Patent Application
20250011356
This application claims priority to Chinese Patent Application No. 202310784339.4 filed on Jun. 29, 2023, the disclosure of which is incorporated herein by reference in its entirety.
The present disclosure relates to compounds for organic electronic devices such as organic light-emitting devices. More particularly, the present disclosure relates to a metal complex comprising a ligand La having a structure of Formula 1, an organic electroluminescent device comprising the metal complex and a compound composition comprising the metal complex.
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-sensitized solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field-quench 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 bilayer organic electroluminescent device, which includes an arylamine hole transporting layer and a tris-8-hydroxyquinolato-aluminum layer as the electron and emitting layer (Applied Physics Letters, 1987, 51 (12): 913-915). Once a bias is applied to the device, green light was emitted from the device. This device laid the foundation for the development of modern organic light-emitting diodes (OLEDs). State-of-the-art OLEDs may include multiple layers such as charge injection and transporting layers, charge and exciton blocking layers, and one or multiple emissive layers between the cathode and anode. Since the OLED is a self-emitting solid state device, it offers tremendous potential for display and lighting applications. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on flexible substrates.
The OLED can be categorized as three different types according to its emitting mechanism. The OLED invented by Tang and van Slyke is a fluorescent OLED. It only utilizes singlet emission. The triplets generated in the device are wasted through nonradiative decay channels. Therefore, the internal quantum efficiency (IQE) of the fluorescent OLED is only 25%. This limitation hindered the commercialization of OLED. In 1997, Forrest and Thompson reported phosphorescent OLED, which uses triplet emission from heavy metal containing complexes as the emitter. As a result, both singlet and triplets can be harvested, achieving 100% IQE. The discovery and development of phosphorescent OLED contributed directly to the commercialization of 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 small singlet-triplet gap that makes the transition from triplet back to singlet possible. In the TADF device, the triplet excitons can go through reverse intersystem crossing to generate singlet excitons, resulting in high IQE.
OLEDs can also be classified as small molecule and polymer OLEDs according to the forms of the 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 well defined structure. Dendrimers with well-defined structures are considered as small molecules. Polymer OLEDs include conjugated polymers and non-conjugated polymers with pendant emitting groups. Small molecule OLED can become the polymer OLED if post polymerization occurred during the fabrication process.
There are various methods for OLED fabrication. Small molecule OLEDs are generally fabricated by vacuum thermal evaporation. Polymer OLEDs are fabricated by solution process such as spin-coating, inkjet printing, and slit printing. If the material can be dissolved or dispersed in a solvent, the small molecule OLED can also be produced by solution process.
The emitting color of the OLED can be achieved by emitter structural design. An OLED may include one emitting layer or a plurality of emitting layers to achieve desired spectrum. In the case of green, yellow, and red OLEDs, phosphorescent emitters have successfully reached commercialization. Blue phosphorescent device still suffers from non-saturated blue color, short device lifetime, and high operating voltage. Commercial full-color OLED displays normally adopt a hybrid strategy, using fluorescent blue and phosphorescent yellow, or red and green. At present, efficiency roll-off of phosphorescent OLEDs at high brightness remains a problem. In addition, it is desirable to have more saturated emitting color, higher efficiency, and longer device lifetime.
From an electronic perspective, a display principle of the OLED is briefly described as follows: under the action of an applied electric field greater than a certain threshold, holes and electrons are injected into an organic film light-emitting layer sandwiched between an anode and a cathode in a form of current from the anode and the cathode, respectively. The holes and the electrons are combined to form excitons, and radiative recombination occurs to cause light emission. Since the organic light-emitting film has very apparent capacitance characteristics, a capacitance of the organic light-emitting film layer is a key factor that affects the response time and refresh rate of an OLED display device at a low grayscale.
CN111655705A has disclosed a metal complex having the following structure:
where R5 is selected from groups such as halogen, a nitrile group, a nitro group, . . . and substituted or unsubstituted alkyl having 3 to 30 carbon atoms, R4 is selected from many groups such as hydrogen, deuterium, halogen, and CN111655705A has further disclosed the following specific structures:
The application does not disclose or teach a metal complex where R5 is a substituent “whose total number of carbon atoms is greater than or equal to 2” and R4 at a particular position is aryl or heteroaryl and an effect of the metal complex on device performance.
US20210403496A1 has disclosed a phosphorescent metal complex having the following structure:
where Ar is selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and combinations thereof, X4 is selected from CRx or N, Rx is selected from many groups such as hydrogen, deuterium and halogen, and US20210403496A1 has further disclosed the following specific structures:
The application does not disclose or teach a metal complex where X4 is selected from CRx and Rx is a substituent “whose total number of carbon atoms is greater than or equal to 2” and an effect of the metal complex on device performance.
The present disclosure aims to provide a series of metal complexes each comprising a ligand La having a structure of Formula 1 to solve at least part of the above-mentioned problems. Applied to an electroluminescent device, these new metal complexes can significantly reduce a full width at half maximum and capacitance of the device, thereby contributing to improving the overall performance of the device.
According to an embodiment of the present disclosure, disclosed is a metal complex comprising a metal M and a ligand La coordinated to the metal M, wherein La has a structure represented by Formula 1:
According to another embodiment of the present disclosure, further disclosed is an organic electroluminescent device comprising an anode, a cathode and an organic layer disposed between the anode and the cathode, wherein at least one layer of the organic layer comprises the metal complex in the preceding embodiment.
According to another embodiment of the present disclosure, further disclosed is a compound composition comprising the metal complex in the preceding embodiment.
The present disclosure aims to provide the series of metal complexes each comprising the ligand La having the structure of Formula 1 to solve at least part of the above-mentioned problems. Applied to the electroluminescent device, these new metal complexes can reduce the full width at half maximum and capacitance of the device. The organic electroluminescent device can improve the response time and refresh rate of an OLED display device at a low grayscale and can maintain excellent device performance, thereby contributing to improving the overall performance of the device. The metal complex has a great advantage and a broad prospect in industrial application.
OLEDs can be fabricated on various types of substrates such as glass, plastic, and metal foil.
More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference herein in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference herein in its entirety. Examples of host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference herein in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference herein in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference herein in their entireties, 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 blocking layers are described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference herein in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference herein in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference herein in its entirety.
The layered structure described above is provided by way of non-limiting examples. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely. It may also include other layers not specifically described. Within each layer, a single material or a mixture of multiple materials can be used to achieve optimum performance. Any functional layer may include several sublayers. For example, the emissive layer may have two layers of different emitting materials to achieve desired emission spectrum.
In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may include a single layer or multiple layers.
An OLED can be encapsulated by a barrier layer.
As used herein, “emissive area” means the area of an organic electroluminescent device in the direction perpendicular to the emissive surface where the anode is in direct contact with the organic layer and at the same time the organic layer is in direct contact with the cathode. Herein, the emissive area in Device Examples and Device Comparative Examples is 0.04 cm2.
Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, smart phones, tablets, phablets, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicles displays, and vehicle tail lights.
The materials and structures described herein may be used in other organic electronic devices listed above.
As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from the substrate. There may be other layers between the first and second layers, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.
As used herein, “solution processible” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistics limit through delayed fluorescence. As used herein, there are two types of delayed fluorescence, i.e. P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence is generated from triplet-triplet annihilation (TTA).
On the other hand, E-type delayed fluorescence does not rely on the collision of two triplets, but rather on the transition between the triplet states and the singlet excited states. Compounds that are capable of generating E-type delayed fluorescence are required to have very small singlet-triplet gaps to convert 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 distinctive feature of TADF is that the delayed component increases as temperature rises. If the reverse intersystem crossing (RISC) rate is fast enough to minimize the non-radiative decay from the triplet state, the fraction of back populated singlet excited states can potentially reach 75%. The total singlet fraction can be 100%, far exceeding 25% of the spin statistics limit for electrically generated excitons.
E-type delayed fluorescence characteristics can be found in an exciplex system or in a single compound. Without being bound by theory, it is believed that E-type delayed fluorescence requires the luminescent material to have a small singlet-triplet energy gap (AEs-T). Organic, non-metal containing, donor-acceptor luminescent materials may be able to achieve this. The emission in these materials is generally characterized as a donor-acceptor charge-transfer (CT) type emission. The spatial separation of the HOMO and LUMO in these donor-acceptor type compounds generally results in small AEs-T. These states may involve CT states. Generally, donor-acceptor luminescent materials are constructed by connecting an electron donor moiety such as amino- or carbazole-derivatives and an electron acceptor moiety such as N-containing six-membered aromatic rings.
Halogen or halide—as used herein includes fluorine, chlorine, bromine, and iodine.
Alkyl—as used herein includes both straight and branched chain alkyl groups. Alkyl may be alkyl having 1 to 20 carbon atoms, preferably alkyl having 1 to 12 carbon atoms, and more preferably alkyl having 1 to 6 carbon atoms. Examples of alkyl groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, a neopentyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 1-pentylhexyl group, a 1-butylpentyl group, a 1-heptyloctyl group, and a 3-methylpentyl group. Of the above, preferred are a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, a neopentyl group, and an n-hexyl group. Additionally, the alkyl group may be optionally substituted.
Cycloalkyl—as used herein includes cyclic alkyl groups. The cycloalkyl groups may be those having 3 to 20 ring carbon atoms, preferably those having 4 to 10 carbon atoms. Examples of cycloalkyl include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcylcohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, and the like. Of the above, preferred are cyclopentyl, cyclohexyl, 4-methylcyclohexyl, and 4,4-dimethylcylcohexyl. Additionally, the cycloalkyl group may be optionally substituted.
Heteroalkyl—as used herein, includes a group formed by replacing one or more carbons in an alkyl chain with a hetero-atom(s) selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a silicon atom, a germanium atom, and a boron atom. Heteroalkyl may be those having 1 to 20 carbon atoms, preferably those having 1 to 10 carbon atoms, and more preferably those having 1 to 6 carbon atoms. Examples of heteroalkyl include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxymethoxymethyl, ethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminomethyl, trimethylgermanylmethyl, trimethylgermanylethyl, trimethylgermanylisopropyl, dimethylethylgermanylmethyl, dimethylisopropylgermanylmethyl, tert-butylmethylgermanylmethyl, triethylgermanylmethyl, triethylgermanylethyl, triisopropylgermanylmethyl, triisopropylgermanylethyl, trimethylsilylmethyl, trimethylsilylethyl, and trimethylsilylisopropyl, triisopropylsilylmethyl, triisopropylsilylethyl. Additionally, the heteroalkyl group may be optionally substituted.
Alkenyl—as used herein includes straight chain, branched chain, and cyclic alkene groups. Alkenyl may be those having 2 to 20 carbon atoms, preferably those having 2 to 10 carbon atoms. Examples of alkenyl include vinyl, 1-propenyl group, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butandienyl, 1-methylvinyl, styryl, 2,2-diphenylvinyl, 1,2-diphenylvinyl, 1-methylallyl, 1,1-dimethylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl, 3-phenylallyl, 3,3-diphenylallyl, 1,2-dimethylallyl, 1-phenyl-1-butenyl, 3-phenyl-1-butenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl, cyclooctatetraenyl, and norbornenyl. Additionally, the alkenyl group may be optionally substituted.
Alkynyl—as used herein includes straight chain alkynyl groups. Alkynyl may be those having 2 to 20 carbon atoms, preferably those having 2 to 10 carbon atoms. Examples of alkynyl groups include ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3,3-dimethyl-1-butynyl, 3-ethyl-3-methyl-1-pentynyl, 3,3-diisopropyl-1-pentynyl, phenylethynyl, phenylpropynyl, etc. Of the above, preferred are ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, and phenylethynyl. Additionally, the alkynyl group may be optionally substituted.
Aryl or an aromatic group—as used herein includes non-condensed and condensed systems. Aryl may be those having 6 to 30 carbon atoms, preferably those having 6 to 20 carbon atoms, and more preferably those having 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene. Examples of non-condensed aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4′-methylbiphenylyl, 4″-t-butyl-p-terphenyl-4-yl, o-cumenyl, m-cumenyl, p-cumenyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesityl, and m-quarterphenyl. Additionally, the aryl group may be optionally substituted.
Heterocyclic groups—as used herein include non-aromatic cyclic groups. Non-aromatic heterocyclic groups include saturated heterocyclic groups having 3 to 20 ring atoms and unsaturated non-aromatic heterocyclic groups having 3 to 20 ring atoms, where at least one ring atom is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, a phosphorus atom, a germanium atom, and a boron atom. Preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms, each of which includes at least one hetero-atom such as nitrogen, oxygen, silicon, or sulfur. Examples of non-aromatic heterocyclic groups include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxolanyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxepinyl, thiepinyl, azepinyl, and tetrahydrosilolyl. Additionally, the heterocyclic group may be optionally substituted.
Heteroaryl—as used herein, includes non-condensed and condensed hetero-aromatic groups having 1 to 5 hetero-atoms, where at least one hetero-atom is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, a phosphorus atom, a germanium atom, and a boron atom. A hetero-aromatic group is also referred to as heteroaryl. Heteroaryl may be those having 3 to 30 carbon atoms, preferably those having 3 to 20 carbon atoms, and more preferably those having 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridoindole, 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, xanthene, acridine, phenazine, phenothiazine, 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. Additionally, the heteroaryl group may be optionally substituted.
Alkoxy—as used herein, is represented by —O-alkyl, —O-cycloalkyl, —O-heteroalkyl, or —O-heterocyclic group. Examples and preferred examples of alkyl, cycloalkyl, heteroalkyl, and heterocyclic groups are the same as those described above. Alkoxy groups may be those having 1 to 20 carbon atoms, preferably those having 1 to 6 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy, and ethoxymethyloxy. Additionally, the alkoxy group may be optionally substituted.
Aryloxy—as used herein, is represented by —O-aryl or —O-heteroaryl. Examples and preferred examples of aryl and heteroaryl are the same as those described above. Aryloxy groups may be those having 6 to 30 carbon atoms, preferably those having 6 to 20 carbon atoms. Examples of aryloxy groups include phenoxy and biphenyloxy. Additionally, the aryloxy group may be optionally substituted.
Arylalkyl—as used herein, contemplates alkyl substituted with an aryl group. Arylalkyl may be those having 7 to 30 carbon atoms, preferably those having 7 to 20 carbon atoms, and more preferably those having 7 to 13 carbon atoms. Examples of arylalkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl-t-butyl, alpha-naphthylmethyl, 1-alpha-naphthylethyl, 2-alpha-naphthylethyl, 1-alpha-naphthylisopropyl, 2-alpha-naphthylisopropyl, beta-naphthylmethyl, 1-beta-naphthylethyl, 2-beta-naphthylethyl, 1-beta-naphthylisopropyl, 2-beta-naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl, and 1-chloro-2-phenylisopropyl. Of the above, preferred are benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, and 2-phenylisopropyl. Additionally, the arylalkyl group may be optionally substituted.
Alkylsilyl—as used herein, contemplates a silyl group substituted with an alkyl group. Alkylsilyl groups may be those having 3 to 20 carbon atoms, preferably those having 3 to 10 carbon atoms. Examples of alkylsilyl groups include trimethylsilyl, triethylsilyl, methyldiethylsilyl, ethyldimethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, methyldiisopropylsilyl, dimethylisopropylsilyl, tri-t-butylsilyl, triisobutylsilyl, dimethyl t-butylsilyl, and methyldi-t-butylsilyl. Additionally, the alkylsilyl group may be optionally substituted.
Arylsilyl—as used herein, contemplates a silyl group substituted with an aryl group. Arylsilyl groups may be those having 6 to 30 carbon atoms, preferably those having 8 to 20 carbon atoms. Examples of arylsilyl groups include triphenylsilyl, phenyldibiphenylylsilyl, diphenylbiphenylsilyl, phenyldiethylsilyl, diphenylethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, phenyldiisopropylsilyl, diphenylisopropylsilyl, diphenylbutylsilyl, diphenylisobutylsilyl, diphenyl t-butylsilyl. Additionally, the arylsilyl group may be optionally substituted.
Alkylgermanyl—as used herein contemplates germanyl substituted with an alkyl group. The alkylgermanyl may be those having 3 to 20 carbon atoms, preferably those having 3 to 10 carbon atoms. Examples of alkylgermanyl include trimethylgermanyl, triethylgermanyl, methyldiethylgermanyl, ethyldimethylgermanyl, tripropylgermanyl, tributylgermanyl, triisopropylgermanyl, methyldiisopropylgermanyl, dimethylisopropylgermanyl, tri-t-butylgermanyl, triisobutylgermanyl, dimethyl-t-butylgermanyl, and methyldi-t-butylgermanyl. Additionally, the alkylgermanyl may be optionally substituted.
Arylgermanyl—as used herein contemplates a germanyl substituted with at least one aryl group or heteroaryl group. Arylgermanyl may be those having 6 to 30 carbon atoms, preferably those having 8 to 20 carbon atoms. Examples of arylgermanyl include triphenylgermanyl, phenyldibiphenylylgermanyl, diphenylbiphenylgermanyl, phenyldimethylgermanyl, phenyldiethylgermanyl, diphenylethylgermanyl, diphenylmethylgermanyl, phenyldiisopropylgermanyl, diphenylisopropylgermanyl, diphenylbutylgermanyl, diphenylisobutylgermanyl, and diphenyl-t-butylgermanyl. Additionally, the arylgermanyl may be optionally substituted.
The term “aza” in azadibenzofuran, azadibenzothiophene, etc. means that one or more of C—H groups in the respective aromatic fragment are replaced by a nitrogen atom. For example, azatriphenylene encompasses dibenzo[f,h]quinoxaline, dibenzo[f,h]quinoline and other analogs with two or more nitrogens in the ring system. One of ordinary skill 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 as set forth herein.
In the present disclosure, unless otherwise defined, when any term of the group consisting of substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted heterocyclic group, substituted arylalkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted alkylgermanyl, substituted arylgermanyl, substituted amino, substituted acyl, substituted carbonyl, a substituted carboxylic acid group, a substituted ester group, substituted sulfinyl, substituted sulfonyl, and substituted phosphino is used, it means that any group of alkyl, cycloalkyl, heteroalkyl, heterocyclic group, arylalkyl, alkoxy, aryloxy, alkenyl, alkynyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amino, acyl, carbonyl, a carboxylic acid group, an ester group, sulfinyl, sulfonyl, and phosphino may be substituted with one or more moieties selected from the group consisting of deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted heteroalkyl having 1 to 20 carbon atoms, an unsubstituted heterocyclic group having 3 to 20 ring atoms, unsubstituted arylalkyl having 7 to 30 carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted aryloxy having 6 to 30 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, unsubstituted alkynyl having 2 to 20 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted heteroaryl having 3 to 30 carbon atoms, unsubstituted alkylsilyl having 3 to 20 carbon atoms, unsubstituted arylsilyl having 6 to 20 carbon atoms, unsubstituted alkylgermanyl having 3 to 20 carbon atoms, unsubstituted arylgermanyl group having 6 to 20 carbon atoms, unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.
It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or an attached fragment are considered to be equivalent.
In the compounds mentioned in the present disclosure, hydrogen atoms may be partially or fully replaced by deuterium. Other atoms such as carbon and nitrogen can also be replaced by their other stable isotopes. The replacement by other stable isotopes in the compounds may be preferred due to its enhancements of device efficiency and stability.
In the compounds mentioned in the present disclosure, multiple substitution refers to a range that includes a di-substitution, up to the maximum available substitution. When substitution in the compounds mentioned in the present disclosure represents multiple substitution (including di-, tri-, and tetra-substitutions, etc.), that means the substituent may exist at a plurality of available substitution positions on its linking structure, the substituents present at a plurality of available substitution positions may be the same structure or different structures.
In the compounds mentioned in the present disclosure, adjacent substituents in the compounds cannot be joined to form a ring unless otherwise explicitly defined, for example, adjacent substituents can be optionally joined to form a ring. In the compounds mentioned in the present disclosure, the expression that adjacent substituents can be optionally joined to form a ring includes a case where adjacent substituents may be joined to form a ring and a case where adjacent substituents are not joined to form a ring. When adjacent substituents can be optionally joined to form a ring, the ring formed may be monocyclic or polycyclic (including spirocyclic, endocyclic, fusedcyclic, and etc.), as well as alicyclic, heteroalicyclic, aromatic, or heteroaromatic. In such expression, adjacent substituents may refer to substituents bonded to the same atom, substituents bonded to carbon atoms which are directly bonded to each other, or substituents bonded to carbon atoms which are more distant from each other. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms which are directly bonded to each other.
The expression that adjacent substituents can be optionally joined to form a ring is also intended to mean that two substituents bonded to the same carbon atom are joined to each other via a chemical bond to form a ring, which can be exemplified by the following formula:
The expression that adjacent substituents can be optionally joined to form a ring is also intended to mean that two substituents bonded to carbon atoms which are directly bonded to each other are joined to each other via a chemical bond to form a ring, which can be exemplified by the following formula:
The expression that adjacent substituents can be optionally joined to form a ring is also intended to mean that two substituents bonded to a further distant carbon atom are joined to each other via a chemical bond to form a ring, which can be exemplified by the following formula:
Furthermore, the expression that adjacent substituents can be optionally joined to form a ring is also intended to mean that, in the case where one of the two substituents bonded to carbon atoms which are directly bonded to each other represents hydrogen, the second substituent is bonded at a position at which the hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following formula:
According to an embodiment of the present disclosure, disclosed is a metal complex comprising a metal M and a ligand La coordinated to the metal M, wherein La has a structure represented by Formula 1:
In the present disclosure, when G1 is selected from a single bond, it indicates that Y1 is directly joined to the metal M, and when G2 is selected from a single bond, it indicates that X1, X2 or X3 is directly joined to the metal M.
In the present disclosure, the expression that “adjacent substituents Ry can be optionally joined to form a ring” is intended to mean that any one or more groups of the group consisting of adjacent substituents Ry can be optionally joined to form a ring. Obviously, it is also possible that none of these substituents are joined to form a ring.
In the present disclosure, the expression that “adjacent substituents Ry and R′ can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents Ry, two substituents R′, and substituents Ry and R′, can be joined to form a ring. Obviously, it is also possible that none of these substituents are joined to form a ring.
In the present disclosure, the expression that “adjacent substituents R1, R2 and R3 can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as substituents R1 and R2, substituents R1 and R3, and substituents R3 and R2, can be joined to form a ring. Obviously, it is also possible that none of these substituents are joined to form a ring.
According to an embodiment of the present disclosure, Cy is, at each occurrence identically or differently, selected from any structure of the group consisting of the following:
According to an embodiment of the present disclosure, the metal complex has a general formula of M(La)m(Lb)n(Lc)q;
In the present disclosure, the expression that “adjacent substituents Ra, Rb, Rc, RN1, RC1 and RC2 can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents Ra, two substituents Rb, substituents Ra and Rb, substituents Ra and Rc, substituents Rb and Rc, substituents Ra and RN1, substituents Rb and RN1, substituents Ra and RC1, substituents Ra and RC2, substituents Rb and RC1, substituents Rb and RC2, and substituents RC1 and RC2, can be joined to form a ring. Obviously, it is also possible that none of these substituents are joined to form a ring. For example, adjacent substituents Ra and Rb in
can be optionally joined to form a ring. When Ra is optionally joined to form a ring,
may form a structure of
According to an embodiment of the present disclosure, G1 and G2 are, at each occurrence identically or differently, selected from a single bond or O.
According to an embodiment of the present disclosure, G1 and G2 each are a single bond.
According to an embodiment of the present disclosure, the metal complex has a general formula structure of Ir(La)m(Lb)3-m, and the structure is represented by Formula 3:
In the present disclosure, the expression that “adjacent substituents Ru can be optionally joined to form a ring” is intended to mean that any one or more groups of the group consisting of adjacent substituents Ru can be optionally joined to form a ring. Obviously, it is also possible that none of these substituents are joined to form a ring.
According to an embodiment of the present disclosure, m is selected from 1 or 2.
According to an embodiment of the present disclosure, m is selected from 1.
According to an embodiment of the present disclosure, R1, R2 and R3 are, at each occurrence identically or differently, 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 aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, a cyano group and combinations thereof, and the total number of carbon atoms in R1, R2 and R3 is greater than or equal to 1.
According to an embodiment of the present disclosure, R1, R2 and R3 are, at each occurrence identically or differently, 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 aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, a cyano group and combinations thereof, and at least one of R1, R2 and R3 is selected from 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 an embodiment of the present disclosure, R1, R2 and R3 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms and combinations thereof, and the total number of carbon atoms in R1, R2 and R3 is greater than or equal to 1.
According to an embodiment of the present disclosure, R1, R2 and R3 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms and combinations thereof, and at least one of R1, R2 and R3 is selected from substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, R1, R2 and R3 are, at each occurrence identically or differently, selected from hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 6 carbon atoms and combinations thereof, and at least one of R1, R2 and R3 is selected from substituted or unsubstituted alkyl having 1 to 6 carbon atoms.
According to an embodiment of the present disclosure, R1, R2 and R3 are, at each occurrence identically or differently, selected from hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, and R1, R2 and R3 are not joined to form a ring, or two of R1, R2 and R3 are joined to form a ring. For example, two of R1, R2 and R3 are joined to form substituted or unsubstituted cycloalkyl.
According to an embodiment of the present disclosure, at least one of R1, R2 and R3 is selected from hydrogen or deuterium.
According to an embodiment of the present disclosure, one of R1, R2 and R3 is selected from hydrogen or deuterium.
According to an embodiment of the present disclosure, two of R1, R2 and R3 are selected from hydrogen or deuterium.
According to an embodiment of the present disclosure, Rn is, at each occurrence identically or differently, selected from the group consisting of:
wherein optionally, hydrogen in the above Rn can be partially or fully substituted with deuterium.
According to an embodiment of the present disclosure, X3 to X6 are, at each occurrence identically or differently, selected from CRx.
According to an embodiment of the present disclosure, X3 to X6 are, at each occurrence identically or differently, selected from CRx or N, and at least one of X3 to X6 is N. For example, one of X3 to X6 is selected from N, or two of X3 to X6 are selected from N.
According to an embodiment of the present disclosure, Y3 to Y6 are, at each occurrence identically or differently, selected from CRy.
According to an embodiment of the present disclosure, Y3 to Y6 are, at each occurrence identically or differently, selected from CRy or N, and at least one of Y3 to Y6 is N. For example, one of Y3 to Y6 is selected from N, or two of Y3 to Y6 are selected from N.
According to an embodiment of the present disclosure, U1 to U8 are, at each occurrence identically or differently, selected from CRu.
According to an embodiment of the present disclosure, U1 to U8 are, at each occurrence identically or differently, selected from CRu or N, and at least one of U1 to U8 is N. For example, one of U1 to U8 is selected from N, or two of U1 to U8 are selected from N, or one of U1 to U4 is selected from N, or one of U5 to U8 is selected from N.
According to an embodiment of the present disclosure, Rx is, at each occurrence identically or differently, 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 aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, a cyano group and combinations thereof.
According to an embodiment of the present disclosure, Rx is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 12 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 12 carbon atoms, a cyano group and combinations thereof.
According to an embodiment of the present disclosure, Rx is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, a cyano group, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, neopentyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated neopentyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridyl, trimethylsilyl, trimethylgermanyl and combinations thereof.
According to an embodiment of the present disclosure, Ry is, at each occurrence identically or differently, 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 aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, a cyano group and combinations thereof.
According to an embodiment of the present disclosure, Ry is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 12 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 12 carbon atoms, a cyano group and combinations thereof.
According to an embodiment of the present disclosure, Ry is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, a cyano group, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, neopentyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated neopentyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridyl, trimethylsilyl, trimethylgermanyl and combinations thereof.
According to an embodiment of the present disclosure, Ru is, at each occurrence identically or differently, 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 aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, a cyano group and combinations thereof.
According to an embodiment of the present disclosure, Ru is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 12 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 12 carbon atoms, a cyano group and combinations thereof.
According to an embodiment of the present disclosure, Ru is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, a cyano group, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, neopentyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated neopentyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridyl, trimethylsilyl, trimethylgermanyl and combinations thereof.
According to an embodiment of the present disclosure, at least one of X3 to X6 is selected from CRx, the Rx is a cyano group or fluorine, and all the carbon atoms in the substituent Rn are selected from a primary carbon, a secondary carbon or a tertiary carbon.
According to an embodiment of the present disclosure, at least one of X4 to X6 is selected from CRy, the Rx is a cyano group or fluorine, and all the carbon atoms in the substituent Rn are selected from a primary carbon, a secondary carbon or a tertiary carbon.
According to an embodiment of the present disclosure, X6 is CRx, the Rx is a cyano group or fluorine, and all the carbon atoms in the substituent Rn are selected from a primary carbon, a secondary carbon or a tertiary carbon.
According to an embodiment of the present disclosure, X3 to X6 are, at each occurrence identically or differently, selected from CRx, the Rx is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, 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, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms and combinations thereof, and at least one of all the carbon atoms in the substituent Rn is a quaternary carbon.
According to an embodiment of the present disclosure, X4 to X6 are, at each occurrence identically or differently, selected from CRx, the Rx is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 12 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 12 carbon atoms and combinations thereof, and at least one of all the carbon atoms in the substituent Rn is a quaternary carbon.
According to an embodiment of the present disclosure, X6 is CRx, the Rx is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, a cyano group, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, neopentyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated neopentyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridyl, trimethylsilyl, trimethylgermanyl and combinations thereof, and at least one of all the carbon atoms in the substituent Rn is a quaternary carbon.
According to an embodiment of the present disclosure, at least one of Y3 to Y6 is selected from CRy, wherein the Ry is selected from the group consisting of: 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 aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, at least one of Y3 to Y6 is selected from CRy, wherein the Ry is selected from the group consisting of: deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, at least one of Y3 to Y6 is selected from CRy, wherein the Ry is selected from the group consisting of: deuterium, fluorine, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, neopentyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated neopentyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, trimethylsilyl, trimethylgermanyl and combinations thereof.
According to an embodiment of the present disclosure, at least one or at least two of U1 to U8 are selected from CRu, the Ru is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms or a combination thereof, and the total number of carbon atoms in all of the Ru is at least 4.
According to an embodiment of the present disclosure, at least one or at least two of U1 to U4 are selected from CRu, the Ru is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms or a combination thereof, and the total number of carbon atoms in all of the Ru is at least 4.
According to an embodiment of the present disclosure, at least one or at least two of U5 to U8 are selected from CRu, the Ru is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms or a combination thereof, and the total number of carbon atoms in all of the Ru is at least 4.
According to an embodiment of the present disclosure, Ar is, at each occurrence identically or differently, selected from the group consisting of Ar1 to Ar147, wherein the specific structures of Ar1 to Ar147 are referred to claim 15.
According to an embodiment of the present disclosure, hydrogen in Ar1 to Ar114, Ar116 to Ar126, Ar129, Ar131 to Ar136, Ar142, Ar143, Ar146 and Ar147 can be partially or fully substituted with deuterium.
According to an embodiment of the present disclosure, La is, at each occurrence identically or differently, selected from the group consisting of La1 to La6954, wherein the specific structures of La1 to La6954 are referred to claim 16.
According to an embodiment of the present disclosure, hydrogen in La1 to La6954 can be partially or fully substituted with deuterium.
According to an embodiment of the present disclosure, Lb is, at each occurrence identically or differently, selected from the group consisting of Lb1 to Lb158, wherein the specific structures of Lb1 to Lb158 are referred to claim 17.
According to an embodiment of the present disclosure, hydrogen in Lb1 to Lb18, Lb20 to Lb26 and Lb31 to Lb158 can be partially or fully substituted with deuterium.
According to an embodiment of the present disclosure, the metal complex has a structure of Ir(La)3 or Ir(La)(Lb)2 or Ir(La)2(Lb), wherein La is, at each occurrence identically or differently, selected from one, two or three of the group consisting of La1 to La6954, and Lb is, at each occurrence identically or differently, selected from one or two of the group consisting of Lb1 to Lb158.
According to an embodiment of the present disclosure, the metal complex is selected from the group consisting of Metal Complex 1 to Metal Complex 6728, wherein the specific structures of Metal Complex 1 to Metal Complex 6728 are referred to claim 18.
According to an embodiment of the present disclosure, further disclosed is an organic electroluminescent device comprising an anode, a cathode and an organic layer disposed between the anode and the cathode, wherein at least one layer of the organic layer comprises the metal complex in any one of the preceding embodiments.
According to an embodiment of the present disclosure, the organic layer comprising the metal complex is a light-emitting layer.
According to an embodiment of the present disclosure, the light-emitting layer further comprises a first host compound.
According to an embodiment of the present disclosure, the light-emitting layer further comprises a first host compound and a second host compound.
According to an embodiment of the present disclosure, the first host compound and/or the second host compound comprise at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, aza-dibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene and combinations thereof.
According to an embodiment of the present disclosure, the first host compound has a structure represented by Formula X-1 or Formula X-2:
In this embodiment, the expression that “adjacent substituents Rg, Rv and Rt can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents Rv, two substituents Rt, two substituents Rg, substituents Rv and Rt, substituents Rv and Rg, and substituents Rg and Rt, can be joined to form a ring. Obviously, it is also possible that none of these substituents are joined to form a ring.
According to an embodiment of the present disclosure, the first host compound has a structure represented by one of Formula X-a to Formula X-p:
According to an embodiment of the present disclosure, the first host compound is selected from the group consisting of the following compounds:
According to an embodiment of the present disclosure, the second host compound has a structure represented by Formula 4:
In the present disclosure, the expression that “adjacent substituents Re, RQ and Rq can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents Re, two substituents RQ, two substituents Rq, and two substituents RQ and Rq, can be joined to form a ring. Obviously, it is also possible that none of these substituents are joined to form a ring.
According to an embodiment of the present disclosure, the second host compound is selected from the group consisting of the following compounds:
According to an embodiment of the present disclosure, the metal complex is doped in the first host compound and the second host compound, and a weight of the metal complex accounts for 1% to 30% of a total weight of the light-emitting layer.
According to an embodiment of the present disclosure, the metal complex is doped in the first host compound and the second host compound, and the weight of the metal complex accounts for 3% to 13% of the total weight of the light-emitting layer.
According to an embodiment of the present disclosure, the organic electroluminescent device further comprises a hole injection layer. The hole injection layer may be a functional layer comprising a single material or a functional layer comprising multiple materials, wherein the comprised multiple materials are most commonly used as hole transporting materials doped with a certain proportion of p-type conductive doping material. Common p-type doping materials are as follows:
According to an embodiment of the present disclosure, disclosed is a compound composition comprising the metal complex in any one of the preceding 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 described in more detail in U.S. Pat. Pub. No. 20160359122 at paragraphs 0132-0161, which is incorporated by reference herein in its entirety. The materials described or referred to the disclosure are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
The materials described herein as useful for a particular layer in an organic light-emitting device may be used in combination with a variety of other materials present in the device. For example, dopants disclosed herein may be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The combination of these materials is described in detail in paragraphs 0080-0101 of U.S. Pat. Pub. No. 20150349273, which is incorporated by reference herein in its entirety. The materials described or referred to the disclosure are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
In the embodiments of material synthesis, all reactions were performed under nitrogen protection unless otherwise stated. All reaction solvents were anhydrous and used as received from commercial sources. Synthetic products were structurally confirmed and tested for properties using one or more conventional equipment in the art (including, but not limited to, nuclear magnetic resonance instrument produced by BRUKER, liquid chromatograph produced by SHIMADZU, liquid chromatograph-mass spectrometry produced by SHIMADZU, gas chromatograph-mass produced by SHIMADZU, differential Scanning calorimeters produced by SHIMADZU, fluorescence spectrophotometer produced by SHANGHAI LENGGUANG TECH., electrochemical workstation produced by WUHAN CORRTEST, and sublimation apparatus produced by ANHUI BEQ, etc.) by methods well known to the persons skilled in the art. In the embodiments of the device, the characteristics of the device were also tested using conventional equipment in the art (including, but not limited to, evaporator produced by ANGSTROM ENGINEERING, optical testing system produced by SUZHOU FATAR, life testing system produced by SUZHOU FATAR, and ellipsometer produced by BEIJING ELLITOP, etc.) by methods well known to the persons skilled in the art. As the persons skilled in the art are aware of the above-mentioned equipment use, test methods and other related contents, the inherent data of the sample can be obtained with certainty and without influence, so the above related contents are not further described in this patent.
Intermediate 1 (7.7 g, 25.1 mmol), Intermediate 2 (5.7 mL, 30.1 mmol), tetrakis(triphenylphosphine) palladium (1.4 g, 1.2 mmol), potassium carbonate (6.9 g, 50.2 mmol), toluene/ethanol/water (5/1/1, 70.0 mL) were added to a dry 250 mL round-bottom flask in sequence. Under N2 protection, a reaction was conducted overnight at 110° C. After the reaction was completed, the reaction solution was extracted with ethyl acetate and purified through column chromatography to obtain a white solid Intermediate 3 (6.0 g, 22.4 mmol, with a yield of 89%).
Intermediate 3 (10.0 g, 37.4 mmol), bis(pinacolato)diboron (10.4 g, 41.1 mmol), potassium acetate (7.3 g, 74.8 mmol), palladium acetate (0.4 g, 1.9 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (1.8 g, 3.7 mmol) and 1,4-dioxane (100.0 mL) were added to a dry 250 mL round-bottom flask in sequence. Under N2 protection, a reaction was conducted overnight at 100° C. After the reaction was completed, the reaction system was filtered through Celite, and a filtrate was concentrated under reduced pressure to obtain Intermediate 4, which was directly used for the next step.
Intermediate 4, 2-bromopyridine (5.9 g, 37.4 mmol), potassium carbonate (10.3 g, 74.8 mmol), [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (1.4 g, 1.9 mmol) and a mixed solvent of 1,4-dioxane/water (90 mL/30 mL) were added to a dry 250 mL round-bottom flask in sequence. Under N2 protection, a reaction was conducted overnight at 100° C. After the reaction was completed, the reaction solution was extracted with dichloromethane and purified through column chromatography to obtain a white solid Intermediate 5 (8.8 g, 28.4 mmol, with a yield of 76% (two steps)).
Intermediate 5 (7.0 g, 22.5 mmol), ethyl acetate (70 mL), ammonium formate (7.1 g, 112.9 mmol) and Pd/C (10%, 1.2 g) were added to a dry 250 mL round-bottom flask in sequence. Under N2 protection, a reaction was conducted overnight at room temperature. After the reaction was completed, the reaction system was filtered through Celite, and a filtrate was concentrated under reduced pressure and purified through column chromatography to obtain a white solid Intermediate 6 (2.4 g, 7.6 mmol, with a yield of 34%).
Intermediate 6 (2.4 g, 7.6 mmol) and tetrahydrofuran (30 mL) were added to a dry 250 mL three-necked round-bottom flask. Under N2 protection, the reaction system was cooled to −70° C. A tetrahydrofuran solution (6 mL) with 2.0 M di-isopropylamino lithium was slowly added dropwise to the reaction system, and a reaction was conducted for 1.5 h at −70° C. N-Fluorobenzenesulfonimide (4.8 g, 15.3 mmol) was added, and a reaction was conducted at room temperature until the reaction was completed. The reaction solution was quenched with a small amount of water, concentrated under reduced pressure and purified through column chromatography to obtain a white solid Intermediate 7 (2.2 g, 6.6 mmol, with a yield of 87%).
Intermediate 7 (2.2 g, 6.6 mmol), deuterated carbazole (1.4 g, 8.0 mmol), potassium t-butoxide (1.0 g, 9.3 mmol) and DMF (30 mL) were added to a dry 100 mL round-bottom flask in sequence. Under N2 protection, a reaction was conducted overnight at 100° C. After the reaction was completed, the reaction solution was concentrated under reduced pressure and purified through column chromatography to obtain a white solid Intermediate 8 (2.3 g, 4.7 mmol, with a yield of 72%).
Intermediate 9 (1.1 g, 1.2 mmol), Intermediate 8 (0.7 g, 1.5 mmol), 2-ethoxyethanol (20 mL) and DMF (20 mL) were added to a dry 250 mL round-bottom flask in sequence and heated to react for 5 days at 100° C. under N2 protection. After the reaction was cooled, the reaction solution was concentrated under reduced pressure and purified through column chromatography to obtain a yellow solid Metal Complex 5343 (0.63 g, 0.52 mmol, with a yield of 43%). The product was confirmed as the target product with a molecular weight of 1209.6.
Intermediate 10 (2.0 g, 2.4 mmol), Intermediate 8 (1.4 g, 2.9 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL) were added to a dry 250 mL round-bottom flask in sequence and heated to react for 5 days at 100° C. under N2 protection. After the reaction was cooled, the reaction solution was concentrated under reduced pressure and purified through column chromatography to obtain a yellow solid Metal Complex 3525 (1.2 g, 1.09 mmol, with a yield of 46%). The product was confirmed as the target product with a molecular weight of 1097.4.
A tetrahydrofuran solution (9 mL) with 1.3 M cyclohexylmagnesium chloride was added to a dry 100 mL three-necked round-bottom flask. Under N2 protection, a tetrahydrofuran solution (3 mL) with 2.0 M zinc chloride was added to the system in an ice bath. After a reaction was conducted for 1 h, Intermediate 1 (2.0 g, 6.5 mmol), palladium acetate (0.07 g, 0.3 mmol) and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.27 g, 0.6 mmol) were added to the system, and a reaction was conducted overnight at room temperature. After the reaction was completed, the reaction solution was extracted with ethyl acetate and purified through column chromatography to obtain a white solid Intermediate 11 (1.3 g, 4.2 mmol, with a yield of 65%).
Intermediate 11 (1.3 g, 4.2 mmol), bis(pinacolato)diboron (1.2 g, 4.6 mmol), potassium acetate (0.8 g, 8.4 mmol), palladium acetate (0.05 g, 0.2 mmol), 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (0.2 g, 0.4 mmol) and 1,4-dioxane (30.0 mL) were added to a dry 100 mL round-bottom flask in sequence. Under nitrogen protection, a reaction was conducted overnight at 100° C. After the reaction was completed, the reaction system was filtered through Celite, and a filtrate was concentrated under reduced pressure to obtain Intermediate 12, which was directly used for the next step.
Intermediate 12, 2-bromopyridine (0.7 g, 4.2 mmol), potassium carbonate (1.2 g, 8.4 mmol), [1,1′-bis(diphenylphosphino)ferrocene]palladium(II) dichloride (0.15 g, 0.2 mmol) and a mixed solvent of 1,4-dioxane/water (30 mL/10 mL) were added to a dry 100 mL round-bottom flask in sequence. Under nitrogen protection, a reaction was conducted overnight at 100° C. After the reaction was completed, the reaction solution was extracted with dichloromethane and purified through column chromatography to obtain a white solid Intermediate 13 (1.0 g, 2.8 mmol, with a yield of 67% (two steps)).
Intermediate 13 (1.0 g, 2.8 mmol) and tetrahydrofuran (30 mL) were added to a dry 100 mL three-necked round-bottom flask. Under nitrogen protection, the reaction system was cooled to −70° C. A tetrahydrofuran solution (2 mL) with 2.0 M di-isopropylamino lithium was slowly added dropwise to the reaction system, and a reaction was conducted for 1.5 h at −70° C. A tetrahydrofuran solution (1 mL) with 2.0 M zinc chloride was added, the reaction system was warmed to room temperature, and the reaction was continuously conducted for 0.5 h. Deuterated iodobenzene (1.2 g, 5.7 mmol), palladium acetate (0.03 g, 0.14 mmol) and 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (0.12 g, 0.28 mmol) were added, and a reaction was conducted overnight at room temperature. After the reaction was completed, the reaction solution was quenched with a small amount of water, concentrated under reduced pressure and purified through column chromatography to obtain a white solid Intermediate 7 (0.7 g, 1.6 mmol, with a yield of 58%).
Intermediate 9 (1.0 g, 1.1 mmol), Intermediate 14 (0.6 g, 1.4 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL) were added to a dry 250 mL round-bottom flask in sequence and heated to react for 5 days at 100° C. under N2 protection. After the reaction was cooled, the reaction solution was concentrated under reduced pressure and purified through column chromatography to obtain a yellow solid Metal Complex 5291 (0.6 g, 0.52 mmol, with a yield of 48%). The product was confirmed as the target product with a molecular weight of 1157.6.
Those skilled in the art will appreciate that the above preparation methods are merely exemplary. Those skilled in the art can obtain other compound structures of the present disclosure through the modifications of the preparation methods.
A glass substrate having an indium tin oxide (ITO) anode with a thickness of 80 nm (with a sheet resistance of 14 to −20 Ω/sq and an emissive area of 0.04 cm2) was cleaned and treated with oxygen plasma and UV ozone. After the treatment, the substrate was dried in a glovebox to remove moisture. Then, the substrate was mounted on a substrate holder and placed in a vacuum chamber. The organic layers specified below were sequentially deposited through vacuum thermal evaporation on the ITO anode at a rate of 0.2 to 2 Angstroms per second and a vacuum degree of about 108 Torr. Compound HT and Compound PD were used as a hole injection layer (HIL). Compound HT was used as a hole transporting layer (HTL). Compound PH-23 was used as an electron blocking layer (EBL). Metal Complex 5343 of the present disclosure was doped in Compound PH-23 and Compound H-40, all of which were co-deposited for use as an emissive layer (EML). On the EML, Compound HB was used as a hole blocking layer (HBL). On the HBL, Compound ET and 8-hydroxyquinolinolato-lithium (Liq) were co-deposited for use as an electron transporting layer (ETL). Finally, 8-hydroxyquinolinolato-lithium (Liq) was deposited for use as an electron injection layer with a thickness of 1 nm and Al was deposited for use as a cathode with a thickness of 120 nm. The device was transferred back to the glovebox and encapsulated with a glass lid and a moisture getter to complete the device.
The implementation mode in Device Example 2 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 5343 of the present disclosure was replaced with Metal Complex 3525.
The implementation mode in Device Example 3 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 5343 of the present disclosure was replaced with Metal Complex 5291.
The implementation mode in Device Comparative Example 1 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 5343 of the present disclosure was replaced with Compound GD1.
The implementation mode in Device Comparative Example 2 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 5343 of the present disclosure was replaced with Compound GD2.
The implementation mode in Device Comparative Example 3 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 5343 of the present disclosure was replaced with Compound GD3.
The implementation mode in Device Comparative Example 4 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 5343 of the present disclosure was replaced with Compound GD4.
Detailed structures and thicknesses of layers of the devices are shown in the following table. A layer using more than one material is obtained by doping different compounds at their weight ratio as recorded.
The materials used in the devices have the following structures:
The IVL characteristics of the devices were measured. The CIE data, maximum emission wavelengths (λmax) and full width at half maxima (FWHM) of the devices were measured at 15 mA/cm2. Capacitance testing was performed on the devices by using an impedance analyzer (Keysight E4990A). A direct current bias voltage of −4 V to 5 V was applied to the electrodes at two ends of the device, and a sinusoidal alternating current voltage signal of 100 mV was superimposed at the same time. The testing was performed at alternating current voltages with a frequency of 500 Hz, separately. The C-V curves of the devices were measured, and the maximum capacitances (Cmax) of the devices were obtained. The data was recorded and shown in Table 2.
Compared with Comparative Example 1, Example 1 has the same ligand Lb. The only difference between Example 1 and Comparative Example 1 is that substituents Rn in ligands La are isopropyl whose number of carbon atoms is greater than 2 and deuterated methyl, respectively. As can be seen from the data in Table 2, at 15 mA/cm2, the full width at half maximum in Example 1 is 7.8 nm narrower than that in Comparative Example 1, and at a frequency of 500 Hz, the maximum capacitance Cmax is 0.69 nF lower.
Compared with Comparative Example 2, Example 2 has the same ligand Lb. The only difference between Example 2 and Comparative Example 2 is that substituents Rn in ligands La are isopropyl whose number of carbon atoms is greater than 2 and hydrogen, respectively. As can be seen from the data in Table 2, at 15 mA/cm2, the full width at half maximum in Example 2 is 4.5 nm narrower than that in Comparative Example 2, and at a frequency of 500 Hz, the maximum capacitance Cmax is 0.54 nF lower.
Compared with Comparative Example 3, Example 2 has the same ligand Lb. The differences between Example 2 and Comparative Example 3 are that substituents Rn in ligands La are isopropyl whose number of carbon atoms is greater than 2 and hydrogen, respectively, and substituents Ar in the ligands La are a deuterated carbazole substituent and deuterium, respectively. When neither Rn nor Ar in Comparative Example 3 meets the limitation in the present application, at 15 mA/cm2, the full width at half maximum in Example 2 is 17.2 nm narrower than that in Comparative Example 3, and at a frequency of 500 Hz, the maximum capacitance Cmax is 0.46 nF lower.
Compared with Comparative Example 4, Example 3 has the same ligand Lb. The only difference between Example 3 and Comparative Example 4 is that substituents Rn in ligands La are cyclohexyl whose number of carbon atoms is greater than 2 and deuterated methyl, respectively. At 15 mA/cm2, the full width at half maximum in Example 3 is 10.5 nm narrower than that in Comparative Example 4, and at a frequency of 500 Hz, the maximum capacitance Cmax is 0.46 nF lower.
The above data indicates that the metal complex comprising the ligand La having the particular substituents Rn and Ar can obtain a narrower full width at half maximum and a lower maximum capacitance compared with the comparative examples without the characteristics in the present disclosure. The organic electroluminescent device can improve the response time and refresh rate of an OLED display device at a low grayscale and can maintain excellent device performance.
It should be understood that various embodiments described herein are merely examples and not intended to limit the scope of the present disclosure. Therefore, it is apparent to the persons skilled in the art that the present disclosure as claimed may include variations of specific embodiments and preferred embodiments described herein. Many of materials and structures described herein may be substituted with other materials and structures 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 limitative.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202310784339.4 | Jun 2023 | CN | national |
