Achieving pure room temperature phosphorescence (RTP) in phenoselenazine-based organic emitters through synergism among heavy atom effect, enhanced n → π* transitions and magnified electron coupling by the A-D-A molecular configuration.

The weak spin-orbit coupling (SOC) in metal-free organic molecules poses a challenge in achieving phosphorescence emission. To attain pure phosphorescence in RTP organic emitters, a promising molecular design concept has been proposed. This involves incorporating n → π* transitions and leveraging the heavy atomic effect within the spin-orbit charge transfer-induced intersystem crossing (SOCT-ISC) mechanism of bipolar molecules. Following this design concept, two bipolar metal-free organic molecules (PhSeB and PhSeDB) with donor-acceptor (D-A) and acceptor-donor-acceptor (A-D-A) configurations have been synthesized. When the molecular configuration changes from D-A to A-D-A, PhSeDB exhibits stronger electron coupling and n → π* transitions, which can further enhance the spin-orbit coupling (SOC) together with the heave atom effect from the selenium atom. By the advanced synergism among enhanced n → π* transitions, heavy atom effect and magnified electron coupling to efficiently promote phosphorescence emission, PhSeDB can achieve pure RTP emission in both the solution and doped solid film. Thanks to the higher spin-orbit coupling matrix elements (SOCMEs) for T1 ↔ S0, PhSeDB attains the highest phosphorescence quantum yield (ca. 0.78) among all the RTP organic emitters reported. Consequently, the purely organic phosphorescent light-emitting diodes (POPLEDs) based on PhSeDB achieve the highest external quantum efficiencies of 18.2% and luminance of 3000 cd m-2. These encouraging results underscore the significant potential of this innovative molecular design concept for highly efficient POPLEDs.

Tailoring D-π-A architectures with hybridized local and charge transfer fluorophores exhibiting high electroluminescence exciton utilization and low threshold amplified spontaneous emission.

Novel amorphous compounds which could simultaneously use 25% singlet excitons and 75% triplet excitons as the energy source for light amplification enable the reduction of the threshold current density for electrically pumped organic semiconductor laser diodes (OSLDs); however, there is always a trade-off between the high radiative decay rate of the local excited (LE) state that is required for amplified spontaneous emission (ASE) and high exciton utilization benefiting from the charge-transfer (CT) state during electroluminescence (EL). Herein, we have explored a delicate balance to achieve both low ASE threshold and high EL exciton utilization by adopting a carefully tailored hybridized local and charge-transfer (HLCT) molecular design. A series of donor-π-acceptor (D-π-A) molecules (SBz-1, SBz-2 and SBz-3) are synthesized, and the structural change mainly refers to the spatial distance between D and A which could regulate the excited-state character via adjusting the CT length. Notably, the ASE phenomenon with a low threshold (2.97 µJ cm-2) and a high exciton utilization of 57.6% are achieved at the same time for SBz-2 with an appropriate CT length. The results provide guidance for molecular design toward harvesting triplet excitons in organic laser materials.

PtII(C

A series of four-coordinated PtII(C^N)(N-donor ligand)Cl-type complexes have been synthesized through a combination of long-size C^N-type and N-donor ligands. In addition, by varying the coordinating site in the N-donor ligand, a distorted molecular configuration has been constructed in these complexes. Their photophysical features, aggregation-induced phosphorescence emission (AIPE) behaviors, electrochemical properties and electroluminescence (EL) performance have been investigated in detail. It has been found that their AIE behaviors can be enhanced by both employing long-size ligands, especially the N-donor ligand, and adopting a distorted molecular configuration, furnishing a high AIE factor (αAIE) of ca. 13.8. Critically, benefitting from their long-size C^N-type and N-donor ligands, these PtII(C^N)(N-donor ligand)Cl-type complexes can exhibit very sensitive AIE behaviors in a mixture of THF-H2O, indicated by their noticeable emission increase with a low H2O volumetric fraction (fw) of ca. 0.1 in their THF solution. In solution-processed organic light-emitting diodes (OLEDs), they can achieve a luminance of 6743 cd m-2 at 13.5 V, a maximum external quantum efficiency (ηext) of 13.8%, a maximum current efficiency (ηL) of 42.4 cd A-1 and a maximum power efficiency (ηP) of 34.4 lm W-1, respectively. Hence, this research can provide key information for developing phosphorescent complexes with a highly sensitive AIE response and impressive EL ability.

The synthesis of cyclometalated platinum(II) complexes with benzoaryl-pyridines as C

A series of (C^N)Pt(acac)-type complexes has been successfully synthesized with a benzo[b]furan, benzo[b]thiophene, benzo[b]selenophene, or benzo[b]tellurophene group in the benzoaryl-pyridine ligand. Using X-ray crystallography, the chemical structures of the complexes with benzo[b]selenophene and benzo[b]tellurophene groups have been clearly revealed. The photophysical, electrochemical, and electroluminescent (EL) behaviors of these (C^N)Pt(acac)-type complexes have been fully characterized. Furthermore, both time-dependent functional theory (TD-DFT) and natural transition orbital (NTO) theoretical results have been obtained to gain insight into the absorption and emission features. It has been shown that both the absorption bands with the lowest energy and the phosphorescence emission behaviors are dominated by the benzoaryl-pyridine cyclometalating ligand. Importantly, the effects of the group VIA atoms on the properties of these (C^N)Pt(acac)-type complexes have been revealed. Owing to the rareness of (C^N)Pt(acac)-type complexes with benzo[b]selenophene and benzo[b]tellurophene groups, their EL abilities have been characterized using solution-processed organic light-emitting diodes (OLEDs). The optimized red OLEDs with the complex bearing a benzo[b]selenophene unit show a maximum external quantum efficiency (ηext) of 6.3%, current efficiency (ηL) of 10.5 cd A-1, and power efficiency (ηP) of 9.1 lm W-1, while the EL device with the complex bearing a benzo[b]tellurophene unit can give deep-red emission at ca. 636 nm with ηext of 6.3%, ηL of 6.5 cd A-1, and ηP of 5.8 lm W-1. This research not only provides novel (C^N)Pt(acac)-type complexes, but also furnishes critical information regarding the photophysical and EL behavior of these new complexes.

Highly Efficient Deep-Red Organic Light-Emitting Devices Based on Asymmetric Iridium(III) Complexes with the Thianthrene 5,5,10,10-Tetraoxide Moiety.

Highly efficient deep-red organic light-emitting devices (OLEDs) are indispensable for developing high-performance red-green-blue (RGB) displays and white OLEDs (WOLEDs). However, the shortage of deep-red emitters with high photoluminescence quantum yields (PLQYs) and balanced charge injection/transport abilities has severely restricted the performance of deep-red OLEDs. Herein, we design and synthesize four efficient emitters by combining the isoquinoline group with the thianthrene 5,5,10,10-tetraoxide group. Benefited from the introduction of the thianthrene 5,5,10,10-tetraoxide group, these Ir(III) complexes show improved electron-injection/-transport abilities. By enhancing the contribution of the triplet metal-to-ligand charge transfer (3MLCT) in emissions, the asymmetric configuration endows the related deep-red Ir(III) complexes with high PLQYs of 0.45-0.50 in solutions. More importantly, PLQYs of these Ir(III) complexes in doped host films increase up to 0.91, which is much higher than PLQYs reported for conventional deep-red Ir(III) complexes with impressive electroluminescent performance. As a result, solution-processed OLEDs based on these Ir(III) complexes exhibit deep-red emissions with Commission Internationale de L'Eclairage (CIE x, y) coordinates very close to the National Television System Committee (NTSC)-recommended standard red CIE coordinates of (0.67, 0.33). Furthermore, a deep-red OLED using the asymmetric Ir(III) complex SOIrOPh as the emitter shows outstanding performance with a peak external quantum efficiency (EQE) of 25.8%, which is the highest EQE reported for solution-processed deep-red OLEDs. This work sheds light on the great potential of utilizing the thianthrene 5,5,10,10-tetraoxide group to develop phosphorescent emitters for highly efficient OLEDs.

Organic Emitters with a Rigid 9-Phenyl-9-phosphafluorene Oxide Moiety as the Acceptor and Their Thermally Activated Delayed Fluorescence Behavior.

With the 9-phenyl-9-phosphafluorene oxide (PhFlOP) moiety as the acceptor (A) and various donors (D), a series of new organic emitters have been synthesized with a D-A-D configuration. Their photophysical and electrochemical behaviors and electroluminescent (EL) performances have been characterized in detail. The photophysical results have indicated that the PhFlOP-based emitters with acridyl, phenoxazyl, and phenothiazyl as donors show efficient, thermally activated delayed fluorescence (TADF) behavior, especially for the TADF emitter with the phenoxazyl donor possessing an exceptionally high rate constant of reverse intersystem crossing (kRISC) of 6.2 × 105 s-1. It has also been found that their TADF behavior can be greatly affected by the substitution position of the donors. Different from the reported aryl phosphine oxide (APO) acceptors in TADF emitters, the PhFlOP moiety adopts a highly rigid configuration to guarantee a photoluminescent quantum yield as high as 0.80 in the 4,4'-N,N'-dicarbazolebiphenyl film, representing the top-ranking emission ability for the TADF emitters with APO-type acceptors. Benefitting from their advanced TADF performances, the doped organic light-emitting diodes/devices based on these PhFlOP-based TADF emitters can achieve exceptional EL performances with the maximum external quantum efficiency (ηext) of 23.3%, current efficiency (ηL) of 83.7 cd A-1, and power efficiency (ηP) of 59.1 lm W-1. These encouraging EL data show the great potential of the PhFlOP moiety in developing highly efficient TADF emitters.

Isomers of Coumarin-Based Cyclometalated Ir(III) Complexes with Easily Tuned Phosphorescent Color and Features for Highly Efficient Organic Light-Emitting Diodes.

Three Ir(C∧N)2(acac)-type and one Ir(C1∧N)(C2∧N)(acac)-type coumarin-based cyclometalated Ir(III) complex isomers (IrC5, IrC7, IrC7-A, and IrC8) have been obtained using three coumarin-based isomers of 2-phenylpyridine (ppy)-type cyclometalating ligands (L-C5, L-C7, and L-C8). Two coordination isomers emerging as principal products (IrC7 and IrC7-A) are obtained in the synthesis of corresponding coumarin-based cyclometalated Ir(III) complexes because of two different coordination sites in ligand L-C7 to form a C-Ir bond. To the best of our knowledge, there are no such isomers reported to date. Interestingly, a broad range of phosphorescent color tuning from green (IrC8, λ = 516 nm) to red (IrC5, λ = 608 nm) has been realized through variation of the pyridyl substitution positions on the fused phenyl ring of the coumarin skeleton. In addition, based on natural transition orbital (NTO) analyses, features of the lowest triplet excited states (T1) from these coumarin-based cyclometalated Ir(III) complex isomers can be tuned easily by these ligand isomers as well. IrC5, IrC7, and IrC7-A show prevailing 3MLCT character associated with their T1 states which emit the phosphorescent signals, while the T1 state of IrC8 exhibits the dominant ligand-centered π-π* transition feature. Importantly, owing to the strong rigidity of the coumarin skeleton, all the coumarin-based cyclometalated Ir(III) complex isomers can show high phosphorescent quantum yields Φp (ca. 0.4-1). Together with the improved electron-injection/electron-transport (EI/ET) ability, all the phosphorescent emitters display impressive electroluminescence (EL) performance. The device based on IrC8 gives the highest EL efficiencies of external quantum efficiency (ηext) 22.7%, current efficiency (ηL) 79.7 cd A-1, and power efficiency (ηP) 58.2 lm W-1, representing the most state-of-the-art EL ability ever achieved by coumarin-based phosphorescent emitters. All these encouraging data definitely suggest the great potential of the coumarin skeleton in both easy tuning of the photophysical properties of ppy-type Ir(III) phosphorescent complexes and developing high-performance phosphorescent emitters.

Asymmetric Heteroleptic Ir(III) Phosphorescent Complexes with Aromatic Selenide and Selenophene Groups: Synthesis and Photophysical, Electrochemical, and Electrophosphorescent Behaviors.

With the aim of evaluating the potential of selenium-containing groups in developing electroluminescent (EL) materials, a series of asymmetric heteroleptic Ir(III) phosphorescent complexes (Ir-Se0F, Ir-Se1F, Ir-Se2F, and Ir-Se3F) have been synthesized by using 2-selenophenylpyridine and one ppy-type (ppy = 2-phenylpyridine) ligand with a fluorinated selenide group. To the best of our knowledge, these complexes represent unprecedented examples of asymmetric heteroleptic Ir(III) phosphorescent emitters bearing selenium-containing groups. Natural transition orbital (NTO) analysis based on optimized geometries of the first triplet state (T1) have shown that the phosphorescent emissions of these Ir(III) complexes dominantly show 3π-π* features of the 2-selenophenylpyridine ligand with slight metal to ligand charge transfer (MLCT) contribution. In comparison with their symmetric parent complex Ir-Se with two 2-selenophenylpyridine ligands, these asymmetric heteroleptic Ir(III) phosphorescent complexes can show much higher phosphorescent quantum yields (ΦP) of ca. 0.90. Both the hole- and electron-trapping ability of these Ir(III) phosphorescent complexes can be enhanced by selenophene and fluorinated selenide groups to improve their EL efficiencies. The EL abilities of these asymmetric heteroleptic Ir(III) phosphorescent emitters fall in the order Ir-Se3F > Ir-Se2F > Ir-Se1F > Ir-Se0F. The highest EL efficiencies have been achieved by Ir-Se3F in the solution-processed OLEDs with external quantum efficiency (ηext), current efficiency (ηL), and power efficiency (ηP) of 19.9%, 65.6 cd A-1, and 57.3 lm W-1, respectively. These encouraging EL results clearly indicate the great potential of selenium-containing groups in developing high-performance Ir(III) phosphorescent emitters.

A Yellow-Emitting Homoleptic Iridium(III) Complex Constructed from a Multifunctional Spiro Ligand for Highly Efficient Phosphorescent Organic Light-Emitting Diodes.

To suppress concentration quenching and to improve charge-carrier injection/transport in the emission layer (EML) of phosphorescent organic light-emitting diodes (PhOLEDs), a facial homoleptic iridium(III) complex emitter with amorphous characteristics was designed and prepared in one step from a multifunctional spiro ligand containing spiro[fluorene-9,9'-xanthene] (SFX) unit. Single-crystal X-ray analysis of the resulting fac-Ir(SFXpy)3 complex revealed an enlarged Ir···Ir distance and negligible intermolecular π-π interactions between the spiro ligands. The emitter exhibits yellow emission and almost equal energy levels compared to the commercial phosphor iridium(III) bis(4-phenylthieno[3,2-c]pyridinato-N,C2')acetylacetonate (PO-01). Dry-processed devices using a common host, 4,4'-bis(N-carbazolyl)-1,1'-biphenyl, and the fac-Ir(SFXpy)3 emitter at a doping concentration of 15 wt % exhibited a peak performance of 46.2 cd A-1, 36.3 lm W-1, and 12.1% for the current efficiency (CE), power efficiency (PE), and external quantum efficiency (EQE), respectively. Compared to control devices using PO-01 as the dopant, the fac-Ir(SFXpy)3-based devices remained superior in the doping range between 8 and 15 wt %. The current densities went up with increasing doping concentration at the same driving voltage, while the roll-offs remain relatively low even at high doping levels. The superior performance of the new emitter-based devices was ascribed to key roles of the spiro ligand for suppressing aggregation and assisting charge-carrier injection/transport. Benefiting from the amorphous stability of the emitter, the wet-processed device also exhibited respectful CE, PE, and EQE of 32.2 cd A-1, 22.1 lm W-1, and 11.3%, respectively, while the EQE roll-off was as low as 1.7% at the luminance of 1000 cd m-2. The three-dimensional geometry and binary-conjugation features render SFX the ideal multifunctional module for suppressing concentration quenching, facilitating charge-carrier injection/transport, and improving the amorphous stability of iridium(III)-based phosphorescent emitters.