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.

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.

Multi-functional bis(alkynyl)gold(iii) N⁁C complexes with distinct mechanochromic luminescence and electroluminescence properties.

A new class of donor-acceptor type luminescent bis(alkynyl)gold(iii) N⁁C complexes has been synthesized and characterized. These gold(iii) complexes not only exhibit high photoluminescence quantum yields of up to 0.81, but also interesting mechanochromic luminescence behaviors that are reversible. Upon grinding, a dramatic luminescence color change from green to red can be observed in solid samples of the gold(iii) complexes, and the mechanochromic luminescence can be readily tuned via a judicious selection of substituents on the pyridine ring. In addition, solution-processable OLEDs based on this class of complexes with EQE values of up to 4.0% have been realized, representing the first demonstration of bis(alkynyl)gold(iii) N⁁C complexes as emissive materials in solution-processable OLEDs.

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 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.

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.

Bifunctional Heterocyclic Spiro Derivatives for Organic Optoelectronic Devices.

A series of heterocyclic spiro derivatives has been successfully synthesized and characterized by photophysical and electrochemical studies. Taking advantage of their excellent hole-transporting properties, highly efficient small-molecular organic photovoltaic devices based on these heterocyclic compounds as donors with very low dopant concentrations have been prepared; particularly, a high open-circuit voltage of up to 1.10 V and a power conversion efficiency of up to 5.12% have been realized. In addition, most of these heterocyclic spiro derivatives are found to be highly emissive in solutions with photoluminescence quantum yields of up to 0.91, and high-performance deep-blue-emitting organic light-emitting diodes (OLEDs) have been achieved. Such devices exhibit a stable deep blue emission with CIE coordinates of (0.16, 0.04) and high external quantum efficiencies of up to 4.7%, which is one of the best values among the reported OLEDs with CIEy < 0.08.

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.

Bipolar gold(III) complexes for solution-processable organic light-emitting devices with a small efficiency roll-off.

A new class of bipolar alkynylgold(III) complexes containing triphenylamine and benzimidazole moieties has been synthesized, characterized, and applied as phosphorescent dopants in the fabrication of solution-processable organic light-emitting devices (OLEDs). The incorporation of methyl groups in the central phenyl unit has been found to rigidify the molecule to reduce nonradiative decay, yielding a high photoluminescence quantum yield of up to 75% in spin-coated thin films. In addition, the realization of highly efficient solution-processable OLEDs with an extremely small external quantum efficiency (EQE) roll-off has been demonstrated. At practical brightness level of 1000 cd m(-2), the optimized devices exhibited a high EQE of up to 10.0% and an extremely small roll-off of less than 1%.

Saturated red-light-emitting gold(III) triphenylamine dendrimers for solution-processable organic light-emitting devices.

A novel isoquinoline-containing C^N^C ligand and its phosphorescent triphenylamine-based alkynylgold(III) dendrimers have been synthesized. These alkynylgold(III) dendrimers serve as phosphorescent dopants in the fabrication of efficient solution-processable organic light-emitting devices (OLEDs). The photophysical, electrochemical, and electroluminescence properties were studied. A saturated red emission with CIE coordinates of (0.64, 0.36) and a high EQE value of 3.62% were achieved. Unlike other red-light-emitting iridium(III) dendrimers, a low turn-on voltage of less than 3 V and a reduced efficiency roll-off at high current densities were observed; this can be accounted for by the enhanced carrier transporting ability and the relatively short lifetimes in the high-generation dendrimers. This class of alkynylgold(III) dendrimers are promising candidates as phosphorescent dopants in the fabrication of solution-processable OLEDs.