DE102021100230A1 - Organic light emitting material - Google Patents

Abstract

An organic light-emitting material is provided. The light-emitting material is a series of metal complexes containing one or more ligands based on isoquinoline, which is substituted in the 3- and 4-position with deuterium, and one or more ligands based on acetylacetone. The compounds can be used as a light emitting material in an emitting layer of an organic electroluminescent device. These new connections can provide better device performance. Furthermore, an electroluminescent device and a connection combination containing the light-emitting material are provided.

Description

CROSS REFERENCE TO RELATED APPLICATION (S)

This application claims priority from Chinese Patent Application No. CN 202010026581.1 filed on January 10, 2020 and Chinese Patent Application No. CN 202011438481.6 , filed on December 11, 2020, the disclosure of which is incorporated herein by reference in its entirety.

TECHNICAL AREA

The present disclosure relates to compounds for organic electronic devices, for example organic light emitting devices. In particular, the present disclosure relates to an organic light-emitting material containing deuterium-substituted ligands and an electroluminescent device and a combination of compounds containing the organic light-emitting material.

BACKGROUND

Organic electronic devices include, but are not limited to, the following types: organic light emitting diodes (OLEDs), organic field effect transistors (O-FETs), organic light emitting transistors (OLETs), organic photovoltaic devices (OPVs), dye solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field quenching devices (OFQDs), light emitting electrochemical cells (LECs), organic laser diodes, and organic plasmon emitting devices.

In 1987 Tang and Van Slyke of Eastman Kodak reported a two-layer organic electroluminescent device containing an arylamine hole transport layer and a tris-8-hydroxyquinolato-aluminum layer as the electron and emission layer (Applied Physics Letters, 1987, 51 (12) : 913-915). As soon as a bias voltage is applied to the device, green light has been emitted from the device. This device laid the foundation for the development of modern organic light-emitting diodes (OLEDs). Modern OLEDs can comprise several layers, such as charge injection and transport layers, charge and exciton barrier layers and one or more emitting layers between the cathode and anode. Since the OLED is a self-emitting solid-state component, it offers enormous potential for display and lighting applications. In addition, the inherent properties of organic materials, such as their flexibility, can make them well suited for certain applications such as manufacturing on flexible substrates.

The OLED can be divided into three different types according to its emission mechanism. The OLED invented by Tang and van Slyke is a fluorescent OLED. It only uses the singlet emission. The triplets generated in the device are wasted by non-radiative decay channels. Therefore, the internal quantum efficiency (IQE) of the fluorescent OLED is only 25%. This limitation hindered the commercialization of the OLED. In 1997 Forrest and Thompson reported on a phosphorescent OLED that uses triplet emission from complexes containing heavy metals as an emitter. As a result, both singlets and triplets can be harvested, achieving an IQE of 100%. The discovery and development of the phosphorescent OLED contributed directly to the commercialization of the active matrix OLED (AMOLED) due to its high efficiency. Recently, Adachi achieved high efficiency through thermally activated delayed fluorescence (TADF) of organic compounds. These emitters have a small singlet-triplet gap that makes the transition from triplet back to singlet possible. In the TADF device, the triplet excitons can reverse intersystem crossing to produce singlet excitons, resulting in a high IQE.

OLEDs can also be classified as small molecule and polymer OLEDs, depending on the types of materials used. A small molecule refers to any organic or organometallic material that is not a polymer. The molecular weight of the small molecule can be large as long as it has a well-defined structure. Dendrimers with well-defined structures are considered to be small molecules. Polymer OLEDs include conjugated polymers and non-conjugated polymers with pendant emitting groups. Small molecule OLEDs can become polymer OLEDs if post-polymerization takes place during the manufacturing process.

There are various methods of manufacturing OLEDs. Small molecule OLEDs are generally produced by thermal evaporation in a vacuum. Polymer OLEDs are made by solution processes such as spin coating, inkjet printing, and slot printing. If the material can be dissolved or dispersed in a solvent, the small molecule OLED can also be made by a solution process.

The emitting color of the OLED can be achieved through the structural design of the emitter. An OLED can comprise an emitting layer or a multiplicity of emitting layers in order to achieve the desired spectrum. In the case of green, yellow, and red OLEDs, phosphorescent emitters have successfully reached commercialization. Blue phosphorescent devices still suffer from unsaturated blue color, short device life, and high operating voltage. Commercial full color OLED displays typically use a hybrid strategy with fluorescent blue and phosphorescent yellow, red, or green. At present, the efficiency roll-off of phosphorescent OLEDs at high brightness remains a problem. In addition, it is desirable to have a more saturated emissive color, higher efficiency, and longer device life.

die eine kondensierte Ringstruktur mit der folgenden Struktur enthält:

oder

Spezifische Beispiele für diese Verbindung schließen

ein. Diese Offenbarung konzentriert sich auf Leistungsänderungen, die durch die Einführung der kondensierten Ringstruktur in einen Liganden hervorgerufen werden. Obwohl die obige Anmeldung verwandte Komplexe von Isochinolin mit zwei an der 5- und 8-Position eingeführten Deuteriumatomen erwähnt, wird keine Studie über die Wirkung der Deuterierung durchgeführt, geschweige denn über die Änderung der Eigenschaften des Metallkomplexes, die durch die Einführung der Deuterierung in spezifischer 3- und 4-Position am Isochinolinring bewirkt wird. US20150171348A1 discloses a connection with the following substructure:

which contains a condensed ring structure with the following structure:

or

Specific examples of this compound include

a. This disclosure focuses on changes in performance caused by the introduction of the fused ring structure into a ligand. Although the above application mentions related complexes of isoquinoline with two deuterium atoms introduced at the 5- and 8-positions, no study is carried out on the effect of deuteration, let alone on the change in the properties of the metal complex caused by the introduction of deuteration in more specific 3- and 4-position on the isoquinoline ring is effected.

wobei

ausgewählt sein kann aus einer Phenylisochinolinstruktur und der Ligand X aus einem Acetylaceton-basierten Liganden ausgewählt sein kann. Spezifische Beispiele für diese Verbindung schließen

ein. Die Erfinder der obigen Anmeldung bemerken die Verbesserung der Vorrichtungseffizienz, die durch die Einführung mehrerer Deuteriumatome in den Iridiumkomplex-Liganden bewirkt wird, aber sie bemerken nicht den besonderen Vorteil der Erhöhung der Vorrichtungslebensdauer, der durch die Einführung der Deuteriumatomsubstitution an der spezifischen 3- und 4-Position am Isochinolinring bewirkt wird. US20080194853A1 discloses an iridium complex with the following structure:

in which

can be selected from a phenylisoquinoline structure and the ligand X can be selected from an acetylacetone-based ligand. Specific examples of this compound include

a. The inventors of the above application note the improvement in device efficiency caused by the introduction of multiple deuterium atoms in the iridium complex ligand, but they do not notice the particular advantage of increasing the device life, which is achieved by the introduction of the deuterium atom substitution at the specific 3 and 4 Position on the isoquinoline ring is effected.

wobei R² und R⁷ bis R¹⁰ jeweils unabhängig ausgewählt sind aus H, D, Alkyl, Hydroxyl, Alkoxy, Sulfhydryl, Alkylthio, Amino und anderen Substituenten, α 0, 1 oder 2 ist und δ 0 oder eine ganze Zahl von 1 bis 4 ist. Beispiele in der obigen Anmeldung werden mit den Fällen beschrieben, in denen α und δ gleich 0 sind, und es werden weder Beispiele offenbart, dass der Isochinolinring R²-Substituenten aufweist, noch werden die durch den Iridiumkomplex aufgrund der Einführung von Deuteriumatomen erzielten Effekte diskutiert. US20030096138A1 discloses an active layer containing a compound with the IrL ₃ following formula: IrL ₃ Z, where the ligand L can be selected from the structure of the following formula:

where R ² and R ⁷ to R ^{10 are} each independently selected from H, D, alkyl, hydroxyl, alkoxy, sulfhydryl, alkylthio, amino and other substituents, α 0, 1 or 2 and δ 0 or an integer from 1 to 4 is. Examples in the above application are described with the cases where α and δ are 0, and no examples are disclosed that the isoquinoline ^{ring has R 2} substituents, nor are the effects achieved by the iridium complex due to the introduction of deuterium atoms discussed .

wobei R₁ bis R₃ ausgewählt sind aus Alkyl/deuteriertem Alkyl. Die Erfinder der obigen Anmeldung bemerken die Verbesserung der Effizienz des Iridiumkomplexes, die durch einen Alkyl-/deuteriertes Alkyl-substituierten Phenylisochinolin-Liganden bewirkt wird, aber sie bemerken nicht die Verbesserung der Eigenschaften des Metallkomplexes, insbesondere die Verbesserung in Bezug auf Lebensdauer und Effizienz, die durch die direkte Deuterierung am Isochinolin-Ring bewirkt wird. WO2018124697A1 discloses an organic electroluminescent compound having the following structure:

where R ₁ to R _{3 are} selected from alkyl / deuterated alkyl. The inventors of the above application note the improvement in the efficiency of the iridium complex brought about by an alkyl / deuterated alkyl substituted phenylisoquinoline ligand, but they do not notice the improvement in the properties of the metal complex, particularly the improvement in terms of durability and efficiency, which is brought about by the direct deuteration on the isoquinoline ring.

US20100051869A1 discloses a composition containing at least one organic iridium complex having the structure of the following formula:

The inventors of the above application concentrate on the ligand having a 2-carbonylpyrrole structure. Although the perdeuterated phenylisoquinoline ligand is mentioned, they fail to note the application of the interaction with the acetylacetone based ligand in the complex, which is apparently different from the overall structure of the metal complex of the present disclosure.

wobei ein oder mehrere Wasserstoffe in diesem Komplex durch Deuterium substituiert sein können und der offenbarte C^N-Ligand die Struktur von Phenylisochinolin oder Phenylchinazolin haben kann. Spezifische Beispiele für diesen Komplex schließen ein:

und

CN109438521A discloses a complex with the following structure:

wherein one or more hydrogens in this complex can be substituted by deuterium and the disclosed C 1 N ligand can have the structure of phenylisoquinoline or phenylquinazoline. Specific examples of this complex include:

and

The inventors of the above application mainly focus on amidinate and guanidine based ligands with dinitrogen coordination. Although the perdeuterated isoquinoline ligand is mentioned, they do not note the application of the cooperation with the acetylacetone-based ligand in the complex, which is apparently different from the overall structure of the metal complex of the present disclosure.

Although iridium complexes containing a ligand with a structure of phenylisoquinoline that is fully deuterated or dideutered in the 5- and 8-positions are described in the literature, these examples involving deuteration are just some of the many disclosed examples of the iridium complex with isoquinoline ligands in the relevant literature, or these examples do not include the use of acetylacetone-based ligands in metal complexes, or these examples do not examine or discuss the deuteration effect and the influence of the deuteration positions on the performance of the device, in particular the service life. The development in related art has yet to be carried out.

SUMMARY

The present disclosure aims to provide a series of organic light-emitting materials which contain one or more ligands based on isoquinoline, which is substituted in the 3- and 4-positions with deuterium, and one or more ligands based on acetylacetone. The compounds can be used as the emitting material in the emitting layer of the organic electroluminescent device. These new metal complexes can effectively improve the efficiency and life of the device.

wobei X₁ bis X₄, bei jedem Auftreten gleich oder verschieden, ausgewählt sind aus CR₁ oder N;
wobei Y₁ bis Y₄, bei jedem Auftreten gleich oder verschieden, ausgewählt sind aus CR₂ oder N;
wobei R₁ und R₂, bei jedem Auftreten gleich oder verschieden, ausgewählt sind aus der Gruppe bestehend aus: Wasserstoff, Deuterium, Halogen, substituiertem oder unsubstituiertem Alkyl mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Cycloalkyl mit 3 bis 20 Ringkohlenstoffatomen, substituiertem oder unsubstituiertem Heteroalkyl mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Arylalkyl mit 7 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkoxy mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Aryloxy mit 6 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkenyl mit 2 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Aryl mit 6 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Heteroaryl mit 3 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkylsilyl mit 3 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Arylsilyl mit 6 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Amino mit 0 bis 20 Kohlenstoffatomen, einer Acylgruppe, einer Carbonylgruppe, einer Carbonsäuregruppe, einer Estergruppe, einer Nitrilgruppe, einer Isonitrilgruppe, einer Sulfanylgruppe, einer Sulfinylgruppe, einer Sulfonylgruppe, einer Phosphinogruppe und Kombinationen davon;
in Formel 1, benachbarte Substituenten gegebenenfalls verbunden sein können, um einen Ring zu bilden;
wobei der zweite Ligand L_b eine durch Formel 2 dargestellte Struktur aufweist:

wobei Rt bis R_z, bei jedem Auftreten gleich oder verschieden, ausgewählt sind aus der Gruppe bestehend aus: Wasserstoff, Deuterium, Halogen, substituiertem oder unsubstituiertem Alkyl mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Cycloalkyl mit 3 bis 20 Ringkohlenstoffatomen, substituiertem oder unsubstituiertem Heteroalkyl mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Arylalkyl mit 7 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkoxy mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Aryloxy mit 6 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkenyl mit 2 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Aryl mit 6 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Heteroaryl mit 3 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkylsilyl mit 3 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Arylsilyl mit 6 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Amino mit 0 bis 20 Kohlenstoffatomen, einer Acylgruppe, einer Carbonylgruppe, einer Carbonsäuregruppe, einer Estergruppe, einer Nitrilgruppe, einer Isonitrilgruppe, einer Sulfanylgruppe, einer Sulfinylgruppe, einer Sulfonylgruppe, einer Phosphinogruppe und Kombinationen davon;
in Formel 2, benachbarte Substituenten gegebenenfalls verbunden sein können, um einen Ring zu bilden;
wobei der dritte Ligand L_c ein monoanionischer zweizähniger Ligand ist.According to one embodiment of the present disclosure, a metal complex is disclosed which has the general structure M (L _a ) _m (L _b ) _n (L _c ) _q , where L _a , L _b and L _{c are} the first ligand, the second ligand, and respectively the third ligand coordinated with the metal M; wherein the metal M is a metal whose relative atomic mass is greater than 40;
wherein L _a , L _b and L _c can optionally be linked to form a multidentate ligand;
where m is 1 or 2, n is 1 or 2, q is 0 or 1, and m + n + q is the same as the oxidation state of the metal M;
when m is greater than 1, L _{a can be the} same or different; and when n is greater than 1, L _{b may be the} same or different;
wherein the first ligand L _{a has} a structure represented by Formula 1:

where X ₁ to X ₄ , identically or differently on each occurrence, are selected from CR ₁ or N;
where Y ₁ to Y ₄ , identically or differently on each occurrence, are selected from CR ₂ or N;
where R ₁ and R ₂ , identically or differently on each occurrence, are selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl with 7 to 30 carbon atoms, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 carbon atoms, substituted or unsubstituted alkenyl with 2 to 20 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl with 6 to 20 carbon atoms omen, substituted or unsubstituted amino with 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
in Formula 1, adjacent substituents may optionally be linked to form a ring;
wherein the second ligand L _{b has} a structure represented by Formula 2:

where Rt to R _z , identically or differently on each occurrence, are selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted Heteroalkyl with 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl with 7 to 30 carbon atoms, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 carbon atoms, substituted or unsubstituted alkenyl with 2 to 20 carbon atoms, substituted or unsubstituted Aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl with 6 to 20 carbon atoms men, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
in Formula 2, adjacent substituents may optionally be linked to form a ring;
wherein the third ligand L _{c is} a monoanionic bidentate ligand.

• eine Anode,
• einer Kathode, und
• eine organische Schicht, die zwischen der Anode und der Kathode angeordnet ist,
• wobei die organische Schicht einen Metallkomplex mit der allgemeinen Struktur M(L_a)_m(L_b)_n(L_c)_q beinhaltet, wobei L_a, L_b und L_c der erste Ligand, der zweite Ligand bzw. der dritte Ligand sind, die mit dem Metall M koordiniert sind; wobei das Metall M ein Metall ist, dessen Atommasse größer als 40 ist;
• wobei L_a, L_b und L_c optional verbunden sein können, um einen mehrzähnigen Liganden zu bilden;
• wobei m 1 oder 2 ist, n 1 oder 2 ist, q 0 oder 1 ist, und m+n+q gleich der Oxidationsstufe des Metalls M ist;
• wenn m größer als 1 ist, kann L_a gleich oder verschieden sein; und wenn n größer als 1 ist, kann L_b gleich oder verschieden sein;
• wobei der erste Ligand L_a eine durch Formel 1 dargestellte Struktur aufweist:
  
• wobei X₁ bis X₄, bei jedem Auftreten gleich oder verschieden, ausgewählt sind aus CR₁ oder N;
• wobei Y₁ bis Y₄, bei jedem Auftreten gleich oder verschieden, ausgewählt sind aus CR₂ oder N;
• wobei R₁ und R₂, bei jedem Auftreten gleich oder verschieden, ausgewählt sind aus der Gruppe bestehend aus: Wasserstoff, Deuterium, Halogen, substituiertem oder unsubstituiertem Alkyl mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Cycloalkyl mit 3 bis 20 Ringkohlenstoffatomen, substituiertem oder unsubstituiertem Heteroalkyl mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Arylalkyl mit 7 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkoxy mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Aryloxy mit 6 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkenyl mit 2 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Aryl mit 6 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Heteroaryl mit 3 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkylsilyl mit 3 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Arylsilyl mit 6 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Amino mit 0 bis 20 Kohlenstoffatomen, einer Acylgruppe, einer Carbonylgruppe, einer Carbonsäuregruppe, einer Estergruppe, einer Nitrilgruppe, einer Isonitrilgruppe, einer Sulfanylgruppe, einer Sulfinylgruppe, einer Sulfonylgruppe, einer Phosphinogruppe und Kombinationen davon;
• in Formel 1, benachbarte Substituenten gegebenenfalls verbunden sein können, um einen Ring zu bilden;
• wobei der zweite Ligand L_b eine durch Formel 2 dargestellte Struktur aufweist:
  
• wobei R_t bis R_z, bei jedem Auftreten gleich oder verschieden, ausgewählt sind aus der Gruppe bestehend aus: Wasserstoff, Deuterium, Halogen, substituiertem oder unsubstituiertem Alkyl mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Cycloalkyl mit 3 bis 20 Ringkohlenstoffatomen, substituiertem oder unsubstituiertem Heteroalkyl mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Arylalkyl mit 7 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkoxy mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Aryloxy mit 6 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkenyl mit 2 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Aryl mit 6 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Heteroaryl mit 3 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkylsilyl mit 3 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Arylsilyl mit 6 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Amino mit 0 bis 20 Kohlenstoffatomen, einer Acylgruppe, einer Carbonylgruppe, einer Carbonsäuregruppe, einer Estergruppe, einer Nitrilgruppe, einer Isonitrilgruppe, einer Sulfanylgruppe, einer Sulfinylgruppe, einer Sulfonylgruppe, einer Phosphinogruppe und Kombinationen davon;
• in Formel 2, benachbarte Substituenten gegebenenfalls verbunden sein können, um einen Ring zu bilden;
• wobei der dritte Ligand L_c ein monoanionischer zweizähniger Ligand ist.

According to another embodiment of the present disclosure, an electroluminescent device is further disclosed that includes:

• an anode,
• a cathode, and
• an organic layer disposed between the anode and the cathode,
• wherein the organic layer includes a metal complex with the general structure M (L _a ) _m (L _b ) _n (L _c ) _q , where L _a , L _b and L _{c are} the first ligand, the second ligand and the third ligand, respectively coordinated with the metal M; wherein the metal M is a metal whose atomic mass is greater than 40;
• wherein L _a , L _b and L _c can optionally be linked to form a multidentate ligand;
• where m is 1 or 2, n is 1 or 2, q is 0 or 1, and m + n + q is the same as the oxidation state of the metal M;
• when m is greater than 1, L _a can be the same or different; and when n is greater than 1, L _b may be the same or different;
• wherein the first ligand L _{a has} a structure represented by Formula 1:
  
• where X ₁ to X ₄ , identically or differently on each occurrence, are selected from CR ₁ or N;
• where Y ₁ to Y ₄ , identically or differently on each occurrence, are selected from CR ₂ or N;
• where R ₁ and R ₂ , identically or differently on each occurrence, are selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl with 7 to 30 carbon atoms, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 carbon atoms, substituted or unsubstituted alkenyl with 2 to 20 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl with 6 to 20 carbon atoms omen, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
• in Formula 1, adjacent substituents may optionally be linked to form a ring;
• wherein the second ligand L _{b has} a structure represented by Formula 2:
  
• where R _t to R _z , identically or differently on each occurrence, are selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl with 7 to 30 carbon atoms, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 carbon atoms, substituted or unsubstituted alkenyl with 2 to 20 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl with 6 to 20 carbon atoms omen, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
• in Formula 2, adjacent substituents may optionally be linked to form a ring;
• wherein the third ligand L _{c is} a monoanionic bidentate ligand.

According to a further embodiment of the present disclosure, a compound formulation is further disclosed that contains the metal complex described above.

The metal complex disclosed by the present disclosure can be used as a light emitting material in the emitting layer of the organic electroluminescent device. Due to the bilateral substitution at the 3- and 4-position of the isoquinoline ligand and the combination with the acetylacetonate ligand to form metal complexes, these metal complexes have unexpectedly many properties, for example the metal complexes can increase the life of the device and the external quantum efficiency improve. The metal complexes are easy to use in the manufacture of OLEDs and can provide efficient and durable electroluminescent devices. After intensive research, the inventors of the present disclosure surprisingly found that by introducing deuterium atoms into the specific positions of the isoquinoline ligand of the metal complex, such a metal complex, when used as a light-emitting material in the organic light-emitting device, the device efficiency and life can greatly improve.

Figure list

• 1 Figure 13 is a schematic representation of an organic light emitting device that may include a metal complex and a compound formulation disclosed by the present disclosure.
• 2 Figure 13 is a schematic representation of another organic light emitting device that may include a metal complex and a compound formulation disclosed by the present disclosure.

DETAILED DESCRIPTION

OLEDs can be made on different types of substrates such as glass, plastic, and metal foil. 1 Fig. 3 schematically shows an organic light emitting device 100 without restriction. The figures are not necessarily drawn to scale. Some of the layers in the figures can also be omitted as desired. The device 100 can be a substrate 101 , an anode 110 , a hole injection layer 120 , a hole transport layer 130 , an electron barrier layer 140 , an emissive layer 150 , a hole barrier 160 , an electron transport layer 170 , an electron injection layer 180 and a cathode 190 include. The device 100 can be produced by applying the layers described in the order described. The properties and functions of these various layers as well as example materials are described in more detail in US Pat. 7,279,704 in Col. 6-10, the entire contents of which are incorporated herein by reference.

More examples of each of these layers are available. For example, a flexible and transparent substrate-anode combination is in U.S. Pat. No. 5,844,363 which is incorporated herein by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ in a molar ratio of 50: 1, as disclosed in US Patent Application Publication No. 2003/0230980, which is incorporated herein by reference in its entirety. Examples of host materials are disclosed in US Pat. No. 6,303,238 to Thompson et al., Which is incorporated herein by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a molar ratio of 1: 1, as disclosed in US Patent Application Publication No. 2003/0230980, which is incorporated herein by reference in its entirety. U.S. Pat. No. 5,703,436 and 5,707,745 , which are incorporated herein by reference in their entirety, disclose examples of cathodes including composite cathodes having a thin layer of metal such as Mg: Ag with an overlying transparent, electrically conductive, sputter deposited ITO layer. The theory and use of barriers are described in more detail in U.S. Pat. No. 6,097,147 and US Patent Application Publication No. 2003/0230980, which are incorporated herein by reference in their entirety. Examples of injection layers can be found in US Patent Application Publication No. 2004/0174116, which is incorporated herein by reference in its entirety. A description of protective layers can be found in US Patent Application Publication No. 2004/0174116, which is incorporated herein by reference in its entirety.

The layered construction described above is provided by way of non-limiting examples. Functional OLEDs can be achieved in different ways by combining the various layers described, or layers can be omitted entirely. It can also contain other layers that are not specifically described. A single material or a mixture of multiple materials can be used within each layer for optimal performance. Each functional layer can contain several sublayers. For example, the emissive layer can have two layers of different emissive materials in order to achieve the desired emission spectrum.

In one embodiment, an OLED can be described as having an “organic layer” disposed between a cathode and an anode. This organic layer can comprise a single layer or multiple layers.

An OLED can be encapsulated by a barrier layer. 2 Fig. 3 schematically shows an organic light emitting device 200 without restriction. 2 differs from 1 in that the organic light emitting device has a barrier layer 102 contains, which is located above the cathode 190 to protect them from harmful environmental species such as moisture and oxygen. Any material that can fulfill the barrier function can be used as the barrier layer, such as glass or organic-inorganic hybrid layers. The barrier layer should be placed directly or indirectly outside the OLED device. The multilayer thin film encapsulation was in U.S. Pat. No. 7,968,146 which is incorporated herein by reference in its entirety.

Devices made in accordance with embodiments of the present disclosure can be incorporated into a variety of consumer products that include one or more of the electronic component modules (or units). Some examples of such consumer products include flat screens, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and / or signaling, head-up displays, fully or partially transparent displays, flexible displays, smartphones, tablets, phablets, portable devices, Smartwatches, laptops, digital cameras, camcorders, viewfinders, microdisplays, 3D displays, vehicle displays and vehicle taillights.

The materials and structures described herein can also be used in other organic electronic devices listed above.

As used herein, "top" means furthest from the substrate, while "bottom" is closest to the substrate. When a first layer is described as being "disposed over" a second layer, the first layer is disposed further from the substrate. There may be additional layers between the first and second layers, unless it is indicated that the first layer is "in contact with" the second layer. For example, a cathode can be described as being “arranged over” an anode, even if there are different organic layers in between.

As used herein, "solution processable" means that something can be dissolved, dispersed, or transported in and / or deposited from a liquid medium, either in the form of a solution or a suspension.

A ligand can be called “photoactive” if it is assumed that the ligand contributes directly to the photoactive properties of an emitting material. A ligand can be referred to as “ancillary” if it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand can alter the properties of a photoactive ligand.

It is assumed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistics limit due to delayed fluorescence. As used herein, there are two types of delayed fluorescence; H. delayed P-type fluorescence and delayed E-type fluorescence. P-type delayed fluorescence is generated by triplet-triplet annihilation (TTA).

On the other hand, the E-type delayed fluorescence is not based on the collision of two triplets, but on the transition between the triplet states and the excited singlet states. Compounds capable of generating E-type delayed fluorescence must have very small singlet-triplet gaps in order to switch between energy states. Thermal energy can activate the transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as thermally activated delayed fluorescence (TADF). A characteristic of the TADF is that the delayed component increases with increasing temperature. If the reverse intersystem crossing rate is fast enough to minimize the non-radiative decay from the triplet state, the proportion of resettled excited singlet states can potentially reach 75%. The total singlet portion can be 100%, which far exceeds the 25% of the spin statistics limit for electrically generated excitons.

The type E delayed fluorescence properties can be found in an exciplex system or in a single compound. While not wishing to be bound by theory, it is believed that Type E delayed fluorescence requires that the luminescent material have a small singlet-triplet energy gap (ΔE _ST ). Organic, non-metal donor-acceptor luminescent materials can achieve this. The emission in these materials is generally characterized as a donor-acceptor charge transfer (CT) emission. The spatial separation of HOMO and LUMO in these donor-acceptor-type compounds generally leads to small ΔE _ST . These conditions can involve CT conditions. In general, donor-acceptor luminescent materials are constructed by combining an electron donor group such as amino or carbazole derivatives and an electron acceptor group such as N-containing six-membered aromatic rings.

Definition of substituent terms

Halogen or halide - as used herein includes fluorine, chlorine, bromine and iodine.

Alkyl - refers to both straight and branched chain alkyl groups. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, the n-octyl group, the n-nonyl group, the n-decyl group, the n-undecyl group, the n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n- Heptadecyl group, n-octadecyl group, neopentyl group, 1-methylpentyl group, 2-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group and 3-methylpentyl group. In addition, the alkyl group can optionally be substituted. The carbons in the alkyl chain can be replaced by other heteroatoms. Of the above, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group and neopentyl group are preferred.

Cycloalkyl - as used herein, refers to cyclic alkyl groups. Preferred cycloalkyl groups are those containing 4 to 10 ring carbon atoms and include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcylcohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, and the like. In addition, the cycloalkyl group can optionally be substituted. The carbons in the ring can be replaced by other heteroatoms.

Alkenyl - as used herein, refers to both straight and branched chain alkene groups. Preferred alkenyl groups are those containing 2 to 15 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 1-methylvinyl group, styryl group, 2,2-diphenylvinyl group, 1 , 2-diphenylvinyl group, 1-methylallyl group, 1,1-dimethylallyl group, 2-methylallyl group, 1-phenylallyl group, 2-phenylallyl group, 3-phenylallyl group, 3,3-diphenylallyl group, 1,2-dimethylallyl group , 1-phenyl-1-butenyl group and 3-phenyl-1-butenyl group. In addition, the alkenyl group can optionally be substituted.

Alkynyl - as used herein, refers to both straight and branched chain alkyne groups. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. In addition, the alkynyl group can optionally be substituted.

Aryl or aromatic group - as used herein includes non-condensed and condensed systems. Preferred aryl groups are those containing six to sixty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Examples of the aryl group include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalin, phenanthrene, fluorene, pyrene, chrysene, perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene.

In addition, the aryl group can optionally be substituted. Examples of the non-condensed aryl group include phenyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, p-terphenyl-4-yl group, p -Terphenyl-3-yl group, the p-terphenyl-2-yl group, the m-terphenyl-4-yl group, the m-terphenyl-3-yl group, the m-terphenyl-2-yl -Group, the o-tolyl group, m-tolyl group, the p-tolyl group, the pt-butylphenyl group, the p- (2-phenylpropyl) phenyl group, the 4'-methylbiphenylyl group, the 4 "-t-butyl-p- terphenyl-4-yl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, 2,3-xylyl group, 3,4-xylyl group, 2,5-xylyl group, mesityl group and m-quarter phenyl group .

Heterocyclic Group or Heterocycle - as used herein includes aromatic and non-aromatic cyclic groups. Hetero-aromatic also means heteroaryl. Preferred non-aromatic heterocyclic groups are those containing 3 to 7 ring atoms which contain at least one hetero atom such as nitrogen, oxygen and sulfur. The heterocyclic group may also be an aromatic heterocyclic group containing at least one hetero atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom.

Heteroaryl - as used herein, includes non-condensed and condensed heteroaromatic groups that can contain one to five heteroatoms. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine , Pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, phenazine, phenazine, oxcrothidine , Benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, Pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine and aza analogs thereof. In addition, the heteroaryl group can optionally be substituted.

Alkoxy - represented by -O-alkyl. Examples and preferred examples thereof are the same as those described above. Examples of the alkoxy group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms, include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group and hexyloxy group. The alkoxy group having 3 or more carbon atoms can be linear, cyclic or branched.

Aryloxy - represented by -O-aryl or -O-heteroaryl. Examples and preferred examples thereof are the same as those described above. Examples of the aryloxy group having 6 to 40 carbon atoms include phenoxy group and biphenyloxy group.

Arylalkyl, as used herein, refers to an alkyl group that has an aryl substituent. In addition, the arylalkyl group can optionally be substituted. Examples of the arylalkyl group include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl group, alpha-naphthylmethyl group, 1-alpha-naphthylethyl group, 2- alpha-naphthylethyl group, the 1-alpha-naphthylisopropyl group, the 2-alpha-naphthylisopropyl group, the beta-naphthylmethyl group, the 1-beta-naphthylethyl group, the 2-beta-naphthylethyl group, the 1-beta-naphthylisopropyl group, the 2-beta-naphthylisopropyl group , the p-methylbenzyl group, the m-methylbenzyl group, the o-methylbenzyl group, the p-chlorobenzyl group, the m-chlorobenzyl group, the o-chlorobenzyl group, the p-bromobenzyl group, the m-bromobenzyl group, the o-bromobenzyl group, the p-iodobenzyl group , the m-iodobenzyl group, the o-iodobenzyl group, the p-hydroxybenzyl group, the m-hydroxybenzyl group, the o-hydroxybenzyl group, the p-aminobenzyl group, the m-aminobenzyl group, the o-aminobenzyl group, the p-nitrobenz yl group, the m-nitrobenzyl group, the o-nitrobenzyl group, the p-cyanobenzyl group, the m-cyanobenzyl group, the o-cyanobenzyl group, the 1-hydroxy-2-phenylisopropyl group and the 1-chloro-2-phenylisopropyl group. Of the above, preferred are benzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group and 2-phenylisopropyl group.

The term “aza” in azadibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C-H groups in the respective aromatic fragment have been replaced by a nitrogen atom. Azatriphenylene, for example, includes dibenzo [f, h] quinoxaline, dibenzo [f, h] quinoline and other analogs with two or more nitrogen atoms in the ring system. One skilled in the art can readily envision other nitrogen analogs of the aza derivatives described above, and all such analogs are intended to be encompassed by the terms herein.

When in the present disclosure, unless otherwise defined, any term from the group consisting of substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted arylalkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl , substituted amine, substituted acyl, substituted carbonyl, substituted carboxylic acid group, substituted ester group, substituted sulfinyl, substituted sulfonyl and substituted phosphino is used, this means that any group of alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, alkenyl, aryl, Heteroaryl, alkylsilyl, arylsilyl, amine, acyl, carbonyl, carboxylic acid group, ester group, sulfinyl, sulfonyl and phosphino can be substituted with one or more groups selected from the group consisting of deuterium, a halogen, an unsubstituted An alkyl group with 1 to 20 carbon atoms, an unsubstituted cycloalkyl group with 3 to 20 ring carbon atoms, an unsubstituted heteroalkyl group with 1 to 20 carbon atoms, an unsubstituted arylalkyl group with 7 to 30 carbon atoms, an unsubstituted alkoxy group with 1 to 20 carbon atoms, an unsubstituted aryloxy group with 6 to 30 Carbon atoms, an unsubstituted alkenyl group having 2 to 20 carbon atoms, an unsubstituted aryl group having 6 to 30 carbon atoms, an unsubstituted heteroaryl group having 3 to 30 carbon atoms, an unsubstituted alkylsilyl group having 3 to 20 carbon atoms, an unsubstituted arylsilyl group having 6 to 20 carbon atoms having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a sulf onyl group and a phosphine group and combinations thereof.

It should be understood that when a molecular fragment is described as a substituent or otherwise attached to another entity, its name may be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or as it the whole molecule (e.g. benzene, naphthalene, Dibenzofuran). As used herein, these different ways of designating a substituent or an attached fragment are considered equivalent.

In the compounds mentioned in the present disclosure, multiple substitutions refer to a range that includes double substitution up to the maximum available substitutions. When a substitution in the compounds mentioned in the present disclosure represents multiple substitutions (including di, tri, tetra substitutions, etc.), it means that the substituent can be present at a variety of available substitution positions on its bond structure, with those at a plurality substituents present on available substitution positions may be the same structure or different structures.

In the compounds mentioned in the present disclosure, adjacent substituents in the compounds may not combine to form a ring unless explicitly defined otherwise, for example, adjacent substituents may optionally be linked to form a ring to build. In the compounds mentioned in the present disclosure, adjacent substituents may optionally be linked to form a ring, including both the case where adjacent substituents may be linked to form a ring and the case where adjacent substituents are not connected to form a ring. When adjacent substituents can optionally be linked to form a ring, the ring formed can be monocyclic or polycyclic as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic. Here, in the same expressions, adjacent substituents can refer to substituents which are bonded to the same atom, to substituents which are bonded to carbon atoms which are bonded directly to one another, or to substituents which are bonded to carbon atoms which are further apart. Preferably, adjacent substituents refer to substituents attached to the same carbon atom and to substituents attached to carbon atoms attached directly to each other.

The expression that adjacent substituents may optionally be linked to form a ring is also intended to mean that two substituents attached to the same carbon atom are chemically bonded to one another to form a ring, as indicated by the the following formula can be illustrated:

The phrase that adjacent substituents may optionally be linked to form a ring is also intended to mean that two substituents attached to carbon atoms that are directly attached to each other are linked through a chemical bond to form a ring, which can be illustrated by the following formula:

Furthermore, the expression that adjacent substituents can optionally be linked to form a ring means that in the event that one of the two substituents that are bonded to carbon atoms directly linked to one another is hydrogen, the second substituent on one Position to which the hydrogen atom is attached, thereby forming a ring. This is illustrated by the following formula:

wobei X₁ bis X₄, bei jedem Auftreten gleich oder verschieden, ausgewählt sind aus CR₁ oder N;
wobei Y₁ bis Y₄, bei jedem Auftreten gleich oder verschieden, ausgewählt sind aus CR₂ oder N;
wobei R₁ und R₂, bei jedem Auftreten gleich oder verschieden, ausgewählt sind aus der Gruppe bestehend aus: Wasserstoff, Deuterium, Halogen, substituiertem oder unsubstituiertem Alkyl mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Cycloalkyl mit 3 bis 20 Ringkohlenstoffatomen, substituiertem oder unsubstituiertem Heteroalkyl mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Arylalkyl mit 7 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkoxy mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Aryloxy mit 6 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkenyl mit 2 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Aryl mit 6 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Heteroaryl mit 3 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkylsilyl mit 3 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Arylsilyl mit 6 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Amino mit 0 bis 20 Kohlenstoffatomen, einer Acylgruppe, einer Carbonylgruppe, einer Carbonsäuregruppe, einer Estergruppe, einer Nitrilgruppe, einer Isonitrilgruppe, einer Sulfanylgruppe, einer Sulfinylgruppe, einer Sulfonylgruppe, einer Phosphinogruppe und Kombinationen davon;
in Formel 1, benachbarte Substituenten gegebenenfalls verbunden sein können, um einen Ring zu bilden;
wobei der zweite Ligand L_b eine durch Formel 2 dargestellte Struktur aufweist:

wobei Rt bis R_z, bei jedem Auftreten gleich oder verschieden, ausgewählt sind aus der Gruppe bestehend aus: Wasserstoff, Deuterium, Halogen, substituiertem oder unsubstituiertem Alkyl mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Cycloalkyl mit 3 bis 20 Ringkohlenstoffatomen, substituiertem oder unsubstituiertem Heteroalkyl mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Arylalkyl mit 7 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkoxy mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Aryloxy mit 6 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkenyl mit 2 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Aryl mit 6 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Heteroaryl mit 3 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkylsilyl mit 3 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Arylsilyl mit 6 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Amino mit 0 bis 20 Kohlenstoffatomen, einer Acylgruppe, einer Carbonylgruppe, einer Carbonsäuregruppe, einer Estergruppe, einer Nitrilgruppe, einer Isonitrilgruppe, einer Sulfanylgruppe, einer Sulfinylgruppe, einer Sulfonylgruppe, einer Phosphinogruppe und Kombinationen davon;
in Formel 2, benachbarte Substituenten gegebenenfalls verbunden sein können, um einen Ring zu bilden;
wobei der dritte Ligand L_c ein monoanionischer zweizähniger Ligand ist.According to one embodiment of the present disclosure, a metal complex is disclosed which has the general structure M (L _a ) _m (L _b ) _n (L _c ) _q , where L _a , L _b and L _{c are} the first ligand, the second ligand, and respectively the third ligand coordinated with the metal M; wherein the metal M is a metal whose relative atomic mass is greater than 40;
wherein L _a , L _b and L _c can optionally be linked to form a multidentate ligand;
where m is 1 or 2, n is 1 or 2, q is 0 or 1, and m + n + q is the same as the oxidation state of the metal M;
when m is greater than 1, L _{a can be the} same or different; and when n is greater than 1, L _{b may be the} same or different;
wherein the first ligand L _{a has} a structure represented by Formula 1:

where X ₁ to X ₄ , identically or differently on each occurrence, are selected from CR ₁ or N;
where Y ₁ to Y ₄ , identically or differently on each occurrence, are selected from CR ₂ or N;
where R ₁ and R ₂ , identically or differently on each occurrence, are selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl with 7 to 30 carbon atoms, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 carbon atoms, substituted or unsubstituted alkenyl with 2 to 20 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl with 6 to 20 carbon atoms, substituted or unsubstituted amino with 0 to 20 carbon atoms, an acyl group , a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
in Formula 1, adjacent substituents may optionally be linked to form a ring;
wherein the second ligand L _{b has} a structure represented by Formula 2:

where Rt to R _z , identically or differently on each occurrence, are selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted Heteroalkyl with 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl with 7 to 30 carbon atoms, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 carbon atoms, substituted or unsubstituted alkenyl with 2 to 20 carbon atoms, substituted or unsubstituted Aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl with 6 to 20 carbon atoms men, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
in Formula 2, adjacent substituents may optionally be linked to form a ring;
wherein the third ligand L _{c is} a monoanionic bidentate ligand.

In this embodiment, the phrase "in Formula 1, adjacent substituents may optionally be linked to form a ring" may include the following cases: in one case there is the case (s) that between adjacent substituents R ₁ , between adjacent substituents R ₂ and / or between adjacent substituents R ₁ and R _{2 are} linked to form a ring; and in the other case, between adjacent substituents R ₁ , between adjacent substituents R ₂ and / or between adjacent substituents R ₁ and R _{2 may} not bond to form a ring.

In this embodiment, the phrase that "in Formula 2, adjacent substituents may optionally be linked to form a ring" may include the following cases: in one case there is the case (s) that between adjacent substituents R _x , R _y , R _z , R _t , R _u , R _v and R _{w are} linked to form a ring, for example one or more of between adjacent substituents R _x and R _y , between adjacent substituents R _y and R _z , are between adjacent substituents R _u and R _v , between adjacent substituents Rt and R _z , between adjacent substituents R _t and R _u , and between adjacent substituents R _w and R _v joined to form a ring; and in the other case, there are cases that between adjacent substituents R _x , R _y , R _z , Rt, R _u , R _v and R _w cannot be connected to form a ring, for example, any or more of between adjacent ones Substituents R _x and R _y , between adjacent substituents R _y and R _z , between adjacent substituents R _u and R _v , between adjacent substituents Rt and R _z , between adjacent substituents Rt and R _u , and between adjacent substituents R _w and R _v not be connected to form a ring.

In the present disclosure, when a substituent is selected from hydrogen, the hydrogen refers to its isotope, protium (H), and not to other isotopes such as deuterium or tritium.

According to one embodiment of the present disclosure, wherein the metal M is selected from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir and Pt.

According to an embodiment of the present disclosure, wherein the metal M is selected from Pt or Ir.

According to an embodiment of the present disclosure, wherein at least one of X ₁ to X _{4 is} selected from CR ₁ .

According to an embodiment of the present disclosure, wherein at least one of X ₁ to X _{4 is} selected from N.

According to one embodiment of the present disclosure, wherein at least one of Y ₁ to Y _{4 is} selected from N.

According to one embodiment of the present disclosure, where X ₁ to X ₄ , identically or differently on each occurrence, are selected from CR ₁ .

According to one embodiment of the present disclosure, wherein X ₁ and / or X ₃ , identically or differently on each occurrence, are selected from CR ₁ , and R ₁ , identically or differently on each occurrence, is selected from the group consisting of: deuterium, Halogen, substituted or unsubstituted alkyl with 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl with 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1 to 20 carbon atoms, substituted or unsubstituted aralkyl with 7 to 30 carbon atoms, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 carbon atoms, substituted or unsubstituted alkenyl with 2 to 20 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl with 6 to 20 carbon atoms, substituted or unsubstituted amino with 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
where adjacent substituents R _{1 may} optionally be linked to form a ring.

According to one embodiment of the present disclosure, wherein X ₁ and X ₃ , identical or different on each occurrence, are selected from CR ₁ and R ₁ , identical or different on each occurrence, are selected from the group consisting of: hydrogen, deuterium, halogen , substituted or unsubstituted alkyl with 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl with 3 to 20 ring carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms and substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms .

According to one embodiment of the present disclosure, where X ₁ and X ₃ , identically or differently on each occurrence, are selected from CR ₁ , and R ₁ , identically or differently on each occurrence, is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms , and X ₂ and X _{4 are} CH.

According to one embodiment of the present disclosure, where X ₁ and X _{4 are} CH and X ₂ and X ₃ , identically or differently on each occurrence, are selected from CR ₁ .

According to one embodiment of the present disclosure, where R ₁ , identically or differently on each occurrence, is selected from the group consisting of: hydrogen, deuterium, fluorine, methyl, ethyl, 2-butyl, isopropyl, tert-butyl, isobutyl, cyclopentyl, Cyclohexyl, deuteromethyl, deuteropropyl, isopropylamino, phenyl, 2,6-dimethylphenyl, pyridyl, vinyl, and combinations thereof;
where adjacent R ₁ substituents may optionally be linked to form a ring.

According to one embodiment of the present disclosure, wherein Y ₁ to Y ₄ , identically or differently on each occurrence, are selected from CR ₂ , and R ₂ , identically or differently on each occurrence, is selected from the group consisting of: hydrogen, halogen, substituted or unsubstituted alkyl with 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl with 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1 to 20 carbon atoms, substituted or unsubstituted aralkyl with 7 to 30 carbon atoms, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 carbon atoms, substituted or unsubstituted alkenyl with 2 to 20 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms, substituted or unsubstituted ituted alkylsilyl with 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl with 6 to 20 carbon atoms, substituted or unsubstituted amino with 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a Sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
where adjacent R ₂ substituents may optionally be linked to form a ring.

According to one embodiment of the present disclosure, wherein Y _{2 is} CR ₂ and R ₂ , identically or differently on each occurrence, is selected from the group consisting of: halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 up to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1 to 20 carbon atoms, substituted or unsubstituted aralkyl with 7 to 30 carbon atoms, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 carbon atoms, substituted or unsubstituted alkenyl with 2 up to 20 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms, substituted or unsubstituted tem arylsilyl with 6 to 20 carbon atoms, substituted or unsubstituted amino with 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a Sulfonyl group, a phosphine group, and combinations thereof; where adjacent R ₂ substituents may optionally be linked to form a ring.

According to one embodiment of the present disclosure, Y _{2 is} CR ₂ and R ₂ is, identically or differently on each occurrence, selected from the group consisting of: halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms and substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms; where adjacent R ₂ substituents may optionally be linked to form a ring.

According to one embodiment of the present disclosure, R _{2 is} an alkyl having 1 to 20 carbon atoms.

According to one embodiment of the present disclosure, Y _{2 is} CR ₂ and R ₂ is, identically or differently on each occurrence, selected from substituted or unsubstituted alkyl or cycloalkyl having 1 to 20 carbon atoms or substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, and Y. ₁ , Y ₃ and Y ₄ are each CH;
where adjacent R ₂ substituents may optionally be linked to form a ring.

According to one embodiment of the present disclosure, where R ₂ , identically or differently on each occurrence, is selected from the group consisting of: hydrogen, fluorine, methyl, ethyl, isopropyl, 2-butyl, isobutyl, tert-butyl, pent-3- yl, cyclopentyl, cyclohexyl, 4,4-dimethylcyclohexyl, neopentyl, 2,4-dimethylpent-3-yl, 1,1-dimethylsilacyclohex-4-yl, cyclopentylmethyl, cyano, trifluoromethyl, trimethylsilyl, phenyldimethylsilyl, bicyclo [2.2, 1] pentyl, adamantyl, deuteroisopropyl, phenyl, pyridyl, and combinations thereof.

According to one embodiment of the present disclosure, wherein the first ligand L _a, identical or different on each occurrence, is selected from one or any two structures from the group consisting of L _a1 to L _a1101 , the specific structures from L _a1 to L _a1101 in Claim 10 are shown.

According to one embodiment of the present disclosure, wherein the first ligand L _a , identical or different on each occurrence, is selected from one or any two structures from the group consisting of L _a1 to L _a1189 , the specific structures from L _a1 to L _a1189 are shown in claim 10.

According to one embodiment of the present disclosure, where in formula 2 Rt to R _{z are,} identically or differently on each occurrence, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms and combinations thereof.

According to one embodiment of the present disclosure, where in formula 2 Rt is selected from hydrogen, deuterium or methyl, and R _u to R _z , identically or differently on each occurrence, are selected from hydrogen, deuterium, fluorine, methyl, ethyl, propyl, Cyclobutyl, cyclopentyl, cyclohexyl, 3-methylbutyl, 3-ethylpentyl, trifluoromethyl, and combinations thereof.

According to one embodiment of the present disclosure, wherein the second ligand L _b , identical or different on each occurrence, is selected from one or any two structures from the group consisting of L _b1 to L _b333 , the specific structures from L _b1 to L _b383 are shown in claim 12.

According to one embodiment of the present disclosure, it being possible for the hydrogens in the first ligand L _a and / or the second ligand L _{b to be} partially or completely substituted by deuterium.

und

wobei R_a, R_b und R_c Monosubstitution, Mehrfachsubstitutionen oder keine Substitution darstellen können;
X_b, bei jedem Auftreten gleich oder verschieden, ausgewählt ist aus der Gruppe bestehend aus: O, S, Se, NR_N1, und CRc₁Rc₂;
X_c und X_d, bei jedem Auftreten gleich oder verschieden, ausgewählt sind aus der Gruppe bestehend aus: O, S, Se und NR_N2;
R_a, R_b, R_c, R_N1, R_N2, R_C1 und R_C2, bei jedem Auftreten gleich oder verschieden, ausgewählt sind aus der Gruppe bestehend aus: Wasserstoff, Deuterium, Halogen, substituiertem oder unsubstituiertem Alkyl mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Cycloalkyl mit 3 bis 20 Ringkohlenstoffatomen, substituiertem oder unsubstituiertem Heteroalkyl mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Arylalkyl mit 7 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkoxy mit 1 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Aryloxy mit 6 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkenyl mit 2 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Aryl mit 6 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Heteroaryl mit 3 bis 30 Kohlenstoffatomen, substituiertem oder unsubstituiertem Alkylsilyl mit 3 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Arylsilyl mit 6 bis 20 Kohlenstoffatomen, substituiertem oder unsubstituiertem Amino mit 0 bis 20 Kohlenstoffatomen, einer Acylgruppe, einer Carbonylgruppe, einer Carbonsäuregruppe, einer Estergruppe, einer Nitrilgruppe, einer Isonitrilgruppe, einer Sulfanylgruppe, einer Sulfinylgruppe, einer Sulfonylgruppe, einer Phosphinogruppe und Kombinationen davon;
in der Struktur von L_c, benachbarte Substituenten optional verbunden sein können, um einen Ring zu bilden.According to one embodiment of the present disclosure, wherein the third ligand L _{c is} selected from one of the following structures:

and

where R _a , R _b and R _{c can represent} monosubstitution, multiple substitutions or no substitution;
X _b , identically or different on each occurrence, is selected from the group consisting of: O, S, Se, NR _N1 , and CRc ₁ Rc ₂ ;
X _c and X _d , identically or different on each occurrence, are selected from the group consisting of: O, S, Se and NR _N2 ;
R _a , R _b , R _c , R _N1 , R _N2 , R _C1 and R _C2 , identical or different on each occurrence, are selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl with 1 to 20 Carbon atoms, substituted or unsubstituted cycloalkyl with 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl with 7 to 30 carbon atoms, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 Carbon atoms, substituted or unsubstituted alkenyl with 2 to 20 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms, substituted or unsubstituted arylsily l having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
in the structure of L _c , adjacent substituents may optionally be linked to form a ring.

In this embodiment, the expression that "adjacent substituents may optionally be linked to form a ring" is intended to mean that any one or more of the group of adjacent substituents, such as between two substituents R _a , between two substituents R _b , between two substituents R _c , between the substituents R _a and R _b , between the substituents R _a and R _c , between the substituents R _b and R _c , between the substituents R _a and R _N1 , between the substituents R _b and R _N1 , between the substituents R _a and R _C1 , between the substituents R _a and R _C2 , between the substituents R _b and R _C1 , between the substituents R _b and R _C2 , between the substituents R _a and R _N2 , between the substituents R _b and R _N2 , and between the substituents R _C1 and R _C2 , may be linked to form a ring. Obviously, these substituents cannot be linked to form a ring.

According to one embodiment of the present disclosure, wherein the third ligand L _c , identical or different on each occurrence, is selected from the group consisting of L _c1 to L _c227 , the specific structures of L _c1 to L _{c227 being shown} in claim 15.

According to an embodiment of the present disclosure, wherein the metal complex is Ir (La) ₂ (L _b ) or Ir (L _a ) (L _b ) (L _c ); when the metal complex is Ir (La) ₂ (L _b ), the first ligand L _a , identical or different on each occurrence, is selected from one or two from the group consisting of L _a1 to L _a1189 , and the second ligand L _b is, identical or different on each occurrence, selected from one of the group consisting of L _b1 to L _b388 ; when the metal complex is Ir (L _a ) (L _b ) (L _e ), the first ligand L _a , identical or different on each occurrence, is selected from one of the group consisting of L _a1 to L _a1189 , is the second ligand L _b , identical or different on each occurrence, selected from one of the group consisting of L _b1 to L _b388 , and the third ligand L _c , identical or different on each occurrence, selected from one of the group consisting of L _c1 to L _c227 .

According to one embodiment of the present disclosure, the metal complex is selected from complexes, the specific structures of which are shown in claim 16.

• eine Anode,
• einer Kathode, und
• eine organische Schicht, die zwischen der Anode und der Kathode angeordnet ist, wobei die organische Schicht den in einer der obigen Ausführungsformen beschriebenen Metallkomplex enthält.

According to another embodiment of the present disclosure, an electroluminescent device is further disclosed that includes:

• an anode,
• a cathode, and
• an organic layer which is arranged between the anode and the cathode, the organic layer containing the metal complex described in one of the above embodiments.

According to an embodiment of the present disclosure, wherein the electroluminescent device emits red light or white light.

According to an embodiment of the present disclosure, wherein the organic layer is an emitting layer and the metal complex is a light-emitting material.

According to an embodiment of the present disclosure, wherein the organic layer further contains a host material.

According to one embodiment of the present disclosure, wherein the host material contains at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, azadibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, , Fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof.

According to a further embodiment of the present disclosure, a compound combination is further disclosed which contains the metal complex described in one of the above embodiments.

Combination with other materials

The materials described in the present disclosure for a particular layer in an organic light emitting device can be used in combination with various other materials present in the device. The combinations of these materials are more fully described in U.S. Patient app. No. 20160359122 in paragraphs 0132-0161, which is incorporated herein by reference in its entirety. The materials described or cited in the disclosure are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one skilled in the art can readily consult the literature to identify other materials that may be useful in combination .

The materials described herein as being useful for a particular layer in an organic light emitting device can be used in combination with a variety of other materials present in the device. For example, the dopants disclosed herein can be used in combination with a variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. The combination of these materials is described in detail in sections 0080-0101 of U.S. Pat. Patient app. No. 20150349273, which is incorporated herein by reference in its entirety. The materials described or cited in the disclosure are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one skilled in the art can readily consult the literature to identify other materials that may be useful in combination .

In the embodiments of the material synthesis, all reactions were carried out under nitrogen protection, unless otherwise stated. All reaction solvents were anhydrous and were used as obtained from commercial sources. The synthetic products have been structurally validated and tested for properties using one or more conventional equipment (including but not limited to limited to a nuclear magnetic resonance apparatus manufactured by BRUKER, a liquid chromatograph manufactured by SHIMADZU, a liquid chromatograph with mass spectrometry manufactured by SHIMADZU, a gas chromatograph with mass spectrometry manufactured by SHIMADZU, a differential dynamic calorimeter manufactured by SHIMADZU, a fluorescence chemo-chemometer manufactured by SHANGHA by WUHAN CORRTEST, and a sublimation device manufactured by ANHUI BEQ, etc.) by methods well known to those skilled in the art. In the embodiments of the device, the properties of the device were also tested using equipment conventional in the art (including, but not limited to, a vaporizer manufactured by ANGSTROM ENGINEERING, an optical test system manufactured by SUZHOU FATAR, a life test system manufactured by SUZHOU FATAR, and an ellipsometer manufactured by BEIJING ELLITOP, etc.) by methods well known to those skilled in the art. Since those skilled in the art are familiar with the use of the above-mentioned devices, test methods and other related contents, the inherent data of the sample can be obtained with certainty and without interference, so that the above related contents are not further described in the present disclosure.

Example of material synthesis

The method for producing the metal complex of the present disclosure is not limited herein. The following is typically described below using the example of the following compounds without limitation, and the synthetic routes and production methods of the compounds are as follows.

Synthesis example 1: Synthesis of the compound Ir (L _a126 ) ₂ (L _b361 )

Step 1: Synthesis of an Iridium Dimer

Intermediate 1 (4.06 g, 14.64 mmol), iridium trichloride trihydrate (1.29 g, 3.66 mmol), ethoxyethanol (39 ml) and water (13 ml) were placed in a 100 ml round bottom flask. The resulting reaction mixture was degassed with nitrogen gas for 3 minutes. The reaction was refluxed under nitrogen for 24 h and the reaction solution changed from yellow-green to dark red. After the completion of the reaction, the mixture was cooled to room temperature and filtered. The filtered solid was washed several times with methanol and then dried to obtain the dimer.

Step 2: Synthesis of the compound Ir (L _a126 ) ₂ (L _b361 )

The mixture of the iridium dimer obtained in step 1 (1.33 g, 0.85 mmol), 3,7-diethyl-1,1,1-trifluorononane-4,6-dione (679 mg, 2.55 mmol), Potassium carbonate (1.17 g, 8.5 mmol) and 2-ethoxyethanol (28 ml) was stirred at room temperature under nitrogen for 24 hours. After TLC showed the reaction was complete, Celite was added to a funnel and the reaction mixture was poured into the funnel. The above mixture was filtered and the filter cake was washed several times with ethanol. The product in the filter cake was washed into the solution with dichloromethane. Then a certain Amount of ethanol was added to the solution and the dichloromethane in the solution was carefully removed with a rotary evaporator. A red solid precipitated out of solution and was filtered. The resulting solid was washed several times with ethanol. The solvent was removed by suction filtration to obtain the compound Ir (L _a126 ) ₂ (L _b361 ) as a red solid (1.29 g, yield: 75%). The obtained product was confirmed to be the target product having a molecular weight of 1,010.

_{Synthesis example} 2: Synthesis of the compound Ir (L a577) ₂ (L _b378 )

Step 1: Synthesis of an Iridium Dimer

Intermediate 2 (3.34 g, 10.53 mmol), iridium trichloride trihydrate (1.24 g, 3.51 mmol), ethoxyethanol (39 ml) and water (13 ml) were placed in a 100 ml round bottom flask. The resulting reaction mixture was degassed with nitrogen gas for 3 minutes. The reaction was refluxed for 24 h under nitrogen and the reaction solution changed from yellow-green to dark red. The reaction was then cooled to room temperature and filtered. The filtered solid was washed several times with methanol and then dried to obtain an iridium dimer (2.65 g, yield: 87.8%).

Step 2: Synthesis of the compound Ir (L _a577 ) ₂ (L _b378 )

The mixture of the iridium dimer obtained in step 1 (1.33 g, 0.77 mmol), 3,7-diethyl-9,9-difluorodecane-4,6-dione (808 mg, 3.1 mmol), potassium carbonate ( 1.06 g, 7.71 mmol) and 2-ethoxyethanol (22 ml) were stirred at room temperature under nitrogen for 24 h. After TLC showed the reaction was complete, Celite was added to a funnel and the reaction mixture was poured into the funnel. The above mixture was filtered and the filter cake was washed several times with ethanol. The product in the filter cake was washed into the solution with dichloromethane. A certain amount of ethanol was then added to the solution and the dichloromethane in the solution was carefully removed using a rotary evaporator. A red solid precipitated out of solution and was filtered. The resulting solid was washed several times with ethanol. The solvent was removed by suction filtration to obtain the compound Ir (L _a577 ) ₂ (L _b378 ) as a red solid (1.4 g, yield: 83.5%). The obtained product was confirmed to be the target product with a molecular weight of 1,087.

_{Synthesis example} 3: Synthesis of the compound Ir (L a577) ₂ (L _b361 )

The mixture of the iridium dimer (1.33 g, 0.77 mmol), 3,7-diethyl-1,1,1-trifluorononane-4,6-dione (820 mg, 3.1 mmol), potassium carbonate (1, 06 g, 7.71 mmol) and 2-ethoxyethanol (22 ml) were stirred at room temperature under nitrogen for 24 h.

After TLC showed that the reaction was complete, Celite was added to a funnel and the reaction mixture was poured into the funnel. The above mixture was filtered and the filter cake was washed several times with ethanol. The product in the filter cake was washed into the solution with dichloromethane. A certain amount of ethanol was then added to the solution and the dichloromethane in the solution was carefully removed with a rotary evaporator. A red solid precipitated out of solution and was filtered. The resulting solid was washed several times with ethanol. The solvent was removed by suction filtration to obtain the compound Ir (L _a577 ) ₂ (L _b361 ) as a red solid (1.4 g, yield: 83.4%). The obtained product was confirmed to be the target product with a molecular weight of 1,091.

Synthesis example 4: Synthesis of the compound Ir (L _a331 ) ₂ (L _b378 )

The mixture of the iridium dimer (1.2 g, 0.72 mmol), 3,7-diethyl-9,9-difluorodecane-4,6-dione (755 mg, 2.88 mmol), potassium carbonate (995 mg, 7 , 2 mmol) and 2-ethoxyethanol (24 ml) was stirred at room temperature under nitrogen for 24 hours. After TLC showed the reaction was complete, Celite was added to a funnel and the reaction mixture was poured into the funnel. The above mixture was filtered and the filter cake was washed several times with ethanol. The product in the filter cake was washed into the solution with dichloromethane. A certain amount of ethanol was then added to the solution and the dichloromethane in the solution was carefully removed using a rotary evaporator. A red solid precipitated out of solution and was filtered. The resulting solid was washed several times with ethanol. The solvent was removed by suction filtration to obtain the compound Ir (L _a331 ) ₂ (L _b378 ) as a red solid (1.4 g, yield: 92%). The obtained product was confirmed to be the target product with a molecular weight of 1,059.

Synthesis example 5: Synthesis of the compound Ir (L _a331 ) ₂ (L _b361 )

The mixture of the iridium dimer (1.24 g, 0.745 mmol), 3,7-diethyl-1,1,1-trifluorononane-4,6-dione (793 mg, 2.98 mmol), potassium carbonate (1.03 g , 7.45 mmol) and 2-ethoxyethanol (25 ml) was stirred at room temperature under nitrogen for 24 h. After TLC showed the reaction was complete, Celite was added to a funnel and the reaction mixture was poured into the funnel. The above mixture was filtered and the filter cake was washed several times with ethanol. The product in the filter cake was washed into the solution with dichloromethane. A certain amount of ethanol was then added to the solution and the dichloromethane in the solution was carefully removed with a rotary evaporator. A red solid precipitated out of solution and was filtered. The resulting solid was washed several times with ethanol. The solvent was removed by suction filtration to obtain the compound Ir (L _a331 ) ₂ (L _b361 ) as a red solid (1.29 g, yield: 82%). The obtained product was confirmed to be the target product with a molecular weight of 1,062.

Synthesis example 6: Synthesis of the compound Ir (L _a577 ) ₂ (L _b31 )

The mixture of the iridium dimer (1.25 g, 0.8 mmol), 3,7-diethylnonane-4,6-dione (650 mg, 3.2 mmol), potassium carbonate (1.11 g, 8 mmol) and 2 Ethoxyethanol (25 ml) was stirred at room temperature under nitrogen for 24 hours. After TLC showed that the reaction was complete, Celite was added to a funnel and the reaction mixture was poured into the funnel. The above mixture was filtered and the filter cake was washed several times with ethanol. The product in the filter cake was washed into the solution with dichloromethane. A certain amount of ethanol was then added to the solution and the dichloromethane in the solution was carefully removed with a rotary evaporator. A red solid precipitated out of solution and was filtered. The resulting solid was washed several times with ethanol. The solvent was removed by suction filtration to obtain the compound Ir (L _a577 ) ₂ (L _b31 ) as a red solid (1.09 g, yield: 66%). The obtained product was confirmed to be the target product with a molecular weight of 1,037.

Synthesis example 7: Synthesis of the compound Ir (L _a577 ) ₂ (L _b116 )

The mixture of the iridium dimer (1.2 g, 0.8 mmol), 3,3,7-triethylnonane-4,6-dione (500 mg, 2.4 mmol), potassium carbonate (1.11 g, 8 mmol) and 2-ethoxyethanol (25 ml) was stirred at room temperature under nitrogen for 24 hours. After TLC showed that the reaction was complete, Celite was added to a funnel and the reaction mixture was poured into the funnel. The above mixture was filtered and the filter cake was washed several times with ethanol. The product in the filter cake was washed into the solution with dichloromethane. A certain amount of ethanol was then added to the solution and the dichloromethane in the solution was carefully removed using a rotary evaporator. A red solid precipitated out of solution and was filtered. The resulting solid was washed several times with ethanol. The solvent was removed by suction filtration to obtain the compound Ir (L _a577 ) ₂ (L _b116 ) as a red solid (1.1 g, yield: 65%). The obtained product was confirmed to be the target product with a molecular weight of 1,065.

Synthesis example 8: Synthesis of the compound Ir (L _a331 ) ₂ (L _b116 )

The mixture of the iridium dimer (1.25 g, 0.75 mmol), 3,3,7-triethylnonane-4,6-dione (540 mg, 2.25 mmol), potassium carbonate (1.04 g, 7.5 mmol) and 2-ethoxyethanol (22 ml) was stirred at room temperature under nitrogen for 24 hours. After TLC showed that the reaction was complete, Celite was added to a funnel and the reaction mixture was poured into the funnel. The above mixture was filtered and the filter cake was washed several times with ethanol. The product in the filter cake was washed into the solution with dichloromethane. A certain amount of ethanol was then added to the solution and the dichloromethane in the solution was carefully removed using a rotary evaporator. A red solid precipitated out of solution and was filtered. The resulting solid was washed several times with ethanol. The solvent was removed by suction filtration to obtain the compound Ir (L _a331 ) ₂ (L _b116 ) as a red solid (1.25 g, yield: 83%). The obtained product was confirmed to be the target product with a molecular weight of 1,037.

Synthesis Example 9: Synthesis of the compound Ir (La ₃₃₁ ) (L _b361 ) (Le ₁₆₁ )

The mixture of the iridium dimer (0.9 g, 0.5 mmol), 3,7-diethyl-1,1,1-trifluorononane-4,6-dione (0.5 g, 2 mmol), potassium carbonate (1 g , 5.3 mmol) and 2-ethoxyethanol (12 ml) was stirred at room temperature under nitrogen for 24 hours. After TLC showed that the reaction was complete, Celite was added to a funnel and the reaction mixture was poured into the funnel. The above mixture was filtered and the filter cake was washed several times with ethanol. The product in the filter cake was washed into the solution with dichloromethane. A certain amount of ethanol was then added to the solution and the dichloromethane in the solution was carefully removed using a rotary evaporator. A red solid precipitated out of solution and was filtered. The resulting solid was washed several times with ethanol. The solvent was removed by suction filtration to obtain Compound Ir (L _a331 ) (L _b361 ) (L _e161 ) as a red solid (0.82 g, yield: 75%). The obtained product was confirmed to be the target product with a molecular weight of 1,061.

Synthesis Example 10: Synthesis of the compound Ir (La ₁₂₆ ) (L _b361 ) (Le ₁₄₁ )

The mixture of the iridium dimer (1.14 g, 0.7 mmol), 3,7-diethyl-1,1,1-trifluorononane-4,6-dione (0.5 g, 2 mmol), potassium carbonate (1 g , 5.3 mmol) and 2-ethoxyethanol (12 ml) was stirred at room temperature under nitrogen for 24 hours.

After TLC showed that the reaction was complete, Celite was added to a funnel and the reaction mixture was poured into the funnel. The above mixture was filtered and the filter cake was washed several times with ethanol. The product in the filter cake was washed into the solution with dichloromethane. Then a certain amount of ethanol was added to the solution and that Dichloromethane in the solution was carefully removed on a rotary evaporator. A red solid precipitated out of solution and was filtered. The resulting solid was washed several times with ethanol. The solvent was removed by suction filtration to obtain Compound Ir (L _a126 ) (L _b361 ) (L _e141 ) as a red solid (1.1 g, yield: 79%). The obtained product was confirmed to be the target product with a molecular weight of 1009.

Those skilled in the art will understand that the above manufacturing methods are illustrative only. Those skilled in the art can obtain other interconnection structures of the present disclosure by modifying the manufacturing methods.

Device example 1

First, a glass substrate was cleaned with an indium tin oxide (ITO) anode with a thickness of 120 nm and then treated with oxygen plasma and UV ozone. After the treatment, the substrate was dried in a glove box to remove water. The substrate was then mounted on a substrate holder and placed in a vacuum chamber. The organic layers indicated below were sequentially deposited by thermal vacuum evaporation on the ITO anode at a rate of 0.2 to 2 angstroms per second at a vacuum level of approximately 10 ^-8 torr. Compound HI was used as a hole injection layer (HIL). The compound HT was used as a hole transport layer (HTL). Compound EB was used as an electron barrier layer (EBL). Then, the compound Ir (L _a126 ) ₂ (L _b361 ) of the present disclosure was doped 3% into a host compound RH and then used as an emission layer (EML). Compound HB was used as a hole barrier (HBL). The compound ET and 8-hydroxyquinolinolato-lithium (Liq) were deposited on the HBL and used as an electron transport layer (ETL). Finally, Liq with a thickness of 1 nm was used as an electron injection layer, and Al with a thickness of 120 nm was deposited as a cathode. The device was transferred back to the glove box and encapsulated with a glass lid and moisture collector to complete the device.

Device comparative example 1

The implementation mode in device comparative example 1 was the same as in device example 1, except that in the emission _layer (EML), the compound Ir (L a126) ₂ (L _b361 ) of the present disclosure was replaced with the comparative compound RD1.

Device comparative example 2

The implementation mode in device comparative example 2 was the same as in device example 1, except that in the emission _layer (EML), the compound Ir (L a126) ₂ (L _b361 ) of the present disclosure was replaced with the comparative compound RD2.

Device example 2

The implementation mode in Device Example 2 was the same as in Device Example 1, except that in the emission _layer (EML) the connection Ir (L a126) ₂ (L _b361 ) of the present disclosure was replaced by the connection Ir (L _a331 ) ₂ (L _b361 ) of the present disclosure (the weight ratio of the compound Ir (L _a331 ) ₂ (L _b361 ) to the compound RH was 5:95) and that in the EBL, the compound EB was replaced by the compound EB1.

Device example 3

The implementation mode in device example 3 was the same as in device example 2, except that in the emission _layer (EML) the connection Ir (L a331) ₂ (L _b361 ) of the present disclosure was replaced by the connection Ir (L _a331 ) ₂ (L _b378 ) of the present disclosure has been replaced.

Device example 4

The implementation mode in Device Example 4 was the same as in Device Example 2, except that in the emission _layer (EML) the compound Ir (L a331) ₂ (L _b361 ) of the present disclosure was replaced by the compound Ir (L _a577 ) ₂ (L _b378 ) of the present disclosure has been replaced.

Device example 5

The implementation mode in Device Example 5 was the same as in Device Example 2, except that in the emission _layer (EML) the connection Ir (L a331) ₂ (L _b361 ) of the present disclosure was replaced by the connection Ir (L _a577 ) ₂ (L _b361 ) of the present disclosure has been replaced.

Device comparative example 3

The implementation mode in device comparative example 3 was the same as in device example 2, except that in the emission _layer (EML), the compound Ir (L a331) ₂ (L _b361 ) of the present disclosure was replaced with the comparative compound RD3.

Device comparative example 4

The implementation mode in device comparative example 4 was the same as in device example 2, except that in the emission _layer (EML), the compound Ir (L a331) ₂ (L _b361 ) of the present disclosure was replaced with the comparative compound RD4.

Device comparative example 5

The implementation mode in device comparative example 5 was the same as in device example 2, except that in the emission _layer (EML), the compound Ir (L a331) ₂ (L _b361 ) of the present disclosure was replaced with the comparative compound RD5.

Detailed structures and layer thicknesses of the devices are shown in the following table. The layers that use more than one material are obtained by doping various compounds in the proportions by weight listed in the table below. TABLE 1 Device Share Structures in Device Examples Device no. HIL HTL EBL EML HBL ETL example 1 Compound Hl (100 Å) Connection HT (400 Å) Connection EB (50 Å) Connection RH: Connection Ir (L _a126 ) 2 (L _b361 ) (97: 3) (400 Å) Connection HB (50 Å) Connection ET: Liq (40:60) (350 Å) Comparative example 1 Compound Hl (100 Å) Connection HT (400 Å) Connection EB (50 Å) Connection RH: Connection RD1 (97: 3) (400 Å) Connection HB (50 Å) Connection ET: Liq (40:60) (350 Å) Comparative example 2 Compound Hl (100 Å) Connection HT (400 Å) Connection EB (50 Å) Connection RH: Connection RD2 (97: 3) (400 Å) Connection HB (50 Å) Connection ET: Liq (40:60) (350 Å) Example 2 Compound Hl (100 Å) Connection HT (400 Å) Connection EB1 (50 Å) Connection RH: Connection Ir (L _a331 ) 2 (L _b361 ) (95: 5) (400 Å) Connection HB (50 Å) Connection ET: Liq (40:60) (350 Å) Example 3 Compound Hl (100 Å) Connection HT (400 Å) Connection EB1 (50 Å) Connection RH: Connection Ir (L _a331 ) 2 (L _b378 ) (95: 5) (400 Å) Connection HB (50 Å) Connection ET: Liq (40:60) (350 Å) Example 4 Compound Hl (100 Å) Connection HT (400 Å) Connection EB1 (50 Å) Connection RH: Connection Ir (L _a577 ) 2 (L _b378 ) (95: 5) (400 Å) Connection HB (50 Å) Connection ET: Liq (40:60) (350 Å) Example 5 Compound Hl (100 Å) Connection HT (400 Å) Connection EB1 (50 Å) Connection RH: Connection Ir (L _a577 ) 2 (L _b361 ) (95: 5) (400 Å) Connection HB (50 Å) Connection ET: Liq (40:60) (350 Å) Comparative example 3 Compound Hl (100 Å) Connection HT (400 Å) Connection EB1 (50 Å) Connection RH: Connection RD3 (95: 5) (400 Å) Connection HB (50 Å) Connection ET: Liq (40:60) (350 Å) Comparative example 4 Compound Hl (100 Å) Connection HT (400 Å) Connection EB1 (50 Å) Connection RH: Connection RD4 (95: 5) (400 Å) Connection HB (50 Å) Connection ET: Liq (40:60) (350 Å) Comparative example 5 Compound Hl (100 Å) Connection HT (400 Å) Connection EB1 (50 Å) Connection RH: Connection RD5 (95: 5) (400 Å) Connection HB (50 Å) Connection ET: Liq (40:60) (350 Å)

und

The structures of the materials used in the devices are shown as follows:

and

Table 2 shows the chromaticity coordinate (CIE) and emission wavelength (λ _max ) data measured at a brightness of 1000 nits and the external quantum efficiency (EQE) measured at a constant current density of 15 mA / cm ² for the devices in the device Example 1 and Comparative Examples 1 to 2 and Device Examples 2 to 5 and Comparative Examples 3 to 5. The device life LT97 was measured ^{at a constant current density of 80 mA / cm 2.} TABLE 2 Device Data Device no. CIE (x, y) Amax (nm) EQE (%) LT97 (h) example 1 0.677, 0.322 620 24.20 106 Comparative example 1 0.677, 0.322 620 23.26 98 Comparative example 2 0.678, 0.322 620 23.11 86 Example 2 0.678, 0.321 622 23.41 64 Example 3 0.682, 0.317 625 23.23 70 Example 4 0.683, 0.316 624 23.97 57 Example 5 0.679, 0.320 622 24.73 57 Comparative example 3 0.679, 0.320 622 22.85 52 Comparative example 4 0.679, 0.320 622 22.91 59 Comparative example 5 0.680, 0.320 622 23.39 54

• Aus den in Tabelle 2 gezeigten Daten und dem Vergleich von Beispiel 1 und den Vergleichsbeispielen 1 und 2 geht hervor, dass die Chromatizitätskoordinaten und Emissionswellenlängen annähernd gleich sind. Am wichtigsten ist jedoch, dass im Vergleich zu der Vorrichtung in Vergleichsbeispiel 1 die Lebensdauer der Vorrichtung in Beispiel 1 um 8,2 % erhöht und die externe Quanteneffizienz um 4,0 % verbessert ist; im Vergleich zu der Vorrichtung in Vergleichsbeispiel 2 ist die Lebensdauer der Vorrichtung in Beispiel 1 um 23,3 % erhöht und die externe Quanteneffizienz um 4,7 % verbessert. Dies zeigt, dass die Di-Deuterium-Substitution an der 3- und 4-Position des Isochinolin-Liganden sowohl zu einer Verbesserung der Lebensdauer als auch der Effizienz führt, insbesondere zu einer signifikanten Erhöhung der Lebensdauer, was die Einzigartigkeit und Bedeutung dieses Strukturmerkmals bestätigt.

Discussion:

• From the data shown in Table 2 and the comparison of Example 1 and Comparative Examples 1 and 2, it can be seen that the chromaticity coordinates and emission wavelengths are approximately the same. Most importantly, compared with the device in Comparative Example 1, the life of the device in Example 1 is increased by 8.2% and the external quantum efficiency is improved by 4.0%; Compared with the device in Comparative Example 2, the life of the device in Example 1 is increased by 23.3% and the external quantum efficiency is improved by 4.7%. This shows that the di-deuterium substitution at the 3- and 4-position of the isoquinoline ligand leads to both an improvement in the lifetime and the efficiency, in particular a significant increase in the lifetime, which confirms the uniqueness and importance of this structural feature .

From the comparison of Example 2 and Comparative Examples 3 to 5, it can be seen that the chromaticity coordinates and emission wavelengths of the device in Example 2 approximately correspond to the chromaticity coordinates and emission wavelengths of the devices in Comparative Examples 3 to 5. Most importantly, compared with the device in Comparative Example 3, the life of the device in Example 2 is increased by 23% and the external quantum efficiency is improved by 2.4%; compared with the device in Comparative Example 4, the device life in Example 2 is increased by 8.5%, and the external quantum efficiency is improved by 2.2%; Compared with the device in Comparative Example 5, the life of the device in Example 2 is increased by 18.5%, and the external quantum efficiency is slightly improved. The data of Examples 3 to 5 also show high life and high efficiency properties, similar to Example 2. These device results show that the di-deuterium substitution at the 3- and 4-positions of the isoquinoline ligand both leads to an improvement in the Service life as well as efficiency leads, in particular, to a significant increase in service life, which in turn confirms the uniqueness and importance of this structural feature.

It should be understood that various embodiments described herein are examples and are not intended to limit the scope of the present disclosure. Therefore, it will be apparent to those skilled in the art that the present disclosure as claimed may include variations of the specific embodiments and preferred embodiments described herein. Other materials and structures may be substituted for many of the materials and structures described herein without departing from the spirit of the present disclosure. It should be understood that various theories as to why the present disclosure works are not intended to be limiting.

QUOTES INCLUDED IN THE DESCRIPTION

This list of the documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

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Claims (20)

A metal complex having the general structure M (L _a ) _m (L _b ) _n (L _c ) _q , where L _a , L _b and L _{c are} the first ligand, the second ligand and the third ligand, respectively, that are associated with the Metal M are coordinated; wherein the metal M is a metal whose atomic mass is greater than 40; wherein L _a , L _b and Lc can optionally be linked to form a multidentate ligand; where m is 1 or 2, n is 1 or 2, q is 0 or 1 and m + n + q is the same as the oxidation state of the metal M; when m is greater than 1, L _{a can be the} same or different; and when n is greater than 1, L _{b may be the} same or different; wherein the first ligand L _{a has} a structure represented by Formula 1:

where X ₁ to X ₄ , identically or differently on each occurrence, are selected from CR ₁ or N; where Y ₁ to Y ₄ , identically or differently on each occurrence, are selected from CR ₂ or N; where R ₁ and R ₂ , identically or differently on each occurrence, are selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl with 7 to 30 carbon atoms, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 carbon atoms, substituted or unsubstituted alkenyl with 2 to 20 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl with 6 to 20 carbon atoms omen, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; in Formula 1, adjacent substituents may optionally be linked to form a ring; wherein the second ligand L _{b has} a structure represented by Formula 2:

where R _t to R _z , identically or differently on each occurrence, are selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl with 7 to 30 carbon atoms, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 carbon atoms, substituted or unsubstituted alkenyl with 2 to 20 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl with 6 to 20 carbon atoms omen, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; in Formula 2, adjacent substituents may optionally be linked to form a ring; wherein the third ligand L _{c is} a monoanionic bidentate ligand. The metal complex according to Claim 1 wherein the metal M is selected from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir and Pt; preferably the metal M is selected from Pt or Ir. The metal complex according to one of the Claims 1 to 2 wherein at least one of X ₁ to X _{4 is} selected from CR ₁ ; preferably, where X ₁ to X ₄ , identically or differently on each occurrence, are selected from CR ₁ . The metal complex according to one of the Claims 1 to 2 , where X ₁ and / or X ₃ , identically or differently on each occurrence, are selected from CR ₁ , and R ₁ , identically or differently on each occurrence, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl with 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl with 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1 to 20 carbon atoms, substituted or unsubstituted aralkyl with 7 to 30 carbon atoms, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 carbon atoms, substituted or unsubstituted alkenyl with 2 to 20 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl with 3 to 20 carbons Substance atoms, substituted or unsubstituted arylsilyl with 6 to 20 carbon atoms, substituted or unsubstituted amino with 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a Phosphino group and combinations thereof; preferably, where X ₁ and X ₃ are selected, identical or different on each occurrence, CR ₁ and R ₁ , identical or different on each occurrence, are selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl with 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl with 3 to 20 ring carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms and substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms; more preferred, where X ₁ and X ₃ , identically or differently on each occurrence, are selected from CR ₁ , and R ₁ , identically or differently on each occurrence, is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, and X ₂ and X _{4 are} CH; where adjacent R ₁ substituents may optionally be linked to form a ring. The metal complex according to one of the Claims 1 to 2 wherein X ₁ and X _{4 are} CH and X ₂ and X ₃ , identically or differently on each occurrence, are selected from CR ₁ . The metal complex according to one of the Claims 1 to 5 , where R ₁ , identically or differently on each occurrence, is selected from the group consisting of: hydrogen, deuterium, fluorine, methyl, ethyl, 2-butyl, isopropyl, tert-butyl, isobutyl, cyclopentyl, cyclohexyl, deuteromethyl, deuteropropyl, Isopropylamino, phenyl, 2,6-dimethylphenyl, pyridyl, vinyl, and combinations thereof; where adjacent R ₁ substituents may optionally be linked to form a ring. The metal complex according to one of the Claims 1 to 6th where Y ₁ to Y ₄ , identically or differently on each occurrence, are selected from CR ₂ , and R ₂ , identically or differently on each occurrence, is selected from the group consisting of: hydrogen, halogen, substituted or unsubstituted alkyl with 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl with 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1 to 20 carbon atoms, substituted or unsubstituted aralkyl with 7 to 30 carbon atoms, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 carbon atoms, substituted or unsubstituted alkenyl with 2 to 20 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl 20 carbon atoms, substituted or unsubstituted amino with 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile oil group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; where adjacent R ₂ substituents may optionally be linked to form a ring. The metal complex according to one of the Claims 1 to 6th , where Y _{2 is} CR ₂ and R ₂ , identically or differently on each occurrence, is selected from the group consisting of: halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1 to 20 carbon atoms, substituted or unsubstituted aralkyl with 7 to 30 carbon atoms, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 carbon atoms, substituted or unsubstituted alkenyl with 2 to 20 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl with 6 to 20 carbon atoms, substitute rtem or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphine group, and combinations thereof; preferably, Y _{2 is} CR ₂ , and R ₂ , identically or differently on each occurrence, is selected from the group consisting of: halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms; more preferably, Y _{2 is} CR ₂ and R ₂ , identically or differently on each occurrence, is selected from substituted or unsubstituted alkyl or cycloalkyl having 1 to 20 carbon atoms or substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, and Y ₁ , Y ₃ and Y _{4 are} each CH; where adjacent R ₂ substituents may optionally be linked to form a ring. The metal complex according to one of the Claims 1 to 8th , where R ₂ , identically or differently on each occurrence, is selected from the group consisting of: hydrogen, fluorine, methyl, ethyl, isopropyl, 2-butyl, isobutyl, tert-butyl, pent-3-yl, cyclopentyl, cyclohexyl, 4,4-dimethylcyclohexyl, neopentyl, 2,4-dimethylpent-3-yl, 1,1-dimethylsilacyclohex-4-yl, cyclopentylmethyl, cyano, trifluoromethyl, trimethylsilyl, phenyldimethylsilyl, bicyclo [2,2,1] pentyl, adamantyl, Deuteroisopropyl, phenyl, pyridyl, and combinations thereof. The metal complex according to one of the Claims 1 to 2 , wherein the first ligand L _a , identically or differently on each occurrence, is selected from one or two structures from the group consisting of L _a1 to L _a1189 :

The metal complex according to one of the Claims 1 to 10 , where, in formula 2, Rt to R _{z are,} identically or differently on each occurrence, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 Ring carbon atoms and combinations thereof; preferably, Rt is selected from hydrogen, deuterium or methyl, and R _u to R _z , identical or different on each occurrence, are selected from hydrogen, deuterium, fluorine, methyl, ethyl, propyl, cyclobutyl, cyclopentyl, cyclohexyl, 3-methylbutyl , 3-ethylpentyl, trifluoromethyl, and combinations thereof. The metal complex according to one of the Claims 1 to 10 , wherein the second ligand L _b , identical or different on each occurrence, is selected from one or two structures from the group consisting of L _b1 to L _b383 :

and

The metal complex according to Claim 10 or 12th , wherein hydrogen in the first ligand L _a and / or in the second ligand L _{b is} partially or completely substituted by deuterium. The metal complex according to one of the Claims 1 to 13th , wherein the third ligand L _{c is selected} from one of the following structures:

and

where R _a , R _b and R _{c can represent} monosubstitution, multiple substitutions or no substitution; X _b , identically or differently on each occurrence, is selected from the group consisting of: O, S, Se, NR _N1 , and CR _C1 R _C2 ; X _c and X _d , identically or different on each occurrence, are selected from the group consisting of: O, S, Se and NR _N2 ; Ra, R _b , Rc, R _N1 , R _N2 , R _C1 and R _C2 , identical or different on each occurrence, are selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl with 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl with 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl with 7 to 30 carbon atoms, substituted or unsubstituted alkoxy with 1 to 20 carbon atoms, substituted or unsubstituted aryloxy with 6 to 30 carbon atoms substituted or unsubstituted alkenyl with 2 to 20 carbon atoms, substituted or unsubstituted aryl with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl with 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl with 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl with 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; in the structure of L _c , adjacent substituents may optionally be linked to form a ring. The metal complex according to one of the Claims 1 to 13th , wherein the third ligand L _c , identically or differently on each occurrence, is selected from the group consisting of:

and

The metal complex according to Claim 15 wherein the metal complex is Ir (L _a ) ₂ (L _b ) or Ir (L _a ) (L _b ) (L _c ); preferably the metal complex is selected from the group consisting of:

and

An electroluminescent device comprising: an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprising the metal complex according to any one of Claims 1 to 16 includes. The electroluminescent device according to Claim 17 wherein the electroluminescent device emits red light or white light. The electroluminescent device according to Claim 17 wherein the organic layer is a light emitting layer and the metal complex is a light emitting material; preferably, wherein the organic layer further comprises a host material; more preferred, the host material having at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, azadibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, Quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof. A compound formulation comprising the metal complex according to any one of Claims 1 to 16 .

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