Realization of Long Operational Lifetimes in Vacuum-Deposited Organic Light-Emitting Devices Based on para-Substituted Pyridine Carbazolylgold(III) C

A new series of robust C^C^N carbazolylgold(III) complexes is designed and synthesized through the introduction of inert and sterically bulky oligophenyl substituents on the pyridyl moiety of the cyclometalating ligand. High photoluminescence quantum yields of up to 96% are recorded with these complexes doped in solid-state thin films, and short excited-state lifetimes of 0.3 µs or less in the solid state at room temperature are found. Promising electroluminescence (EL) performances are shown by the vacuum-deposited organic light-emitting devices (OLEDs) based on this series of gold(III) complexes. High external quantum efficiencies of up to 19.5% with efficiency roll-offs of down to 10% at a practical luminance brightness level of 1000 cd m-2 are achieved. More importantly, record-long operational lifetimes (LT50) of up to 470,700 h at 100 cd m-2 are realized, which is currently the highest value among all classes of gold(III) complexes with tridentate pincer ligands. Particularly, by introducing a sterically bulky terphenyl moiety on the reactive site of the pyridine ring, the LT50 value is shown to attain ∼7 times longer half-lifetime than that based on the unsubstituted complex. These unprecedented EL performances and the simple synthetic route in a mercury-free fashion make them promising emitting materials for practical OLEDs toward commercialization.

Tetradentate C∧C∧N∧N Ligand-Containing Gold(III) Complexes with Orange to Deep-Red Thermally Activated Delayed Fluorescence (TADF) and Their Application in Organic Light-Emitting Devices.

A new class of thermally activated delayed fluorescence (TADF) tetradentate C∧C∧N∧N ligand-containing gold(III) complexes containing acridinyl moieties has been designed and synthesized. These complexes exhibit orange-red to deep-red emission with photoluminescence quantum yields (PLQYs) of up to 0.76 in solid-state thin films. Short excited-state lifetimes of ≤2.0 µs and large radiative decay rate constants (kr) in the order of 105 s-1 have also been found in the complexes. High-performance solution-processed and vacuum-deposited organic light-emitting devices (OLEDs) based on these complexes have been fabricated, demonstrating high maximum external quantum efficiencies (EQEs) of 12.2 and 12.7%, respectively, which are among the best values ever reported for red-emitting gold(III)-based OLEDs. In addition, satisfactory operational half-lifetime (LT50) values of up to 34,058 h have been attained in these red-emitting devices. It is found that the operational stability is strongly dependent on the choice of functional groups on the acridinyl moieties, of which the incorporation of -O- and -S- linkers can effectively prolong the LT50 value by an order of magnitude. The TADF properties of the complexes are substantiated by the hypsochromic shift in emission energies and the remarkable enhancement in the emission intensity upon increasing temperature. The TADF properties have also been supported by temperature-dependent ultrafast transient absorption studies, with the direct observation of reverse intersystem crossing (RISC) and the determination of the activation parameters for the very first time, together with their excited-state dynamics.

Molecular Design of Luminescent Gold(III) Emitters as Thermally Evaporable and Solution-Processable Organic Light-Emitting Device (OLED) Materials.

The advancement of high-efficiency luminescent and thermally stable organometallic complexes has offered opportunities for the commercialization of metal phosphors for fabricating organic light-emitting devices (OLEDs). Since the first report on the potential use of iridium(III) and platinum(II) complexes for applications in OLEDs in the late 1990s, extensive efforts have been made by researchers on the development of various heavy metal-containing compounds with rich photophysical and luminescence properties and the engineering of device architectures to improve device efficiencies. Apart from the more well-studied iridium(III) and platinum(II) complexes, complexes of gold(III) recently have demonstrated their capabilities to serve as phosphorescent or thermally stimulated delayed phosphorescent or thermally activated delayed fluorescent emitters, and their promising performances in OLEDs have attracted growing interest in the past decade. Nowadays, complexes of gold(III) with emission energies ranging from sky-blue to near-infrared with high electroluminescence performances have been obtained. In addition, high-efficiency vacuum-deposited and solution-processed OLEDs with benchmark efficiencies comparable to those of the iridium(III) and platinum(II) complexes have been realized. This Focus Review summarizes the development of various series of luminescent gold(III) complexes to date and highlights important milestones in the development and advancement of gold(III)-based OLEDs. Focus will be made on the molecular design strategies for gold(III) emitters for application as dopants in OLEDs, including those fabricated by vacuum-deposition and solution-processing techniques.

Thermally Stimulated Delayed Phosphorescence (TSDP)-Based Gold(III) Complexes of Tridentate Pyrazine-Containing Pincer Ligand with Wide Emission Color Tunability and Their Application in Organic Light-Emitting Devices.

A new class of pyrazine-based carbazole-containing gold(III) complexes featuring thermally stimulated delayed phosphorescence (TSDP) properties has been designed and synthesized. The emission colors are found to be sensitive to the coordinating atom of the carbazolyl ligands at the gold(III) center, with emission energies spanning from green to red. The efficiency of TSDP can be enhanced by lowering the polarity of the solvent, as supported by the variable-temperature emission and computational studies. Interestingly, a significant spectral shift in electroluminescence with the change of Commission Internationale de L'Eclairage (CIE) coordinates from (0.35, 0.60) to (0.44, 0.54) has been achieved by simply changing the host material from CBP to TmPyPB. Solution-processable organic light-emitting devices (OLEDs) have also been fabricated, with maximum current efficiencies of up to 22.4 cd A-1 and maximum external quantum efficiencies (EQEs) approaching 7.0%. A higher current efficiency of 35.1 cd A-1 and EQE of 10.7% can be achieved for the vacuum-deposited device based on 1, representing the first demonstration of pyrazine-based tridentate ligand-containing gold(III) complexes as phosphorescent material for OLED application.

Photoresponsive Dithienylethene-Containing Tris(8-hydroxyquinolinato)aluminum(III) Complexes with Photocontrollable Electron-Transporting Properties for Solution-Processable Optical and Organic Resistive Memory Devices.

The rational design of a new class of photoresponsive tris(8-hydroxyquinolinato)aluminum(III) (Alq3) complexes has been developed. By incorporating the photochromic dithienylethene units with different peripheral heterocycles into the Alq3 framework, the photochromic properties as well as photoswitching efficiency can be readily modulated, through effective photocyclization of the Al(III) complex. Such intrinsic photochromic behavior leads to the unprecedented enhancement in the electron-transporting properties as demonstrated by the as-fabricated electron-only device, rendering the realization of photoswitchable electron mobility. In addition, one of these complexes is capable of serving as an active layer for solution-processable resistive memory devices. Photocontrollable memory performance has been achieved with a binary memory behavior, with high ON/OFF ratio and long retention time. This work represents not only the first example of photoresponsive Alq3-based electron-transporting materials but also the solution-processable Alq3-based optical and resistive memory devices with photocontrollable performance.

Isomeric Tetradentate Ligand-Containing Cyclometalated Gold(III) Complexes.

A simple one-pot two bond-forming reaction for the rapid construction of cyclometalated gold(III) complexes with fully π-conjugated tetradentate ligand is reported. The coupling of the bifunctional gold(III) precursor with the bifunctional aromatic compound has led to the formation of two regioisomers with either C- or N-coordination. Through monitoring by high-throughput high performance liquid chromatography, the regioselectivity of the reaction has been effectively tuned toward the formation of a single isomer, allowing easy separation of the metal complexes. The structures of the complexes have been determined by X-ray crystallography, and the photophysical, electrochemical, and electroluminescence (EL) studies have been carried out. Computational study has been performed to provide insights into the nature of the excited states. Isomeric effect has been shown to have a significant influence on the EL behavior of the organic light-emitting devices.

Design Strategy Towards Horizontally Oriented Luminescent Tetradentate-Ligand-Containing Gold(III) Systems.

Phosphorescent dopants are promising candidates for organic light-emitting diodes (OLEDs). Although it has been established that the out-coupling efficiency and overall performances of vacuum-deposited OLEDs can be significantly improved by a horizontal orientation of the dopants, no horizontally oriented gold(III) complexes have been reported to date. Herein, a novel class of tetradentate C^C^N^N ligand-containing gold(III) complexes with a preferential horizontal orientation successfully generated through a one-pot reaction is reported. These complexes demonstrate high photoluminescence quantum yields of 70 % and a high horizontal dipole ratio of 0.87 in solid-state thin films. Green-emitting OLEDs based on these complexes operate with a maximum external quantum efficiency of 20.6 % with an estimated out-coupling efficiency of around 30 %. A promising device stability has been achieved in the vacuum-deposited OLEDs, with operational half-lifetimes of around 37 500 h at 100 cd m-2 .

Judicious Choice of N-Heterocycles for the Realization of Sky-Blue- to Green-Emitting Carbazolylgold(III) C

A new class of sky-blue- to green-emitting carbazolylgold(III) C^C^N complexes containing pyrazole or benzimidazole moieties has been successfully designed and synthesized. Through the judicious choice of the N-heterocycles in the cyclometalating ligand and the tailor-made carbazole moieties, maximum photoluminescence quantum yields of 0.52 and 0.39 have been realized in the green- and sky-blue-emitting complexes, respectively. Solution-processed and vacuum-deposited organic light-emitting devices (OLEDs) based on the benzimidazole-containing complexes have been prepared. The sky-blue-emitting device shows an emission peaking at 484 nm with a narrow full-width at half-maximum of 57 nm (2244 cm-1 ), demonstrating the potential of this class of complexes in the application of OLEDs with high color purity. In addition, high maximum external quantum efficiencies of 12.3 % and a long operational half-lifetime of over 5300 h at 100 cd m-2 have been achieved in the vacuum-deposited green-emitting devices.

Ligand Mediated Luminescence Enhancement in Cyclometalated Rhodium(III) Complexes and Their Applications in Efficient Organic Light-Emitting Devices.

A series of luminescent cyclometalated rhodium(III) complexes have been designed and prepared. The improved luminescence property is realized by the judicious choice of a strong σ-donor cyclometalating ligand with a lower-lying intraligand (IL) state that would raise the d-d excited state and introduction of a lower-lying emissive IL excited state. These complexes exhibit high thermal stability and considerable luminescence quantum yields as high as up to 0.65 in thin film, offering themselves as promising light-emitting materials in OLEDs. Respectable external quantum efficiencies of up to 12.2% and operational half-lifetimes of over 3000 h at 100 cd m-2 have been achieved. This work demonstrates a breakthrough as the first example of an efficient rhodium(III) emitter for OLED application and opens up a new avenue for diversifying the development of OLED materials with rhodium metal being utilized as phosphors.

Four-Coordinate Boron Emitters with Tridentate Chelating Ligand for Efficient and Stable Thermally Activated Delayed Fluorescence Organic Light-Emitting Devices.

A new class of four-coordinate donor-acceptor fluoroboron-containing thermally activated delayed fluorescence (TADF) compounds bearing a tridentate 2,2'-(pyridine-2,6-diyl)diphenolate (dppy) ligand has been successfully designed and synthesized. Upon varying the donor moieties from carbazole to 10H-spiro[acridine-9,9'-fluorene] to 9,9-dimethyl-9,10-dihydroacridine, these boron derivatives exhibit a wide range of emission colors spanning from blue to yellow with a large spectral shift of 2746 cm-1 , with high PLQYs of up to 96 % in the doped thin film. Notably, vacuum-deposited organic light-emitting devices (OLEDs) made with these boron compounds demonstrate high performances with the best current efficiencies of 55.7 cd A-1 , power efficiencies of 58.4 lm W-1 and external quantum efficiencies of 18.0 %. More importantly, long operational stabilities of the green-emitting OLEDs based on 2 with half-lifetimes of up to 12 733 hours at an initial luminance of 100 cd m-2 have been realized. This work represents for the first time the design and synthesis of tridentate dppy-chelating four-coordinate boron TADF compounds for long operational stabilities, suggesting great promises for the development of stable boron-containing TADF emitters.

Realization of Thermally Stimulated Delayed Phosphorescence in Arylgold(III) Complexes and Efficient Gold(III) Based Blue-Emitting Organic Light-Emitting Devices.

To address and overcome the difficulties associated with the increased reactivity and susceptibility of blue emitters to deactivation pathways arising from the high-lying triplet excited states, we have successfully demonstrated an innovative strategy of harvesting triplet emission via the "thermally stimulated delayed phosphorescence" mechanism, where thermal up-conversion of excitons from the lower-energy triplet excited states (T1) to higher-energy triplet excited states (T1') are observed to generate blue emission. The lower-lying T1 excited state could serve as a mediator to populate the emissive T1' state by up-conversion via reverse internal conversion, which could enhance the photoluminescence quantum yield by over 20-folds. Organic light-emitting devices with respectable external quantum efficiencies of up to 7.7% and sky-blue emission with CIE coordinates of (0.17, 0.37) have been realized. The operational stability for the device based on complex 1 has also been explored, and the device is found to show fairly respectable lifetime. This work opens up a new avenue to the design and synthesis of blue phosphorescent emitters.

The DNA Ligase IV Syndrome R278H Mutation Impairs B Lymphopoiesis via Error-Prone Nonhomologous End-Joining.

Hypomorphic mutations in the nonhomologous end-joining (NHEJ) DNA repair protein DNA ligase IV (LIG4) lead to immunodeficiency with varying severity. In this study, using a murine knock-in model, we investigated the mechanisms underlying abnormalities in class switch recombination (CSR) associated with the human homozygous Lig4 R278H mutation. Previously, we found that despite the near absence of Lig4 end-ligation activity and severely reduced mature B cell numbers, Lig4(R278H/R278H) (Lig4(R/R)) mice exhibit only a partial CSR block, producing near normal IgG1 and IgE but substantially reduced IgG3, IgG2b, and IgA serum levels. In this study, to address the cause of these abnormalities, we assayed CSR in Lig4(R/R) B cells generated via preassembled IgH and IgK V region exons (HL). This revealed that Lig4(R278H) protein levels while intact exhibited a higher turnover rate during activation of switching to IgG3 and IgG2b, as well as delays in CSR kinetics associated with defective proliferation during activation of switching to IgG1 and IgE. Activated Lig4(R/R)HL B cells consistently accumulated high frequencies of activation-induced cytidine deaminase-dependent IgH locus chromosomal breaks and translocations and were more prone to apoptosis, effects that appeared to be p53-independent, as p53 deficiency did not markedly influence these events. Importantly, NHEJ instead of alternative end-joining (A-EJ) was revealed as the predominant mechanism catalyzing robust CSR. Defective CSR was linked to failed NHEJ and residual A-EJ access to unrepaired double-strand breaks. These data firmly demonstrate that Lig4(R278H) activity renders NHEJ to be more error-prone, and they predict increased error-prone NHEJ activity and A-EJ suppression as the cause of the defective B lymphopoiesis in Lig4 patients.

Highly Emissive Fused Heterocyclic Alkynylgold(III) Complexes for Multiple Color Emission Spanning from Green to Red for Solution-Processable Organic Light-Emitting Devices.

A new class of fused heterocyclic tridentate ligand-containing alkynylgold(III) complexes with tunable emission color has been successfully designed and synthesized. Structural modification of the σ-donating fused heterocyclic alkynyl ligands, including substituted fluorene, carbazole, and triphenylamine, enables a large spectral shift of about 110 nm (ca. 3310 cm-1 ) that covers the green to red region to be realized with the same tridentate ligand-containing alkynylgold(III) complexes in solid-state thin films. Interestingly, the energy of the excimeric emission can be controlled by the rational design of the fused heterocyclic alkynyl ligands. Superior solution-processable organic light-emitting devices (OLEDs) with high external quantum efficiencies (EQEs) of 12.2, 13.5, 9.3, and 5.2 % were obtained with green, yellow, orange, and red emission. These high EQE values are comparable to those of the vacuum-deposited OLEDs based on structurally related alkynylgold(III) complexes.

Synthesis and Characterization of Luminescent Cyclometalated Platinum(II) Complexes with Tunable Emissive Colors and Studies of Their Application in Organic Memories and Organic Light-Emitting Devices.

A series of luminescent cyclometalated N^C^N [N^C^N = 1,3-bis(N-alkylbenzimidazol-2'-yl)benzene]platinum(II) alkynyl and carbazolyl complexes has been prepared. The structure of one platinum(II) carbazolyl complex has been characterized by X-ray crystallography. The corresponding electrochemical and photophysical properties have been explored and analyzed. The N^C^N platinum(II) complexes displayed rich luminescence in degassed dichloromethane solution, with their emission profiles dependent on the coordinated alkynyl and carbazolyl ligands. Their emission energies are correlated to the electronic properties of the alkynyl and carbazolyl ligands. By varying the electronic properties of the alkynyl and carbazolyl ligands, emission energies could be fine-tuned to cover a wide range of the visible spectrum, as supported by computational studies. A donor-acceptor platinum(II) complex has been utilized to fabricate memory devices that exhibit binary memory performances with low operating voltages, high ON/OFF ratios, and long retention times. Solution-processable OLEDs have been fabricated based on another platinum(II) carbazolyl complex, resulting in a maximum external quantum efficiency of up to 7.2%, which is comparable to that of the vacuum-deposited devices based on the small-molecule counterpart, illustrating the multifunctional nature of the platinum(II)-containing materials.

Sky-Blue-Emitting Dendritic Alkynylgold(III) Complexes for Solution-Processable Organic Light-Emitting Devices.

A new class of tridentate ligand-containing cyclometalated gold(III) complexes featuring dendritic alkynyl ligands with carbazole moieties as dendrons and peripheral groups has been synthesized up to the third generation. High-performance solution-processable organic light-emitting devices (OLEDs) with maximum current efficiency of up to 23.7 cd A-1 and external quantum efficiency of up to 6.9% have been realized by a simple spin-coating technique. With the incorporation of bulky carbazole moieties to form higher generation dendrimers, the undesirable excimeric emission could be effectively reduced, allowing the fine-tuning of the emission color toward the blue region. This represents the first successful demonstration of sky-blue-emitting alkynylgold(III) complexes and its application in solution-processable OLEDs.

Strategy for the Realization of Efficient Solution-Processable Phosphorescent Organic Light-Emitting Devices: Design and Synthesis of Bipolar Alkynylplatinum(II) Complexes.

A new class of highly luminescent bipolar alkynylplatinum(II) complexes has been synthesized, characterized, and applied as phosphorescent dopants in the fabrication of solution-processable organic light-emitting devices (OLEDs). Through the incorporation of a delicate balance of electron-donating carbazole moieties and electron-accepting phenylbenzimidazole or oxadiazole moieties into the platinum(II) core, the platinum(II) complexes have been demonstrated to exhibit bipolar charge transport character with high photoluminescence quantum yields of up to 0.75 in thin films. The introduction of meta-linkages into the complexes further helps weaken the donor-acceptor interactions, facilitating better carrier-transporting abilities. More importantly, high-performance solution-processable green-emitting OLEDs with maximum current efficiencies of up to 57.4 cd A-1 and external quantum efficiencies of up to 16.0% have been realized. This is among the best performances for solution-processable phosphorescent OLEDs reported based on platinum(II) complexes as well as bipolar metal complexes.

Versatile Design Strategy for Highly Luminescent Vacuum-Evaporable and Solution-Processable Tridentate Gold(III) Complexes with Monoaryl Auxiliary Ligands and Their Applications for Phosphorescent Organic Light Emitting Devices.

A new class of brightly blue-green-emitting arylgold(III) complexes has been synthesized, characterized, and applied as phosphorescent dopants in the fabrication of solution-processable and vacuum-deposited organic light-emitting devices (OLEDs). These arylgold(III) complexes can be readily synthesized by reacting the corresponding arylboronic acids with the gold(III) precursor complexes in a one-pot Suzuki-Miyaura coupling reaction. When compared to the structurally related alkynylgold(III) complex, arylgold(III) complexes 1 and 2 exhibit much higher photoluminescence quantum yields in solution state. High photoluminescence quantum yields are also observed in solid-state thin films. More importantly, the solid-state emission spectra show strong resemblance to those in solution, irrespective of the dopant concentration, leading to significant improvement in the color purity of the OLEDs by suppressing any excimer emission resulting from the π-stacking of the tridentate ligand. High performance solution-processable and vacuum-deposited blue-green-emitting OLEDs have also been realized, with maximum external quantum efficiencies of 7.3% and 14.7%, respectively, representing the first demonstration of efficient blue-green-emitting OLEDs based on cyclometalated arylgold(III) complexes.

Versatile Synthesis of Luminescent Tetradentate Cyclometalated Alkynylgold(III) Complexes and Their Application in Solution-Processable Organic Light-Emitting Devices.

A new class of cyclometalated tetradentate alkynylgold(III) complexes has been successfully synthesized by post-synthetic modification. Through the judicious design and choice of pincer ligands, post-synthetic cyclization could be achieved to produce the robust and structurally rigid class of tetradentate gold(III) C^N^C^C complexes with high photoluminescence quantum yields of up to 0.49 in solution and 0.78 in doped thin films at room temperature, at least an order of magnitude higher than those of the structurally related uncyclized tridentate alkynylgold(III) analogues. High-performance yellow to orange-red emitting solution-processable organic light-emitting devices have also been achieved with external quantum efficiency of 11.1 %. This work describes for the first time of the use of post-synthetic ligand modification approach to overcome the synthetic challenge for tetradentate alkynylgold(III) complexes.

Design Strategy for High-Performance Dendritic Carbazole-Containing Alkynylplatinum(II) Complexes and Their Application in Solution-Processable Organic Light-Emitting Devices.

A new class of luminescent dendritic carbazole-containing alkynylplatinum(II) complexes has been synthesized, characterized, and applied as phosphorescent dopants in the fabrication of solution-processable organic light-emitting devices (OLEDs). These complexes exhibit high photoluminescence quantum yields of up to 80% in spin-coated thin films. In addition, the incorporation of carbazole dendrons into the platinum(II) center can significantly suppress intermolecular interactions in solid-state thin films, giving rise to emission spectra that are similar to those found in solution irrespective of dopant concentrations. High-performance solution-processable OLEDs have also been fabricated, with a maximum external quantum efficiency of up to 10.4%, which is comparable to that of the vacuum-deposited devices based on the small-molecule counterpart. This is one of the highest ever reported values for solution-processable devices based on platinum(II) complexes with tridentate ligands.

Air-Stable Spirofluorene-Containing Ladder-Type Bis(alkynyl)borane Compounds with Readily Tunable Full Color Emission Properties.

A series of air-stable spiro-fused ladder-type boron(III) compounds has been designed, synthesized, and the electrochemistry and photophysical behavior have been characterized. By simply varying the substituents on the pyridine ring and extending the π-conjugation of the spiro framework, the emission color of these compounds can be easily fine-tuned spanning the visible spectrum from blue to red. All compounds exhibit a broad and structureless emission band across the entire visible region, assigned as an intramolecular charge-transfer transition originating from the thiophene of the spiro framework to the pyridine-borane moieties. In addition, these compounds demonstrate high photoluminescence quantum yields of up to 0.81 in dichloromethane solution and 0.86 in doped thin films. Some of the compounds have also been employed as emissive materials, in which solution-processed organic light-emitting devices (OLEDs) with tunable emission colors spanning the visible spectrum from blue, green to red have been realized, demonstrating the potential applications of these boron compounds in OLEDs.