Patent Application
20230309375
This application claims priority to Chinese Patent Application No. 202210287785.X filed on Mar. 25, 2022, 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 electroluminescent devices. More particularly, the present disclosure relates to a metal complex comprising a ligand La having a structure of Formula 1 and an organic electroluminescent device and 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.
US20210054010A1 discloses a metal complex comprising a ligand structure represented by
wherein the ring D is selected from a 5- or 6-membered carbocyclic ring or heterocyclic ring and at least one RD is a carbocyclic ring or a heterocyclic group, and further discloses an iridium complex having the following structure
However, this application has neither disclosed nor taught metal complexes comprising ligands having specific fused polycyclic substituents and the effects of such metal complexes on device performance.
US20200251666A1 discloses a metal complex comprising a ligand structure represented by
wherein at least one of X1 to X8 is selected from C—CN, and further discloses that the metal complex has the following structure
Such a metal complex is applied in organic electroluminescent devices, can improve device performance and color saturation and has reached a high level in the industry, but there is still room for improvement. This application has neither disclosed nor taught metal complexes comprising ligands having specific fused polycyclic substituents and the effects of such metal complexes on device performance.
US20200091442A1 discloses a metal complex comprising a ligand structure represented by
and further discloses that the metal complex has the following structure
This application discloses that fluorine at a particular position of the ligand can improve device performance comprising a device lifetime and thermal stability. Although such a metal complex has reached a high level in the industry, there is still room for improvement. This application has neither disclosed nor taught metal complexes comprising ligands having specific fused polycyclic substituents and the effects of such metal complexes 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. These metal complexes can be used as light-emitting materials in electroluminescent devices. These new metal complexes are applied in organic electroluminescent devices, are capable of providing better device performance such as improved device efficiency and an improved device lifetime, especially a greatly improved device lifetime, and can significantly improve the overall device performance.
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 described in the preceding embodiments.
According to another embodiment of the present disclosure, further disclosed is a compound composition comprising the metal complex described in the preceding embodiments.
The present disclosure discloses a series of metal complexes each comprising a ligand La having a structure of Formula 1, wherein the ligand La comprises a fused polycyclic structure fused by rings A, B and C, and the fused polycyclic structure is specifically joined to any one of X1 to X8 in Formula 1 by a Y group in the ring B. These novel metal complexes can be used as light-emitting materials in organic electroluminescent devices, when applied in organic electroluminescent devices, are capable of providing excellent device performance such as improved device efficiency and an improved device lifetime, especially a greatly improved device lifetime, and can significantly improve the overall device performance.
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.
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 (ΔES-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 ΔES-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, an 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 or heterocycle—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, phenyldiethylgermanyl, diphenylethylgermanyl, phenyldimethylgermanyl, 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, alkylgermanyl, arylgermanyl, 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 substitutions refer 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, fused cyclic, 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, the expression that “adjacent substituents RA, RB, RC, RY 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, two substituents RC, substituents RA and RB, substituents RA and RC, substituents RB and RC, substituents RA and RY, substituents RY and RC, and substituents RY and RB, 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 ring formed by optionally joining the substituents may be a carbocyclic ring or a heterocyclic ring, and the heterocyclic ring may comprise one or more heteroatoms of O, S, N, Se, P, Si, Ge or B. The carbocyclic ring or heterocyclic ring may be aromatic or non-aromatic. For example, when any one or more of these groups of adjacent substituents, such as two substituents RA, two substituents RB, two substituents RC, substituents RA and RB, substituents RA and RC, and substituents RB and RC, are joined to form a ring, the formed ring may be a carbocyclic ring or a heterocyclic ring comprising one or more heteroatoms of O, S, N, Se, P, Si, Ge or B.
In the present disclosure, the expression that “adjacent substituents R′, Rx 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 R′, two substituents Rx, and substituents Rx 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 group represented by
represents a fused polycyclic structure having at least three rings, wherein the ring A is fused with the ring B, the ring B is fused with the ring C, and the fused polycyclic structure is joined to any one of X1 to X8 in Formula 1 by Y in the ring B. For example, when the ring A, the ring B and the ring C are all selected from a benzene ring, the fused polycyclic structure may form a group having the following structure:
Obviously, in some cases, the ring A and the ring C in the fused polycyclic structure can also be fused with each other.
According to an embodiment of the present disclosure, Cy is any structure selected from the group consisting of:
In the present disclosure, the expression that “adjacent substituents R can be optionally joined to form a ring” is intended to mean that any one or more of groups of any two adjacent substituents R 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, La is, at each occurrence identically or differently, selected from the group consisting of:
In the present disclosure, the expression that “adjacent substituents R′, R, Rx 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 R′, two substituents R, two substituents Rx, and substituents R and Rx, 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 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.
According to an embodiment of the present disclosure, the metal complex has a general structure of Ir(La)m(Lb)3-m which is represented by Formula 2:
In the present disclosure, the expression that “adjacent substituents R1 to R8 can be optionally joined to form a ring” is intended to mean that any one or more groups of the group consisting of any two adjacent substituents of R1 to R8 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 R′, Rx, Ry 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 R′, two substituents Rx, and two substituents Ry, 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 metal complex has a general structure of Ir(La)m(Lb)3-m which is represented by Formula 2a:
In the present disclosure, the expression that “adjacent substituents Rx, Ry 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 Rx and two substituents Ry, 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, X is selected from O or S.
According to an embodiment of the present disclosure, X is selected from O.
According to an embodiment of the present disclosure, Y is selected from C.
According to an embodiment of the present disclosure, X3 to X8 are, at each occurrence identically or differently, selected from C or CRx, and one of X3 to X8 is selected from C and joined to Y; the substituent 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 arylalkyl having 7 to 30 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 arylsilyl having 6 to 20 carbon atoms, a cyano group, and combinations thereof.
According to an embodiment of the present disclosure, X3 to X8 are, at each occurrence identically or differently, selected from C or CRx, and one of X3 to X8 is selected from C and joined to Y; at least one of the substituent Rx 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, a cyano group, and combinations thereof.
According to an embodiment of the present disclosure, at least one of X3 to X8 is N. For example, one of X3 to X8 is selected from N, or two of X3 to X8 are selected from N.
According to an embodiment of the present disclosure, at least one of X1 to X8 is N. For example, one of X1 to X8 is selected from N, or two of X1 to X8 are selected from N.
According to an embodiment of the present disclosure, at least one of Y1 to Y4 is N. For example, one of Y1 to Y4 is selected from N, or two of Y1 to Y4 are selected from N.
According to an embodiment of the present disclosure,
has the following general structure:
wherein Z1 is selected from CRB or N, Z2 to Z5 are, at each occurrence identically or differently, selected from CRA or N, and Z6 to Z9 are, at each occurrence identically or differently, selected from CRC or N.
According to an embodiment of the present disclosure, at least one of Z1 to Z9 is selected from N. For example, one of Z1 to Z9 is selected from N, or two of Z1 to Z9 are selected from N.
According to an embodiment of the present disclosure, at least one of Z1 to Z9 is selected from N, for example, Z1 is selected from N, or one of Z2 to Z5 is selected from N, or one of Z6 to Z9 is selected from N.
According to an embodiment of the present disclosure, the ring A, the ring B and the ring C are, at each occurrence identically or differently, selected from a carbocyclic ring having a monocyclic or polycyclic structure and having 5 to 10 ring atoms, a heterocyclic ring having a monocyclic or polycyclic structure and having 5 to 10 ring atoms or a combination thereof.
According to an embodiment of the present disclosure, the ring A, the ring B and the ring C are, at each occurrence identically or differently, selected from an aromatic ring having 5 to 10 ring atoms, a heteroaromatic ring having 5 to 10 ring atoms or a combination thereof.
According to an embodiment of the present disclosure, the ring A, the ring B and the ring C are, at each occurrence identically or differently, selected from an aromatic ring having a monocyclic or polycyclic structure and having 5 to 10 ring atoms, a heteroaromatic ring having a monocyclic or polycyclic structure and having 5 to 10 ring atoms or a combination thereof.
According to an embodiment of the present disclosure, the ring A, the ring B and the ring C are, at each occurrence identically or differently, selected from a carbocyclic ring having 5 to 6 ring atoms, a heterocyclic ring having 5 to 6 ring atoms or a combination thereof.
According to an embodiment of the present disclosure, the ring A, the ring B and the ring C are, at each occurrence identically or differently, selected from a benzene ring, a heterocyclic ring having 5 to 6 ring atoms or a combination thereof.
According to an embodiment of the present disclosure, the ring A, the ring B and the ring C are, at each occurrence identically or differently, selected from a benzene ring, a pyridine ring, a pyrimidine ring, a thiophene ring or a furan ring.
According to an embodiment of the present disclosure, the ring A, the ring B and the ring C are, at each occurrence identically or differently, selected from a benzene ring.
According to an embodiment of the present disclosure, at least one of X3 to X8 is selected from C and joined to Y.
According to an embodiment of the present disclosure, at least one of X5 to X8 is selected from C and joined to Y.
According to an embodiment of the present disclosure, at least one of X7 or X8 is selected from C and joined to Y.
According to an embodiment of the present disclosure, at least one of X3 to X8 is selected from CRx, and the Rx is selected from cyano or fluorine.
According to an embodiment of the present disclosure, at least one of X5 to X8 is CRx, and the Rx is selected from cyano or fluorine.
According to an embodiment of the present disclosure, at least one of X7 or X8 is selected from CRx, and the Rx is selected from cyano or fluorine.
According to an embodiment of the present disclosure, at least one of X3 to X8 is CRx, and the Rx is selected from cyano or fluorine; at least one of X3 to X8 is selected from C and joined to Y.
According to an embodiment of the present disclosure, at least one of X5 to X8 is CRx, and the Rx is selected from cyano or fluorine; at least one of X5 to X8 is selected from C and joined to Y.
According to an embodiment of the present disclosure, one of X7 and X8 is selected from CRx, and the Rx is selected from cyano or fluorine; the other one is selected from C and joined to Y.
According to an embodiment of the present disclosure, X7 is selected from CRx, and the Rx is selected from cyano or fluorine; X8 is selected from C and joined to Y.
According to an embodiment of the present disclosure, the substituents RA, RB and RC 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 arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 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 arylsilyl having 6 to 20 carbon atoms, a cyano group, and combinations thereof.
According to an embodiment of the present disclosure, the substituents RA, RB and RC 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 alkenyl having 2 to 20 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, the substituents RA, RB and RC are, at each occurrence identically or differently, selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted alkenyl having 2 to 6 carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, and combinations thereof.
According to an embodiment of the present disclosure, the substituents RA, RB and RC are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, methyl, ethyl, propyl, butyl, pentyl, cyclohexyl, cyclopentyl, phenyl, pyridyl, pyrimidinyl, and combinations thereof; hydrogens in the above substituents can be partially or fully deuterated.
According to an embodiment of the present disclosure,
is selected from the group consisting of the following groups:
According to an embodiment of the present disclosure, Y1 to Y4 are, at each occurrence identically or differently, selected from CRy, and the substituent 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 arylalkyl having 7 to 30 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 arylsilyl having 6 to 20 carbon atoms, and combinations thereof.
According to an embodiment of the present disclosure, Y1 to Y4 are, at each occurrence identically or differently, selected from CRy, and at least one of the substituent 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, the substituents R1 to R8 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 heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 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 arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanyl having 6 to 20 carbon atoms, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, and combinations thereof.
According to an embodiment of the present disclosure, the substituents R1 to R8 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 alkenyl having 2 to 20 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, an isocyano group, a hydroxyl group, a sulfanyl group, and combinations thereof.
According to an embodiment of the present disclosure, the substituents R1 to R8 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, 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 18 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 18 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 15 carbon atoms, and combinations thereof.
According to an embodiment of the present disclosure, at least one or at least two of the substituents R1 to R8 are 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 substituents R1 to R4 and/or the substituents R5 to R8 is at least 4.
According to an embodiment of the present disclosure, at least one or at least two of the substituents R1 to R4 are 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 substituents R1 to R4 is at least 4.
According to an embodiment of the present disclosure, at least one or at least two of the substituents R5 to R8 are 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 substituents R5 to R8 is at least 4.
According to an embodiment of the present disclosure, at least one, at least two, at least three or all of the substituents R2, R3, R6 and R7 are selected from the group consisting of: 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, and combinations thereof.
According to an embodiment of the present disclosure, at least one, at least two, at least three or all of the substituents R2, R3, R6 and R7 are selected from the group consisting of: deuterium, 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, at least one, at least two, at least three or all of the substituents R2, R3, R6 and R7 are selected from the group consisting of: deuterium, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, neopentyl, t-pentyl, and combinations thereof; optionally, hydrogens in the above groups can be partially or fully deuterated.
According to an embodiment of the present disclosure, the substituents RY to R′ 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 arylalkyl having 7 to 30 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 arylsilyl having 6 to 20 carbon atoms, a cyano group, and combinations thereof.
According to an embodiment of the present disclosure, the substituents RY to R′ 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, and combinations thereof.
According to an embodiment of the present disclosure, the substituents RY to R′ are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, 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, and combinations thereof.
According to an embodiment of the present disclosure, the substituents RY to Ry are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, methyl, ethyl, propyl, butyl, pentyl, cyclohexyl, cyclopentyl, phenyl, pyridyl, pyrimidinyl, and combinations thereof; hydrogens in the above substituents can be partially or fully deuterated.
According to an embodiment of the present disclosure, R is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms or substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms.
According to an embodiment of the present disclosure, wherein R is methyl or deuterated methyl.
According to an embodiment of the present disclosure, the ligand La is, at each occurrence identically or differently, selected from the group consisting of La1 to La258, wherein the specific structures of La1 to La258 are referred to claim 15.
According to an embodiment of the present disclosure, hydrogens in La1 to La258 can be partially or fully deuterated.
According to an embodiment of the present disclosure, the ligand Lb is, at each occurrence identically or differently, selected from the group consisting of Lb1 to Lb334, wherein the specific structures of Lb1 to Lb334 are referred to claim 16.
According to an embodiment of the present disclosure, hydrogens in Lb1 to Lb334 can be partially or fully deuterated.
According to an embodiment of the present disclosure, the ligand Lc is, at each occurrence identically or differently, selected from the group consisting of Lc1 to Lc50, wherein the specific structures of Lc1 to Lc50 are referred to claim 17.
According to an embodiment of the present disclosure, the metal complex has a structure of Ir(La)3, IrLa(Lb)2, Ir(La)2Lb, Ir(La)2Lc, IrLa(Lc)2 or IrLaLbLc, wherein the ligand La is, at each occurrence identically or differently, selected from any one, any two or any three of the group consisting of La1 to La258, the ligand Lb is, at each occurrence identically or differently, selected from any one or any two of the group consisting of Lb1 to Lb334, and the ligand Lc is, at each occurrence identically or differently, selected from any one or any two of the group consisting of Lc1 to Lc50.
According to an embodiment of the present disclosure, the metal complex has a structure of IrLa(Lb)2, wherein the two La are the same or different, the ligand La is, at each occurrence identically or differently, selected from any one of the group consisting of La1 to La258, and the ligand Lb is, at each occurrence identically or differently, selected from any one or any two of the group consisting of Lb1 to Lb334.
According to an embodiment of the present disclosure, the metal complex is selected from the group consisting of Metal Complex 1 to Metal Complex 495, wherein the specific structures of Metal Complex 1 to Metal Complex 495 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 described in any one of the preceding embodiments.
According to an embodiment of the present disclosure, the organic layer comprising the metal complex is an emissive layer.
According to an embodiment of the present disclosure, the organic electroluminescent device emits green light.
According to an embodiment of the present disclosure, the organic electroluminescent device emits yellow light.
According to an embodiment of the present disclosure, the emissive layer comprises a first host compound.
According to an embodiment of the present disclosure, the emissive layer further comprises a second host compound.
According to an embodiment of the present disclosure, at least one of the first host compound and the second host compound comprises 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 3:
In the present disclosure, the expression that “adjacent substituents Re, R″, 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 substituents Re, substituents R″, two substituents Rq, and substituents R″ 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 first host compound has a structure represented by Formula 3a or Formula 3b:
In the present disclosure, the expression that “adjacent substituents R″, 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 R″, two substituents Rq, and substituents R″ 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 has a structure represented by Formula 5 or Formula 6:
In the present disclosure, the expression that “adjacent substituents Rt can be optionally joined to form a ring” is intended to mean that one or more groups of the group consisting ofany two adjacent substituents 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 Rt, Rg 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 Rt, two substituents Rg, and substituents Rt and Rg, 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 metal complex is doped in the first host compound and the second host compound, and the weight of the metal complex accounts for 1% to 30% of the total weight of the emissive 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 emissive layer.
According to an embodiment of the present disclosure, disclosed is a compound composition comprising the metal complex described 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. App. 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. App. 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 spectrometry 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.
The method for preparing the compound in the present disclosure is not limited herein. Typically, the following compounds are used as examples without limitation, and synthesis routes and preparation methods thereof are described below.
Step 1:
5-t-butyl-2-phenylpyridine (10.0 g, 59.2 mmol), iridium trichloride trihydrate (5.0 g, 14.2 mmol), 300 mL of 2-ethoxyethanol and 100 mL of water were sequentially added to a dry 500 mL round-bottom flask, purged with nitrogen three times, and heated and stirred at 130° C. for 24 h under nitrogen protection. After the reaction was cooled, the reaction solution was filtered. The upper solid was washed three times with methanol and n-hexane respectively and suctioned under reduced pressure to give 7.5 g of Intermediate 1 as a yellow solid (with a yield of 97%).
Step 2:
Intermediate 1 (7.5 g, 6.8 mmol), silver trifluoromethanesulfonate (3.8 g, 14.8 mmol), 250 mL of anhydrous dichloromethane and 10 mL of methanol were sequentially added to a dry 500 mL round-bottom flask, purged with nitrogen three times, and stirred overnight at room temperature under nitrogen protection. The reaction product was filtered through Celite and washed twice with dichloromethane. The organic phase below was collected and concentrated under reduced pressure to give 9.2 g of Intermediate 2 (with a yield of 93%).
Step 3:
Intermediate 2 (2.2 g, 2.7 mmol), Intermediate 3 (1.7 g, 3.8 mmol), 50 mL of 2-ethoxyethanol and 50 mL of N,N-dimethylformamide (DMF) were sequentially added to a dry 250 mL round-bottom flask, purged with nitrogen three times, and heated at 100° C. for 72 h under nitrogen protection. After the reaction was cooled, the reaction solution was filtered through Celite. The upper solid was washed twice with methanol and n-hexane respectively to give a yellow solid. The solid was dissolved with dichloromethane. The organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give the product Metal Complex 216 as a yellow solid (0.8 g, with a yield of 30.0%). The product was confirmed as the target product with a molecular weight of 1058.4.
Step 1:
Intermediate 2 (2.2 g, 2.7 mmol), Intermediate 4 (1.8 g, 3.9 mmol), 50 mL of 2-ethoxyethanol and 50 mL of DMF were sequentially added to a dry 250 mL round-bottom flask, purged with nitrogen three times, and heated at 100° C. for 96 h under nitrogen protection. After the reaction was cooled, the reaction solution was filtered through Celite. The upper solid was washed twice with methanol and n-hexane respectively to give a yellow solid. The solid was dissolved with dichloromethane. The organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give the product Metal Complex 226 as a yellow solid (0.88 g, with a yield of 30.7%). The product was confirmed as the target product with a molecular weight of 1059.4.
Step 1:
Intermediate 2 (1.7 g, 2.0 mmol), Intermediate 5 (0.9 g, 2.1 mmol), 30 mL of 2-ethoxyethanol and 30 mL of DMF were sequentially added to a dry 250 mL round-bottom flask, purged with nitrogen three times, and heated at 100° C. for 96 h under nitrogen protection. After the reaction was cooled, the reaction solution was filtered through Celite. The upper solid was washed twice with methanol and n-hexane respectively to give a yellow solid. The solid was dissolved with dichloromethane. The organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give the product Metal Complex 246 as a yellow solid (0.35 g, with a yield of 16.7%). The product was confirmed as the target product with a molecular weight of 1046.4.
Step 1:
Intermediate 2 (1.5 g, 1.8 mmol), Intermediate 6 (1.2 g, 2.7 mmol), 50 mL of 2-ethoxyethanol and 50 mL of DMF were sequentially added to a dry 250 mL round-bottom flask, purged with nitrogen three times, and heated at 100° C. for 96 h under nitrogen protection. After the reaction was cooled, the reaction solution was filtered through Celite. The upper solid was washed twice with methanol and n-hexane respectively to give a yellow solid. The solid was dissolved with dichloromethane. The organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give the product Metal Complex 255 as a yellow solid (0.88 g, with a yield of 61.2%). The product was confirmed as the target product with a molecular weight of 1052.4.
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.
First, a glass substrate having an indium tin oxide (ITO) anode with a thickness of 80 nm was cleaned and then 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. 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 at a vacuum degree of about 10−8 torr. Compound HI was used as a hole injection layer (HIL). Compound HT was used as a hole transport layer (HTL). Compound H1 was used as an electron blocking layer (EBL). Metal complexes 216 of the present disclosure, as dopant, was co-deposited with compounds H1 and H2 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 as an electron transport layer (ETL). Finally, 8-hydroxyquinolinolato-lithium (Liq) with a thickness of 1 nm was deposited as an electron injection layer (EIL), and Al with a thickness of 1200 nm was deposited as a cathode. The device was transferred back to the glovebox and encapsulated with a glass lid to complete the device.
The implementation in Device Example 2 was the same as that in Device Example 1, except that in the EML, Metal Complex 216 of the present disclosure was replaced with Metal Complex 226 of the present disclosure.
The implementation in Device Comparative Example 1 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 216 of the present disclosure was replaced with Compound GD1.
The implementation in Device Comparative Example 2 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 216 of the present disclosure was replaced with Compound GD2.
The implementation in Device Comparative Example 3 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 216 of the present disclosure was replaced with Compound GD3.
Detailed structures and thicknesses of layers of the devices are shown in Table 1. A layer using more than one material is obtained by doping different compounds at their weight ratios as recorded.
The materials used in the devices have the following structures:
IVL characteristics of the devices were measured. The CIE data, maximum emission wavelength λmax, full width at half maximum (FWHM) and voltage (V) of the devices were measured at 1000 cd/m2; the external quantum efficiency (EQE) data was tested at a constant current of 15 mA/cm2; the lifetime (LT97) data was tested at a constant current of 80 mA/cm2; the voltage, external quantum efficiency and lifetime were normalized based on the device results of Comparative Example 1, and these data were recorded and presented in Table 2.
Discussion:
Table 2 shows the device properties of Examples and Comparative Examples. As can be seen from the comparison between Example 1 and Comparative Example 1, the difference was only that the fused polycyclic substituent on the ligand La of the metal complex was different and the fused ring substituent of Comparative Example 1 had only two rings fused. As can be seen from the above device results, compared with Comparative Example 1, the drive voltage of Example 1 was reduced by 3%, the full width at half maximum was narrowed by 0.6 nm, the EQE was increased by 5%, and especially the device lifetime was increased by 120%. It can be seen that the overall performance of the device of Example 1 was significantly improved.
As can be seen from the comparison between Example 1 and Comparative Example 2, the difference was only that the substituent on the ligand La of the metal complex was different and Comparative Example 1 had only a phenyl substituent instead of a fused polycyclic substituent. As can be seen from the above device results, compared with Comparative Example 2, the drive voltage of Example 1 was equivalent to that of Comparative Example 2, the full width at half maximum was narrowed by 0.9 nm, the EQE was increased by 7%, and the device lifetime was increased by 10%. In the case that the performance of Comparative Example 2 had been relatively excellent, Example 1 could improve the color purity of the device and further significantly improve the overall performance of the device, which was even rarer.
As can be seen from the above results, the metal complex comprising the ligand La having a specific fused polycyclic substituent in the present application can improve the device performance in many aspects, especially the device lifetime, and can significantly improve the overall performance of the device, compared with the metal complex having no specific fused polycyclic substituent.
As can be seen from the comparison between Example 1 and Comparative Example 3, the difference was only that the substitution site of the fused polycyclic substituent on the ligand La of the metal complex was different. As can be seen from the above device results, compared with Comparative Example 3, the drive voltage and the EQE of Example 1 were equivalent to those of Comparative Example 3, and although the full width at half maximum was widened by 0.6 nm, the device lifetime was increased by 17.6%. It indicates that the metal complex comprising the ligand La having a specific specifically-linked fused ring substituent in the present application can significantly improve the device lifetime, compared with the metal complex having no specifically-linked fused ring substituent.
Furthermore, on the basis that the metal complex used in Example 1 could improve the device performance compared with the metal complex that was not provided by the present disclosure, Example 2 further optimized the metal complex. On the basis of the excellent device performance of Example 1, Example 2 further improved the device performance and especially further increased the device lifetime by 13.6%.
The above results indicate that the metal complex comprising the ligand La having a specific specifically-linked fused polycyclic substituent in the present application can improve the device performance in many aspects, especially the device lifetime, and can significantly improve the overall performance of the device, compared with the metal complex that is not provided by the present disclosure.
The implementation in Device Example 3 was the same as that in Device Example 1, except that in the emissive layer, Metal Complex 216 of the present disclosure was replaced with Metal Complex 255 of the present disclosure.
The implementation in Device Comparative Example 4 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 216 of the present disclosure was replaced with Compound GD4.
Detailed structures and thicknesses of layers of the devices are shown in Table 3. A layer using more than one material is obtained by doping different compounds at their weight ratios as recorded.
The new materials used in the devices have the following structures:
IVL characteristics of the devices were measured. The CIE data, maximum emission wavelength λmax, full width at half maximum (FWHM) and voltage (V) of the devices were measured at 1000 cd/m2; the external quantum efficiency (EQE) data was tested at a constant current of 15 mA/cm2; the lifetime (LT97) data was tested at a constant current of 80 mA/cm2; the voltage, external quantum efficiency and lifetime were normalized based on the device results of Comparative Example 4, and these data were recorded and presented in Table 4.
Discussion:
Table 4 shows the device properties of Example and Comparative Example. As can be seen from the comparison between Example 3 and Comparative Example 4, the difference was mainly that the fused polycyclic substituent on the ligand La of the metal complex was different and the fused ring substituent of Comparative Example 4 had only two rings fused. As can be seen from the above device results, compared with Comparative Example 4, the drive voltage of Example 3 was equivalent to that of Comparative Example 4, and although the full width at half maximum was widened by 0.7 nm, the EQE was increased by 3%, and especially the device lifetime was increased by 16%. It can be seen that the overall performance of the device of Example 3 was significantly improved.
The above results indicate that the metal complex comprising the ligand La having a specific specifically-linked fused ring substituent in the present application can improve the device performance in many aspects, especially the device lifetime, and can significantly improve the overall performance of the device, compared with the metal complex that is not provided by the present disclosure.
It is to 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 is to be understood that various theories as to why the present disclosure works are not intended to be limitative.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202210287785.X | Mar 2022 | CN | national |
