condition for reduced ΔEST. Integrating short conjugation length and carbonyl or triazine acceptors into the complanation molecules, deep‐blue TADF organic light‐emitting diodes demonstrate maximum external quantum efficiencies of 11.5% and 10.9% with Commission Internationale de l'Eclairage coordinates of (0.16, 0.09) and (0.15, 0.11), respectively, which is quite close to the stringent National Television System Committee blue standard.

Investigation of the Mechanisms Giving Rise to TADF in Exciplex States

The donor–acceptor systems studied in this work have been demonstrated to show strong exciplex formation by their red-shifted PL emission when compared with the individual donor and acceptor molecules, and all give rise to delayed fluorescence. In all cases, the channels by which this delayed fluorescence is generated, along with the energy levels involved in reverse intersystem crossing (rISC), that is, which triplet levels the charge-transfer states couple to yield spin flip, have not previously been identified. Here the intermolecular charge transfer states formed in the donor–acceptor molecular pairs are studied. It is demonstrated that the local triplet excited states are the states that couple to the singlet charge-transfer excited state, defining the rISC process and hence thermally activated delayed fluorescence (TADF) mechanism. Moreover, in most systems there is a competition between delayed fluorescence mechanisms, triplet triplet annihilation and TADF, and this is analysed in detail. New desig...

The Role of Local Triplet Excited States and D-A Relative Orientation in Thermally Activated Delayed Fluorescence: Photophysics and Devices.

Here, a comprehensive photophysical investigation of a the emitter molecule DPTZ‐DBTO2, showing thermally activated delayed fluorescence (TADF), with near‐orthogonal electron donor (D) and acceptor (A) units is reported. It is shown that DPTZ‐DBTO2 has minimal singlet–triplet energy splitting due to its near‐rigid molecular geometry. However, the electronic coupling between the local triplet (3LE) and the charge transfer states, singlet and triplet, (1CT, 3CT), and the effect of dynamic rocking of the D–A units about the orthogonal geometry are crucial for efficient TADF to be achieved. In solvents with low polarity, the guest emissive singlet 1CT state couples directly to the near‐degenerate 3LE, efficiently harvesting the triplet states by a spin orbit coupling charge transfer mechanism (SOCT). However, in solvents with higher polarity the emissive CT state in DPTZ‐DBTO2 shifts below (the static) 3LE, leading to decreased TADF efficiencies. The relatively large energy difference between the 1CT and 3LE states and the extremely low efficiency of the 1CT to 3CT hyperfine coupling is responsible for the reduction in TADF efficiency. Both the electronic coupling between 1CT and 3LE, and the (dynamic) orientation of the D–A units are thus critical elements that dictate reverse intersystem crossing processes and thus high efficiency in TADF.

Rational Design of TADF Polymers Using a Donor–Acceptor Monomer with Enhanced TADF Efficiency Induced by the Energy Alignment of Charge Transfer and Local Triplet Excited States

The sentence “The EQE of our devices is, therefore, better than the performance recently reported in Nikolaenko et al.'s paper[19] at the same brightness, 100 cd m−2.” on page 606, should be “The EQE of our devices is therefore similar to the performance recently reported in Nikolaenko et al.'s paper[19] at the same brightness, 100 cd m−2, but without making use of an interlayer, and thus with wide scope for optimization.” The arguments and conclusions of the original article are not affected. The authors apologize for any inconvenience caused.