Efficient Direct Reverse Intersystem Crossing between Charge Transfer-Type Singlet and Triplet States in a Purely Organic Molecule

In the field of organic light-emitting diodes, thermally activated delayed fluorescence (TADF) materials have achieved great performance. The key factor for this performance is the small energy gap (ΔE_ST) between the lowest triplet (T₁) and singlet excited (S₁) states, which can be realized in a well-separated donor-acceptor system. Such systems are likely to possess similar charge transfer (CT)-type T₁ and S₁ states. Recent investigations have suggested that the intervention of other type-states, such as locally excited triplet state(s), is necessary for efficient reverse intersystem crossing (RISC). Here, we theoretically and experimentally demonstrate that our blue TADF material exhibits efficient RISC even between singlet CT and triplet CT states without any additional states. The key factor is dynamic flexibility of the torsion angle between the donor and acceptor, which enhances spin-orbit coupling even between the charge transfer-type T₁ and S₁ states, without sacrificing the small ΔE_ST. This results in excellent photoluminescence and electroluminescence performances in all the host materials we investigate, with sky-blue to deep-blue emissions. Among the hosts investigated, the deepest blue emission with CIE coordinates of (0.15, 0.16) and the highest EQE_MAX of 23.9 % are achieved simultaneously.     

Nonstationary perturbation theory for open-shell molecules

Nonstationary perturbation theory equations have been obtained for open-shell molecules. The equations were formulated in terms of a density matrix in the MO-LCAO method. The first variant is coupled perturbation theory in the framework of the restricted Hartree-Fock method for open shells, and the second variant is variational perturbation theory for ground and excited electronic states of molecules, in which the perturbed wave function of the system is constructed in the form of a superposition of the ground and singly excited configurations composed of the Hartree-Fock orbitals of the open shell. A calculation of the Cauchy moments of the dynamic dipole polarizability of several molecules of conjugated open-shell hydrocarbons, viz., doublet states of odd alternant hydrocarbons, as well as triplet excited states and doublet states of radical ions of even alternant hydrocarbons, has been carried out in the framework of both methods.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 1, pp. 18–27, January–February, 1985.     

Diradicaloid Boron-Doped Molecular Carbons Achieved by Pentagon-Fusion

Molecular carbons (MCs) are molecular cutouts of carbon materials. Doping with heteroatoms and constructing open-shell structures are two powerful approaches to achieve unexpected and unique properties of MCs. Herein, we disclose a new strategy to design open-shell boron-doped MCs (BMCs), namely by pentagon-fusion of an organoborane π-system. We synthesized two diradicaloid BMC molecules that feature C₂₄B and C₃₈B π-skeletons containing a pentagonal ring. A thorough investigation reveals that such pentagon-fusion not only leads to their local antiaromaticity, but also incorporates an internal quinoidal substructure and thereby induces open-shell singlet diradical states. Moreover, their fully fused structures enable efficient π conjugation, which is expanded over the whole frameworks. Consequently, some intriguing physical properties are achieved, such as narrow energy gaps, very broad light absorptions, and superior photothermal capability, along with excellent photostability. Notably, the solid of the C₃₈B molecule exhibits absorption that covers the range of 300–1200 nm and an efficiency of 93.5 % for solar-driven water evaporation, thus demonstrating the potential of diradicaloid BMCs as high-performance organic photothermal materials.     

Facile Generation of Thermally Activated Delayed Fluorescence and Fabrication of Highly Efficient Non-Doped OLEDs Based on Triazine Derivatives

A series of donor–acceptor–donor triazine-based molecules with thermally activated delayed fluorescence (TADF) properties were synthesized to obtain highly efficient blue-emitting OLEDs with non-doped emitting layers (EMLs). The targeted molecules use a triazine core as the electron acceptor, and a benzene ring as the conjugated linker with different electron donors to alternate the energy level of the HOMO to further tune the emission color. The introduction of long alkyl chains on the triazine core inhibits the unwanted intermolecular D –D/A–A-type π–π interactions, resulting in the intermolecular D–A charge transfer. The weak aggregation-caused quenching (ACQ) effect caused by the suppressed intermolecular D –D/A–A-type π–π interaction further enhances the emission. The crowded molecular structure allows the electron donor and acceptor to be nearly orthogonal, thereby reducing the energy gap between triplet and singlet excited states (ΔE_ST). As a result, blue-emitting devices with TH-2DMAC and TH-2DPAC non-doped EMLs showed satisfactory efficiencies of 12.8 % and 15.8 %, respectively, which is one of the highest external quantum efficiency (EQEs) reported for blue TADF emitters (λ_peak<475 nm), demonstrating that our tailored molecular designs are promising strategies to endow OLEDs with excellent electroluminescent performances.     

Thermally Activated Delayed Near-Infrared Photoluminescence from Functionalized Lead-Free Nanocrystals

As an analogue to thermally activated delayed fluorescence (TADF) of organic molecules, thermally activated delayed photoluminescence (TADPL) observed in molecule-functionalized semiconductor nanocrystals represents an exotic mechanism to harvest energy from dark molecular triplets and to obtain controllable, long-lived PL from nanocrystals. The reported TADPL systems have successfully covered the visible spectrum. However, TADF molecules already emit very efficiently in the visible, diminishing the technological impact of the less-efficient nanocrystal-molecule TADPL. Here we report bright, near-infrared TADPL in lead-free CuInSe₂ nanocrystals functionalized with carboxylated tetracene ligands, which results from efficient triplet energy transfer from photoexcited nanocrystals to ligands, followed with thermally activated reverse energy transfer from ligand triplets back to nanocrystals. This strategy prolonged the nanocrystal exciton lifetime from 100 ns to 60 μs at room temperature.     

Electronic and photophysical properties of selected organic boron-containing molecules: Insight into effects of heteroatom substitution and aggregation

The density functional theory (DFT) and time-dependent DFT methods were used to investigate the electronic and optoelectronic properties of several main group atom-doped polycyclic aromatic hydrocarbons, such as oxygen-substituted PHO1 and PHO2, and sulfur-substituted PHS1 and PHS2. The ground-state structures of these molecules generally have an open-shell singlet configuration with a certain diradical character. In comparison with PHO1 and PHO2, PHS1 and PHS2 own larger diradical character indices due to their increased anti-aromaticity. Although the substitution of sulfur for the peripheral oxygen has a significant effect on the molecular geometry, the adiabatic excitation energy levels of the corresponding low-lying excited states of these molecules are less changed. Calculations reveal that here the intersystem crossing (ISC) and reverse intersystem crossing processes in CH₂Cl₂ mainly occur between the S₁ and T₂ states, and the cis molecules PHO2 and PHS2 have better charge transportation performance. Furthermore, the electronic and photophysical properties of these B-containing molecules are predicted to be tuned by the peripheral atom substitution and the structural and aggregation changes.     

Theoretical studies on excited-state properties and luminescence mechanism of a Carbene–Metal–Amide Au(I) complex with thermally activated delayed fluorescence

Two-coordinate Carbene−Metal−Amide (CMA) complexes with thermally activated delayed fluorescence (TADF) have attracted much attention owing to their excellent luminescence properties and potential applications in organic light-emitting devices. However, the luminescence mechanism remains unclear. Herein, we took one CMA Au(I) complex as an example and investigate its relevant photophysics using both density functional theory (DFT) and time-dependent DFT methods with a polarizable continuum model. The calculated absorption and emission spectra agree with the experimental data and the S₁ and T₁ states show mixed ligand to ligand charge transfer (CT) and ligand to metal CT characters. Small spatial overlap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) minimizes the energy difference between the S₁ and T₁ states (ΔE_ST). Properly large spin-orbit coupling promotes the reverse intersystem crossing (rISC) process. At 300 K, the rISC process is much more efficient than the T₁ phosphorescent emission, which leads to the TADF emission.     

Productive harvesting of triplet excitons in anthracene-based emitters toward high-performance deep-blue nondoped organic light-emitting diodes

Developing efficient deep-blue non-doped organic light-emitting diodes (OLEDs) is of great significance in practical applications. Here, two highly efficient asymmetric anthracene-based fluorescent emitters, 1-phenyl-2-(4-(10-(4-(2-phenyl-1H-phenanthro[9,10-d]imidazole-1-yl)phenyl)anthracen-9-yl)phenyl)-1H-phenanthro [9,10-d]imidazole (PPI-An-NPPI) and 1-phenyl-2-(4-(10-(4-(2,4,5-triphenyl-1H-imidazole-1-yl)phenyl) anthracen-9-yl)phenyl)-1H-phenanthro[9,10-d]imidazole (PPI-An-NPIM), have been designed and synthesized by introducing large steric hindrance imidazole moieties to regulate molecular excited states and photophysical properties. Experimental data show that they have high photoluminescence efficiencies, good thermal stabilities, and suitable energy levels for carrier injection. Theoretical calculations present that their high-lying excited states exhibit dominant locally excited-state characteristics with enhancing oscillator strength compared with anthracene core. The calculated transition dipole moments data show that two molecules are preferentially oriented along the horizontal direction. In addition, some hot exciton mechanism-like channels are also observed and confirmed, which are beneficial for the productive triplet-singlet exciton conversion. The non-doped OLED using PPI-An-NPPI as the emitting layer achieves a maximum external quantum efficiency (EQE_max) of 7.75% and Commission Internationale de L’Eclairage (CIE) coordinates of (0.15, 0.11), whereas PPI-An-NPIM gives a better color purity of CIE (0.14, 10) with an EQE_max of 7.48%. Moreover, all devices exhibit an insignificant efficiency roll-off at high luminescence and still yield an EQE of 7.61% and 7.14% at 1,000 cd/m². This work provides an interesting insight into developing efficient deep-blue fluorescent emitters for high-performance non-doped OLEDs.     

Excited-State THz Vibrations in Aggregates of PtII Complexes Contribute to the Enhancement of Near-Infrared Emission Efficiencies**

The exploration of deactivation mechanisms for near-infrared(NIR)-emissive organic molecules has been a key issue in chemistry, materials science and molecular biology. In this study, based on transient absorption spectroscopy and transient grating photoluminescence spectroscopy, we demonstrate that the aggregated Pt^II complex 4H (efficient NIR emitter) exhibits collective out-of-plane motions with a frequency of 32 cm⁻¹ (0.96 THz) in the excited states. Importantly, similar THz characteristics were also observed in analogous Pt^II complexes with prominent NIR emission efficiency. The conservation of THz motions enables excited-state deactivation to proceed along low-frequency vibrational coordinates, contributing to the suppression of nonradiative decay and remarkable NIR emission. These novel results highlight the significance of excited-state vibrations in nonradiative processes, which serve as a benchmark for improving device performance.     

Excited states of the benzyl radical

The CI method is used in the -electron approximation with orbitals for closed and open shells to calculate the properties of excited doublet states with allowance for all singly excited configurations and some doubly excited ones, and also for the first quartet and sextet states, which are calculated in the one-configuration approximation via the open-shell theory. The energies and transition moments agree satisfactorily with the available experimental evidence. A classification and assignment is given for the excited terms. Truncation of the complete set of singly excited configurations greatly distorts the calculated spectrum. Inclusion of doubly excited configurations in the CI also produces a substantial change in the spectrum; in some cases it alters the order of adjacent terms. Conversion in CI from basis closed-shell orbitals to open-shell ones produces a considerable lowering of all terms in the spectrum. As in the case of triplet terms for molecules, weakening of electron interaction brings the lowest excited term of the radical closer to the ground-state term. The electron-density and spin-density distributions are calculated for the excited states.     

Excited state geometries within time-dependent and restricted open-shell density functional theories

Singlet excited state geometries of a set of medium sized molecules with different characteristic lowest excitations are studied. Geometry optimizations of excited states are performed with two closely related restricted open-shell Kohn–Sham methods and within linear response to time-dependent density functional theory. The results are compared to wave-function based methods. Excitation energies (vertical and adiabatic) calculated from the open-shell methods show systematic errors depending on the type of excitation. However, for all states accessible by the restricted methods a good agreement for the geometries with time-dependent density functional theory and wave-function based methods is found. An analysis of the energy with respect to the mixing angle for the singly occupied orbitals reveals that some states (mostly [n→π^*]) are stable when symmetry constraints are relaxed and others (mostly [π→π^*]) are instable. This has major implications on the applicability of the restricted open-shell methods in molecular dynamics simulations.     

Donor–σ–Acceptor Motifs: Thermally Activated Delayed Fluorescence Emitters with Dual Upconversion

A family of organic emitters with a donor–σ–acceptor (D‐σ‐A) motif is presented. Owing to the weakly coupled D‐σ‐A intramolecular charge‐transfer state, a transition from the localized excited triplet state (³LE) and charge‐transfer triplet state (³CT) to the charge‐transfer singlet state (¹CT) occurred with a small activation energy and high photoluminescence quantum efficiency. Two thermally activated delayed fluorescence (TADF) components were identified, one of which has a very short lifetime of 200–400 ns and the other a longer TADF lifetime of the order of microseconds. In particular, the two D‐σ‐A materials presented strong blue emission with TADF properties in toluene. These results will shed light on the molecular design of new TADF emitters with short delayed lifetimes.     

Nonradiative Energy Transfer through Distributed Bands in Piezochemically Synthesized Cesium and Formamidinium Lead Halide Perovskites

Repeated absorption of emitted photons, also called photon recycling, in large crystals and thick films of perovskites leads to delayed photoluminescence (PL) and decrease of PL intensity. The role of distinct band gaps, which act as donors and acceptors of energy, and nonradiative energy transfer on such delayed, low intensity emission is yet to be rationalized. Here we report delayed emission by nonradiative energy transfer across a distribution of energy states in close-packed crystallites of cesium lead bromide CsPbBr₃, formamidinium lead bromide FAPbBr₃, or the mixed halide FAPb(BrI)₃ perovskite synthesized in the form of thick pellets by the piezochemical method. The PL lifetime of the bromide-rich domain in the mixed halide pellet is considerably decreased when compared with a pure FAPbBr₃ pellet. Here the domains with higher bromide composition act as the energy donor, whereas the iodide-rich domains are the acceptors. Time-resolved PL measurements of CsPbBr₃, FAPbBr₃, and the mixed halide FAPb(BrI)₃ perovskite pellets help us to clarify the role of nonradiative energy transfer on photon recycling.     

Red/Near‐Infrared Thermally Activated Delayed Fluorescence OLEDs with Near 100 % Internal Quantum Efficiency

Developing red thermally activated delayed fluorescence (TADF) emitters, attainable for both high‐efficient red organic light‐emitting diodes (OLEDs) and non‐doped deep red/near‐infrared (NIR) OLEDs, is challenging. Now, two red emitters, BPPZ‐PXZ and mDPBPZ‐PXZ, with twisted donor–acceptor structures were designed and synthesized to study molecular design strategies of high‐efficiency red TADF emitters. BPPZ‐PXZ employs the strictest molecular restrictions to suppress energy loss and realizes red emission with a photoluminescence quantum yield (Φ_PL) of 100±0.8 % and external quantum efficiency (EQE) of 25.2 % in a doped OLED. Its non‐doped OLED has an EQE of 2.5 % owing to unavoidable intermolecular π–π interactions. mDPBPZ‐PXZ releases two pyridine substituents from its fused acceptor moiety. Although mDPBPZ‐PXZ realizes a lower EQE of 21.7 % in the doped OLED, its non‐doped device shows a superior EQE of 5.2 % with a deep red/NIR emission at peak of 680 nm.     

Combining Open-Shell Verdazyl Environment and Co(II) Spin-Crossover: Spinmerism in Cobalt Oxoverdazyl Compound

The spin states of a Co(II) oxoverdazyl compound are investigated by means of wavefunction-based calculations. Within a ca. 233 K energy window, the ground state and excited states display a structure-sensitive admixture of low-spin S_M=1/2 in a dominant high-spin S_M=3/2 Co(II) ion as indicated by the localized molecular orbitals. The puzzling spin zoology that results from the coupling between open-shell radical ligands and a spin-crossover metal ion gives rise to this unusual scenario, which extends the views in molecular magnetism. In agreement with experimental observation, the low-energy spectroscopy is very sensitive to deformations of the coordination sphere, and a growing admixture of Co(II) low-spin is evidenced from the calculations. In analogy with mesomerism that accounts for charge delocalization, entanglement combines different local spin states to generate a given total spin multiplicity, a spinmerism phenomenon.     

Molecular design of efficient yellow- to red-emissive alkynylgold(iii) complexes for the realization of thermally activated delayed fluorescence (TADF) and their applications in solution-processed organic light-emitting devices

Here, we report the design and synthesis of a new class of fused heterocyclic alkynyl ligand-containing gold(iii) complexes, which show tunable emission colors spanning from the yellow to red region in the solid state and exhibit thermally activated delayed fluorescence (TADF) properties. These complexes display high photoluminescence quantum yields of up to 0.87 and short excited-state lifetimes in sub-microsecond timescales, yielding high radiative decay rate constants on the order of up to 10⁶ s⁻¹. The observation of the drastic enhancement in the emission intensity of the complexes with insignificant change in the excited-state lifetime upon increasing the temperature from 200 to 360 K indicates an increasing radiative decay rate. The experimentally estimated energy splitting between the lowest-lying singlet excited state (S₁) and the lowest-lying triplet excited state (T₁), ΔE_S1–T1, is found to be as small as ∼0.03 eV (250 cm⁻¹), comparable to the value of ∼0.05 eV (435 cm⁻¹) obtained from computational studies. The delicate choice of the cyclometalating ligand and the fused heterocyclic ligand is deemed the key to induce TADF through the control of the energy levels of the intraligand and the ligand-to-ligand charge transfer excited states. This work represents the realization of highly emissive yellow- to red-emitting gold(iii) TADF complexes incorporated with fused heterocyclic alkynyl ligands and their applications in organic light-emitting devices.

We report the design of a new class of fused heterocyclic alkynyl ligand-containing gold(iii) complexes, which shows tunable emission colors spanning yellow to red region and exhibits thermally activated delayed fluorescence (TADF) properties.     

BaGdB~9O~16中Dy^3+的发光和Ce^3+, Gd^3+驿Dy^3+的能量传递

我们研究了在紫外光(UV)激发下, Dy^3+单掺杂和Ce^3+, Dy^3+共掺杂的BaGdB~9O~16的发射光谱、激发光谱及发光强度随组成变化的规律性, 发现Ce^3+,Gd^3+均对Dy^3+的发光起敏化作用。Ce^3+吸收的能量大部分直接传递给Dy^3+, 小部分以Ce^3+→Gd^3+→(Gd^3+)~n→Dy^3+形式传递给Dy^3+。Ce^3+→Dy^3+能量传递和Dy^3+自身浓度猝灭机理分别为电偶极-电偶极和电偶极-电四级相互作用。     

Dicyano-Imidazole: A Facile Generation of Pure Blue TADF Materials for OLEDs

A series of dicyano-imidazole-based molecules with thermally activated delayed fluorescence (TADF) properties were synthesized to obtain pure blue-emitting organic light-emitting diodes (OLEDs). The targeted molecules used dicyano-imidazole with a short-conjugated system as the electron acceptor to strong intermolecular π-π interactions, and provide a relatively shallow energy level of the lowest unoccupied molecular orbital (LUMO). The cyano group was selected to improve imidazole as an electron acceptor due to its prominent electron-transporting characteristics. Four different electron donors, that is, 9,9-dimethyl-9,10-dihydroacridine (DMAC), 10H-spiro(acridine-9,9’-fluoren) (SPAC), and 9,9-diphenyl-9,10-dihydroacridine (DPAC), were used to alternate the highest occupied molecular orbital (HOMO) energy level to tune the emission color further. The crowded molecular structure in space makes the electron donor and acceptor almost orthogonal, reducing the energy gap (ΔE_ST) between the first excited singlet (S₁) and the triplet (T₁) states and introducing significant TADF property. The efficiencies of the blue-emissive devices with imM-SPAC and imM-DMAC obtained in this work are the highest among the reported imidazole-based TADF-OLEDs, which are 13.8 % and 13.4 %, respectively. Both of Commission Internationale de l′Eclairage (CIE) coordinates are close to the saturated blue region at (0.17, 0.18) and (0.16, 0.19), respectively. Combining these tailor-made TADF compounds with specific device architectures, electroluminescent (EL) emission from sky-blue to deep-blue could be achieved, proving their great potential in EL applications.