Patent Application
20240008356
This application claims priority to Chinese Patent Application No. 202210755442.1 filed on Jun. 30, 2022 and Chinese Patent Application No. 202310421323.7 filed on Apr. 19, 2023, the disclosure of which are incorporated herein by reference in their entireties.
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 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.
Phosphorescent metal complexes can be used as phosphorescent doping materials of light-emitting layers and applied to the field of organic electroluminescence lighting or display. To meet requirements in different cases, a color of a material can be adjusted on a certain basis by adjusting a structure type of a ligand of the material so that phosphorescent metal complexes with different emission wavelengths are obtained.
The previous patent application CN114437134A of the applicant of the present disclosure has disclosed a metal complex having a structure of
and discloses the compound
in a specific structure. This patent application does not disclose or teach an effect on device performance when a fused ring system formed by fusing rings is further introduced at a particular position of an isoquinoline ring or other fused heteroaromatic rings.
The currently developed metal complexes still have various deficiencies in performance when used in electroluminescent devices. To meet the increasing requirements of the industry such as higher current efficiency, higher power efficiency and a longer device lifetime, the research and development related to metal complexes still needs to be deepened.
The present disclosure aims to provide a series of new metal complexes to solve at least part of the above-mentioned problems. The metal complex comprises a metal M and a ligand La having a structure of Formula 1. When the metal complex is applied to an organic electroluminescent device as a light-emitting material, the metal complex, while maintaining a very narrow full width at half maximum, can effectively adjust a light emission wavelength to better meet a requirement of saturated red light emission and obtain higher device efficiency at a lower voltage, thereby providing better device performance.
According to an embodiment of the present disclosure, disclosed is a metal complex, which comprises a metal M and a ligand La coordinated to the metal M, wherein the metal M is selected from a metal with a relative atomic mass greater than 40, and the ligand La has a structure represented by Formula 1:
According to another embodiment of the present disclosure, disclosed is an electroluminescent device, which comprises an anode, a cathode and an organic layer disposed between the anode and the cathode, wherein 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, which comprises the metal complex in the preceding embodiment.
The present disclosure discloses a type of metal complex comprising the metal M and the ligand La having the structure of Formula 1. When this type of metal complex is used as the light-emitting material of the organic electroluminescent device, the device can have a very narrow full width at half maximum and saturated red light emission, and the current efficiency, power efficiency and external quantum efficiency of the device are improved at a low voltage, thereby significantly improving the overall performance of the device.
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, a 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 or heterocycle—as used herein include non-aromatic cyclic groups. Non-aromatic heterocyclic groups includes 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 group having 6 to 20 carbon atoms, unsubstituted alkylgermanyl having 3 to 20 carbon atoms, unsubstituted arylgermanyl 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 may 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, which comprises a metal M and a ligand La coordinated to the metal M, wherein the metal M is selected from a metal with a relative atomic mass greater than 40, and the ligand La has a structure represented by Formula 1:
In this embodiment, the expression that “adjacent substituents RA, RB, Rx and 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 adjacent substituents RA, adjacent substituents RB, adjacent substituents Rx, adjacent substituents Ry, adjacent substituents Rx and Ry, adjacent substituents Rx and RB, adjacent substituents Ry and RB, and adjacent substituents Ry and RA, can be joined to form a ring. Obviously, it is also possible that none of these groups of substituents are joined to form a ring.
In this embodiment, “the ring A and the ring B are each independently selected from a five-membered unsaturated carbocyclic ring, an aromatic ring having 6 to 30 carbon atoms or a heteroaromatic ring having 3 to 30 carbon atoms, and when the ring A is a monocyclic ring, the ring A is selected from a five-membered unsaturated carbocyclic ring, a benzene ring or a six-membered heteroaromatic ring”, wherein “an aromatic ring having 6 to 30 carbon atoms or a heteroaromatic ring having 3 to 30 carbon atoms” includes a plurality of cases such as a monocyclic ring, a polycyclic ring and a fusedcyclic ring, for example, both a benzene ring and a pyridine ring belong to the monocyclic ring, both biphenyl and bipyridine belong to the polycyclic ring, and both a naphthalene ring and a quinoline ring belong to the fusedcyclic ring.
According an embodiment of the present disclosure, in Formula 1, the ring A and the ring B are each independently selected from a five-membered unsaturated carbocyclic ring, an aromatic ring having 6 to 18 carbon atoms or a heteroaromatic ring having 3 to 18 carbon atoms, and when the ring A is a monocyclic ring, the ring A is selected from a five-membered unsaturated carbocyclic ring, a benzene ring or a six-membered heteroaromatic ring.
According an embodiment of the present disclosure, in Formula 1, the ring A or the ring B is each independently selected from a five-membered unsaturated carbocyclic ring, an aromatic ring having 6 to 18 carbon atoms or a heteroaromatic ring having 3 to 18 carbon atoms, and when the ring A is a monocyclic ring, the ring A is selected from a five-membered unsaturated carbocyclic ring, a benzene ring or a six-membered heteroaromatic ring.
According an embodiment of the present disclosure, in Formula 1, the ring A and the ring B are each independently selected from a five-membered unsaturated carbocyclic ring, an aromatic ring having 6 to 10 carbon atoms or a heteroaromatic ring having 3 to 10 carbon atoms, and when the ring A is a monocyclic ring, the ring A is selected from a five-membered unsaturated carbocyclic ring, a benzene ring or a six-membered heteroaromatic ring.
According an embodiment of the present disclosure, in Formula 1, the ring A or the ring B is each independently selected from a five-membered unsaturated carbocyclic ring, an aromatic ring having 6 to 10 carbon atoms or a heteroaromatic ring having 3 to 10 carbon atoms, and when the ring A is a monocyclic ring, the ring A is selected from a five-membered unsaturated carbocyclic ring, a benzene ring or a six-membered heteroaromatic ring.
According to an embodiment of the present disclosure, T1 to T4 are all selected from C.
According to an embodiment of the present disclosure, the ligand La is selected from a structure represented by any one of Formula 2 to Formula 40:
In the present disclosure, the expression that “adjacent substituents Rx, Ry, RA and Rz can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as adjacent substituents Rx, adjacent substituents Ry, adjacent substituents Rz, adjacent substituents RA, adjacent substituents RA and Ry, adjacent substituents Rx and Ry, adjacent substituents RA and Rz, and adjacent substituents Ry and Rz, can be joined to form a ring. Obviously, it is also possible that none of these groups of substituents are joined to form a ring.
According to an embodiment of the present disclosure, the ligand La is selected from a structure represented by Formula 2, Formula 3, Formula 20 or Formula 21.
According to an embodiment of the present disclosure, the ligand La is selected from a structure represented by Formula 20 or Formula 21.
According to an embodiment of the present disclosure, in Formula 2 to Formula 40, at least one of X1 to Xn and/or A1 to Am is selected from N, wherein the Xn corresponds to the one with the largest serial number among X1 to X9 in any one of Formula 2 to Formula 40, and the Am corresponds to the one with the largest serial number among A1 to A7 in any one of Formula 2 to Formula 40. For example, in Formula 2, the Xn corresponds to X9 whose serial number is the largest among X1 to X9 in Formula 2, and the Am corresponds to A3 whose serial number is the largest among A1 to A7 in Formula 2, that is, in Formula 2, at least one of X1, X2, X3, X5, X6, X7, X8 and X9 and/or A1 to A3 is selected from N.
According to an embodiment of the present disclosure, in Formula 2 to Formula 40, at least one of X1 to Xn is selected from N, wherein the Xn corresponds to the one with the largest serial number among X1 to X9 in any one of Formula 2 to Formula 40.
According to an embodiment of the present disclosure, in Formula 2 to Formula 40, X2 is N.
According to an embodiment of the present disclosure, in Formula 2 to Formula 40, X1 to X3 and X5 to X9 are each independently selected from CRx; A1 to A7 are each independently selected from CRA; and the Rx and RA 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, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon 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 alkynyl 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, substituted or 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, adjacent substituents Rx and RA can be optionally joined to form a ring.
In the present disclosure, the expression that “adjacent substituents Rx and RA can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as adjacent substituents Rx, and adjacent substituents RA, can be joined to form a ring. Obviously, it is also possible that none of these groups of substituents are joined to form a ring.
According to an embodiment of the present disclosure, in Formula 2 to Formula 40, X1 to X3 and X5 to X9 are each independently selected from CRx; A1 to A7 are each independently selected from CRA; and the Rx and RA 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, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, a cyano group and combinations thereof.
According to an embodiment of the present disclosure, in Formula 2 to Formula 40, X1 to X3 and X5 to X9 are each independently selected from CRx; A1 to A7 are each independently selected from CRA; at least one, two or three of the Rx and RA is(are), at each occurrence identically or differently, 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, 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.
In this embodiment, the expression that at least one, two or three of the Rx and RA is(are), at each occurrence identically or differently, selected from the group of consisting of these substituents is intended to mean that at least one, two or three substituents in the group consisting of all substituents Rx and all substituents RA is(are), at each occurrence identically or differently, selected from the group of consisting of these substituents.
According to an embodiment of the present disclosure, in Formula 2 to Formula 40, X1 to X3 and X5 to X9 are each independently selected from CRx; A1 to A7 are each independently selected from CRA; at least one, two or three of the Rx and/or at least one, two or three of the RA is(are), at each occurrence identically or differently, 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, 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, in Formula 2 to Formula 40, X1 and X2 are each independently selected from CRx; and the 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 heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon 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 alkynyl 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, substituted or 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.
According to an embodiment of the present disclosure, in Formula 2 to Formula 40, X1 and X2 are each independently selected from CRx; the 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 arylsilyl having 6 to 20 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, in Formula 2 to Formula 40, X1 is selected from CRx, X2 is N, and the 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 heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon 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 alkynyl 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, substituted or 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.
According to an embodiment of the present disclosure, in Formula 2 to Formula 40, X1 is selected from CRx, X2 is N, and the 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 arylsilyl having 6 to 20 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, in Formula 2 to Formula 13 and Formula 20 to Formula 33, X7 and/or X8 is selected from CRx; in Formula 14 to Formula 19 and Formula 34 to Formula 40, X6 and/or X7 is selected from CRx; and the Rx is, at each occurrence identically or differently, 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, a substituted or unsubstituted heterocyclic group having 3 to 20 ring 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 amino having 0 to 20 carbon atoms, a cyano group, a hydroxyl group, a sulfanyl group, a phosphino group and combinations thereof.
According to an embodiment of the present disclosure, in Formula 2 to Formula 13 and Formula 20 to Formula 33, X7 and/or X8 is selected from CRx; in Formula 14 to Formula 19 and Formula 34 to Formula 40, X6 and/or X7 is selected from CRx; and the Rx is, at each occurrence identically or differently, selected from the group consisting of: deuterium, fluorine, methyl, ethyl, isopropyl, isobutyl, t-butyl, neopentyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, tetrahydrofuranyl, tetrahydropyranyl, deuterated methyl, deuterated ethyl, deuterated isopropyl, deuterated isobutyl, deuterated t-butyl, deuterated neopentyl, deuterated cyclopentyl, deuterated cyclopentylmethyl, deuterated cyclohexyl, norbornyl, adamantyl, trimethylsilyl, isopropyldimethylsilyl, phenyldimethylsilyl, trifluoromethyl, a cyano group, phenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, pyridyl, triazinyl, thienyl, carbazolyl, a hydroxyl group, a sulfanyl group, a phosphino group and combinations thereof.
According to an embodiment of the present disclosure, in Formula 2 to Formula 5, Formula 14, Formula 15, Formula 24 to Formula 27 and Formula 38, at least one of A1 to A3 is selected from CRA, in Formula 6 to Formula 13 and Formula 16 to Formula 19, at least one of A1 to A4 is selected from CRA, in Formula 20 to Formula 23, Formula 32, Formula 34 to Formula 37, Formula 39 and Formula 40, at least one of A1 to A5 is selected from CRA, and in Formula 28 to Formula 31 and Formula 33, at least one of A1 to A7 is selected from CRA; and the RA is, at each occurrence identically or differently, 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 heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon 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 alkynyl 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, substituted or 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.
According to an embodiment of the present disclosure, in Formula 2 to Formula 40, A1 is selected from CRA; and the RA is, at each occurrence identically or differently, 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, a substituted or unsubstituted heterocyclic group having 3 to 20 ring 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 amino having 0 to 20 carbon atoms, a cyano group and combinations thereof.
According to an embodiment of the present disclosure, the RA is, at each occurrence identically or differently, selected from the group consisting of: deuterium, fluorine, methyl, ethyl, isopropyl, isobutyl, t-butyl, neopentyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, tetrahydrofuranyl, tetrahydropyranyl, deuterated methyl, deuterated ethyl, deuterated isopropyl, deuterated isobutyl, deuterated t-butyl, deuterated neopentyl, deuterated cyclopentyl, deuterated cyclopentylmethyl, deuterated cyclohexyl, norbornyl, adamantyl, trimethylsilyl, isopropyldimethylsilyl, phenyldimethylsilyl, trifluoromethyl, a cyano group, phenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl and combinations thereof.
According to an embodiment of the present disclosure, in Formula 2 to Formula 40, A1 is selected from CRA, and at least one or two of A2 to A5 is(are) selected from CRA; and the RA is, at each occurrence identically or differently, 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 heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon 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 alkynyl 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, substituted or 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.
According to an embodiment of the present disclosure, in Formula 2 to Formula 40, A1 is selected from CRA, and in Formula 2 to Formula 5, Formula 14, Formula 15 and Formula 20 to Formula 40, at least one or two of A2 to A5 is(are) selected from CRA; and the RA is, at each occurrence identically or differently, 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, a substituted or unsubstituted heterocyclic group having 3 to 20 ring 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 amino having 0 to 20 carbon atoms, a cyano group and combinations thereof.
According to an embodiment of the present disclosure, in Formula 2 to Formula 40, A1 is selected from CRA, and in Formula 2 to Formula 5, Formula 14, Formula 15 and Formula 20 to Formula 40, at least one or two of A2 to A5 is(are) selected from CRA; and the RA is, at each occurrence identically or differently, selected from the group consisting of: deuterium, fluorine, methyl, ethyl, isopropyl, isobutyl, t-butyl, neopentyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, tetrahydrofuranyl, tetrahydropyranyl, deuterated methyl, deuterated ethyl, deuterated isopropyl, deuterated isobutyl, deuterated t-butyl, deuterated neopentyl, deuterated cyclopentyl, deuterated cyclopentylmethyl, deuterated cyclohexyl, norbornyl, adamantyl, trimethylsilyl, isopropyldimethylsilyl, phenyldimethylsilyl, trifluoromethyl, a cyano group, phenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl and combinations thereof.
According to an embodiment of the present disclosure, in Formula 2 to Formula 40, Y is, at each occurrence identically or differently, selected from CRyRy, O or S.
According to an embodiment of the present disclosure, in Formula 2 to Formula 40, Y is, at each occurrence identically or differently, selected from O or S.
According to an embodiment of the present disclosure, the ligand La has a structure represented by one of Formula 41 to Formula 44:
According to an embodiment of the present disclosure, in Formula 41 to Formula 44, at least one of Rx1 to Rx7 and RA1 to RA5 is, at each occurrence identically or differently, selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring 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 amino having 0 to 20 carbon atoms, a cyano group and combinations thereof.
According to an embodiment of the present disclosure, in Formula 41 to Formula 44, at least one of Rx1 to Rx7 and RA1 to RA5 is, at each occurrence identically or differently, selected from the group consisting of: deuterium, fluorine, methyl, ethyl, isopropyl, isobutyl, t-butyl, neopentyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, tetrahydrofuranyl, tetrahydropyranyl, deuterated methyl, deuterated ethyl, deuterated isopropyl, deuterated isobutyl, deuterated t-butyl, deuterated neopentyl, deuterated cyclopentyl, deuterated cyclopentylmethyl, deuterated cyclohexyl, norbornyl, adamantyl, trimethylsilyl, isopropyldimethylsilyl, phenyldimethylsilyl, trifluoromethyl, a cyano group, phenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl and combinations thereof.
According to an embodiment of the present disclosure, in Formula 41 to Formula 44, at least one or two of Rx1 to Rx7 and/or at least one or two of RA1 to RA5 is(are), at each occurrence identically or differently, 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 heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring 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, in Formula 41 and Formula 44, at least one or two of Rx1 to Rx7 and/or at least one or two of RA1 to RA5 is(are), at each occurrence identically or differently, selected from the group consisting of: 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 arylsilyl having 6 to 20 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, in Formula 41 to Formula 44, Rx5 and/or Rx6 is, at each occurrence identically or differently, 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, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms and combinations thereof; RA1 is, at each occurrence identically or differently, selected from the group consisting of: halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms and combinations thereof; at least one or two of RA2 to RA5 is(are), at each occurrence identically or differently, 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, 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, in Formula 41 to Formula 44, Rx5 and/or Rx6 is, at each occurrence identically or differently, selected from the group consisting of: 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 arylsilyl having 6 to 20 carbon atoms and combinations thereof; RA1 is, at each occurrence identically or differently, selected from the group consisting of: 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 arylsilyl having 6 to 20 carbon atoms and combinations thereof at least one or two of RA2 to RA5 is(are), at each occurrence identically or differently, selected from the group consisting of: 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 arylsilyl having 6 to 20 carbon atoms and combinations thereof.
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 La4489, wherein the specific structures of La1 to La4489 are referred to claim 15.
According to an embodiment of the present disclosure, the metal complex has a structure of M(La)m(Lb)n(Lc)q;
In this embodiment, the expression that adjacent substituents Ra, Rb, Rc, RN1, RN2, 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, two substituents Rc, substituents Ra and Rb, substituents Ra and Rc, substituents Rb and Rc, substituents Ra and RN1, substituents Rb and RN11, substituents Ra and RC1, substituents Ra and RC2, substituents Rb and RC1, substituents Rb and RC2, substituents Ra and RN2, substituents Rb and RN2, and substituents RC1 and RC2, can be joined to form a ring. For example, adjacent substituents Ra and Rb in
can be optionally joined to form a ring, which can form one or more of the following structures including but not limited to:
wherein W is selected from O, S, Se, NR′ or CR′R′, and the definition of each of the R′, Ra′ and Rb′ is the same as that of the Ra. 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 M is selected from Ir, Rh, Re, Os, Pt, Au or Cu.
According to an embodiment of the present disclosure, the metal M is selected from Ir, Pt or Os.
According to an embodiment of the present disclosure, the metal M is Ir.
According to an embodiment of the present disclosure, Lb is, at each occurrence identically or differently, selected from the following structure:
In this embodiment, the expression that “adjacent substituents R1, R2, R3, R4, R5, R6 and R7 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, substituents R2 and R3, substituents R4 and R5, substituents R4 and R6, substituents R5 and R6, substituents R1 and R7, substituents R2 and R7, substituents R3 and R7, substituents R4 and R7, substituents R5 and R7, and substituents R6 and R7, 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, at least one or two of R1 to R3 is(are), at each occurrence identically or differently, selected from 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 or a combination thereof; and/or at least one or two of R4 to R6 is(are), at each occurrence identically or differently, selected from 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 or a combination thereof.
According to an embodiment of the present disclosure, at least two of R1 to R3 are, at each occurrence identically or differently, selected from substituted or unsubstituted alkyl having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 2 to 20 carbon atoms or a combination thereof; and/or at least two of R4 to R6 are, at each occurrence identically or differently, selected from substituted or unsubstituted alkyl having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 2 to 20 carbon atoms or a combination thereof.
According to an embodiment of the present disclosure, Lb is, at each occurrence identically or differently, selected from the group consisting of Lb1 to Lb322, wherein the specific structures of Lb1 to Lb322 are referred to claim 19.
According to an embodiment of the present disclosure, Lc is, at each occurrence identically or differently, selected from the group consisting of Lc1 to Lc231, wherein the specific structures of Lc1 to Lc231 are referred to claim 19.
According to an embodiment of the present disclosure, the metal complex has a structure of Ir(La)2(Lb) or Ir(La)2(Lc) or Ir(La)(Lc)2 or Ir(La)(Lb)(L);
According to an embodiment of the present disclosure, the metal complex is selected from the group consisting of Compound 1 to Compound 1646, wherein the specific structures of Compound 1 to Compound 1646 are referred to claim 20.
According to an embodiment of the present disclosure, disclosed is an electroluminescent device, which comprises:
According to an embodiment of the present disclosure, the organic layer is a light-emitting layer, and the metal complex is a light-emitting material.
According to an embodiment of the present disclosure, the electroluminescent device emits red light or white light.
According to an embodiment of the present disclosure, the light-emitting layer further comprises at least one host material.
According to an embodiment of the present disclosure, the at least one host material 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 at least one host material may be a conventional host material in the related art. For example, the at least one host material may typically include the following host materials without limitation:
According to an embodiment of the present disclosure, disclosed is a compound composition, which comprises 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. US20160359122A1 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. US20150349273A1, 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 a 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: Synthesis of Intermediate 3
A mixture of Intermediate 1 (1.0 g, 2.39 mmol), Intermediate 2 (0.66 g, 4.78 mmol), Pd(OAc)2 (27.8 mg, 0.12 mmol), Sphos (2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl) (98 mg, 0.24 mmol), K3PO4·3H2O (1.91 g, 7.17 mmol), 1,4-dioxane (12 mL) and water (4 mL) was added to a reaction flask. The reaction system underwent a refluxing reaction under a nitrogen atmosphere, and the reaction was monitored through TLC. Intermediate 1 disappeared, and the reaction system was cooled to room temperature. Water and ethyl acetate were added to the reaction system to extract a product, and the organic phases were collected and concentrated, and isolated and purified through column chromatography to obtain Intermediate 3 (0.64 g, with a yield of 62%).
Step 2: Synthesis of Intermediate 4
A mixture of Intermediate 3 (0.2 g, 0.46 mmol), Pd(OAc)2 (5.2 mg, 0.023 mmol), IPr (1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) (16 mg, 0.046 mmol), MesCOONa (sodium 2,4,6-trimethylbenzoate) (43 mg, 0.23 mmol), K2CO3 (0.13 g, 0.93 mmol), 4,5-diazafluoren-9-one (8.4 mg, 0.046 mmol) and mesitylene (20 mL) was added to a reaction flask. The reaction system was evacuated, purged with nitrogen, heated to a reaction temperature of 140° C. under a nitrogen atmosphere and reacted overnight. The reaction system was cooled to room temperature and concentrated, and isolated and purified through column chromatography to obtain Intermediate 4 (58 mg, with a yield of 29%).
Step 3: Synthesis of an Iridium Dimer
A mixture of Intermediate 4 (0.17 g, 0.4 mmol), iridium trichloride trihydrate (48 mg, 0.14 mmol), ethylene glycol monoethyl ether (12 mL) and water (4 mL) was added to a reaction flask and refluxed at 130° C. for 24 h under a nitrogen atmosphere. The reaction system was cooled to room temperature and filtered. The obtained solids were washed several times with methanol and dried so that an iridium dimer was obtained.
Step 4: Synthesis of Compound 557
A mixture of the iridium dimer obtained in the previous step, 3,7-diethyl-3-methylnonane-4,6-dione (50 mg, 0.2 mmol), K2CO3 (95 mg, 0.68 mmol) and ethylene glycol monoethyl ether (12 mL) was stirred at 45° C. for 24 h under a nitrogen atmosphere. After the reaction was finished, the precipitate was filtered by Celite and washed with ethanol. The obtained solids were added with dichloromethane and the filtrate was collected. Ethanol was added and the resulting solution was concentrated, but not to dryness. The residue was filtered to obtain Compound 557 (90 mg, with a yield of 52%). The structure was confirmed through NMR. 1H NMR (400 MHz, CDCl3): δ 8.14 (d, J=7.7 Hz, 2H), 7.98-7.92 (m, 6H), 7.74 (d, J=8.2 Hz, 2H), 7.64-7.57 (m, 4H), 7.50 (dd, J=13.2, 5.7 Hz, 2H), 7.20-7.17 (m, 2H), 6.90 (dd, J=20.9, 7.9 Hz, 2H), 6.63-6.58 (m, 2H), 5.23 (s, 1H), 3.30 (dt, J=26.9, 13.8 Hz, 4H), 2.24-2.20 (m, 1H), 1.12 (d, J=4.6 Hz, 18H), 0.97-0.80 (m, 8H), 0.68 (s, 3H), 0.62 (t, J=7.4 Hz, 3H), 0.32 (t, J=7.4 Hz, 3H), 0.22 (t, J=7.3 Hz, 3H), 0.11 (t, J=7.4 Hz, 3H).
Step 1: Synthesis of Intermediate 6
A mixture of Intermediate 5 (0.2 g, 0.63 mmol), Intermediate 2 (0.11 g, 0.82 mmol), Pd(OAc)2 (8 mg, 0.03 mmol), Sphos (26 mg, 0.06 mmol), K3PO4·3H2O (0.5 g, 1.9 mmol), 1,4-dioxane (9 mL) and water (3 mL) was added to a reaction flask. The reaction system was evacuated, purged with nitrogen and underwent a refluxing reaction under a nitrogen atmosphere, and the reaction was monitored through TLC. Intermediate 5 disappeared, and the reaction system was cooled to room temperature. Water and ethyl acetate were added to the reaction system to extract a product, and the organic phases were collected and concentrated, and isolated and purified through column chromatography to obtain Intermediate 6 (0.14 g, with a yield of 58%).
Step 2: Synthesis of Intermediate 7
A mixture of Intermediate 6 (0.14 g, 0.37 mmol), Pd(OAc)2 (4 mg, 0.018 mmol), IPr (13 mg, 0.037 mmol), MesCOONa (34 mg, 0.18 mmol), K2CO3 (0.10 g, 0.74 mmol), 4,5-diazafluoren-9-one (7 mg, 0.037 mmol) and mesitylene (12 mL) was added to a reaction flask. The reaction system was evacuated, purged with nitrogen, heated to 140° C. under a nitrogen atmosphere and reacted overnight. The reaction system was cooled to room temperature and concentrated, and isolated and purified through column chromatography to obtain Intermediate 7 (40 mg, with a yield of 29%).
Step 3: Synthesis of an Iridium Dimer
A mixture of Intermediate 7 (70 mg, 0.18 mmol), iridium trichloride trihydrate (22 mg, 0.06 mmol), ethylene glycol monoethyl ether (9 mL) and water (3 mL) was added to a reaction flask and refluxed at 130° C. for 24 h under a nitrogen atmosphere. The reaction system was cooled to room temperature and filtered. The obtained solids were washed several times with methanol and dried so that an iridium dimer was obtained.
Step 4 Synthesis of Compound 553
A mixture of the iridium dimer obtained in the previous step, 3,7-diethyl-3-methylnonane-4,6-dione (23 mg, 0.093 mmol), K2CO3 (43 mg, 0.31 mmol) and ethylene glycol monoethyl ether (10 mL) was stirred at 45° C. for 24 h under a nitrogen atmosphere. After the reaction was finished, the precipitate was filtered by Celite and washed with ethanol. The obtained solids were added with dichloromethane and the filtrate was collected. Ethanol was added and the resulting solution was concentrated, but not to dryness. The residue was filtered to obtain Compound 553 (20 mg, with a yield of 27%). The structure was confirmed through NMR. H NMR (400 MHz, CDCl3): δ 8.14 (d, J=7.6 Hz, 2H), 7.98 (m, 4H), 7.82 (d, J=8.3 Hz, 2H), 7.74 (d, J=8.2 Hz, 2H), 7.65 (dd, J=6.6, 4.2 Hz, 2H), 7.60 (t, J=7.8 Hz, 2H), 7.49 (t, J=7.6 Hz, 2H), 7.24-7.20 (m, 2H), 6.85 (dd, J=8.5, 3.7 Hz, 2H), 6.64-6.60 (m, 2H), 5.28 (s, 1H), 2.74 (s, 6H), 2.22 (m, 1H), 0.9-0.83 (m, 8H), 0.72 (s, 3H), 0.60 (t, J=7.4 Hz, 3H), 0.38 (t, J=7.4 Hz, 3H), 0.20 (dt, J=14.9, 7.3 Hz, 6H).
Those skilled in the art will appreciate that the above preparation methods are merely exemplary. Those skilled in the art can obtain the compound structures of the present disclosure through the modifications of the preparation methods.
The method for preparing an electroluminescent device is not limited. The preparation methods in the following examples are merely examples and are not to be construed as limitations. Those skilled in the art can make reasonable improvements on the preparation methods in the following examples based on the related art. For example, the proportions of various materials in a light-emitting layer are not particularly limited. Those skilled in the art can reasonably select the proportions within a certain range based on the related art. For example, taking the total weight of the materials in the light-emitting layer for reference, a host material may account for 80% to 99% and a light-emitting material may account for 1% to 20%; or the host material may account for 90% to 99% and the light-emitting material may account for 1% to 10%; or the host material may account for 95% to 99% and the light-emitting material may account for 1% to 5%. Further, the host material may include one material or two materials, where the ratio of two host materials may be 100:0 to 1:99; or the ratio may be 80:20 to 20:80; or the ratio may be 60:40 to 40:60.
Measurement of Photoluminescence Spectroscopy of Compound 557 and Compound 553
The photoluminescence (PL) spectroscopy data of Compound 557 and Compound 553 of the present disclosure was measured using a fluorescence spectrophotometer LENGGUANG F98 produced by SHANGHAI LENGGUANG TECHNOLOGY CO., LTD. A sample of Compound 557 or a sample of Compound 553 was prepared into a solution with a concentration of 1×10−6 mol/L by using an HPLC-grade toluene solution and then excited at room temperature (298 K) using light with a wavelength of 500 nm, and its emission spectrum was measured. The light emission wavelength λmax (nm) and the full width at half maximum FWHM (nm) of the photoluminescence spectroscopy were recorded and shown in Table 1.
As can be seen from the data in Table 1, the light emission wavelengths of Compound 557 and Compound 553 each comprising a ligand having a structure of Formula 1 disclosed in the present disclosure are 625 nm and 629 nm, respectively, and the full widths at half maximum are both extremely narrow, which are only 29.3 nm and 30.1 nm, respectively, so that very saturated light emission can be achieved, indicating that Compound 557 and Compound 553 of the present disclosure have very excellent light emission performance and have the potential to become excellent red light-emitting materials.
Firstly, a glass substrate having an indium tin oxide (ITO) anode with a thickness of 120 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 0.06 to 2 Angstroms per second and a vacuum degree of about 10−8 torr. Compounds HT and HI were co-deposited at a weight ratio of 97:3 for use as a hole injection layer (HIL) with a thickness of 100 Å. Compound HT was used as a hole transport layer (HTL) with a thickness of 400 Å. Compound EB was used as an electron blocking layer (EBL) with a thickness of 50 Å. Compound 557 of the present disclosure was doped in a host compound RH at a weight ratio of 3:97 for use as an emissive layer (EML) with a thickness of 400 Å. Compound HB was used as a hole blocking layer (HBL) with a thickness of 50 Å. On the HBL, Compound ET and 8-hydroxyquinolinolato-lithium (Liq) were co-deposited at a weight ratio of 40:60 as an electron transport layer (ETL) with a thickness of 350 Å. Finally, Liq was deposited as an electron injection layer with a thickness of 1 nm, and Al was deposited 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 preparation method in Comparative Example 1 was the same as that in Example 1, except that in the emissive layer (EML), Compound 557 of the present disclosure was replaced with Compound RD.
Structures and thicknesses of part of layers of the devices are shown in the following Table 2. A layer using more than one material is obtained by doping different compounds at their weight ratio as recorded.
The structures of the materials used in the devices are shown as follows:
Table 3 shows the color coordinate (CIE), drive voltage (Voltage), maximum emission wavelength (λmax), full width at half maximum (FWHM), current efficiency (CE), power efficiency (PE) and external quantum efficiency (EQE) data of Example 1 and Comparative Example 1 measured at a constant current of 15 mA/cm2.
As can be seen from the data in Table 3, the maximum emission wavelength of Example 1 reached 628 nm, which was 5 nm red-shifted compared to the maximum emission wavelength (623 nm) of Comparative Example 1, and the full width at half maximum of Example 1 was substantially the same as that of Comparative Example 1, both of which had an extremely narrow full width at half maximum. It can be seen that in Example 1, such a narrow full width at half maximum can be maintained while the maximum emission wavelength is red-shifted. Therefore, very saturated light emission can be achieved in Example 1. In addition, compared to Comparative Example 1, the drive voltage of Example 1 was reduced by 0.15 V, the current efficiency (CE) was improved by 4%, and the power efficiency (PE) was improved by 8.2%. More surprisingly, on the basis of the fact that Comparative Example 1 had already had a very high level of EQE (20.33%), the external quantum efficiency of Example 1 was further significantly improved by 20%, which is very rare. All the above data proves that the compound disclosed in the present disclosure has very excellent performance.
In conclusion, the compound disclosed in the present disclosure, while maintaining a very narrow full width at half maximum, can effectively adjust the emission wavelength to better meet the requirement of saturated red light emission, reduce the drive voltage and significantly improve the device efficiency. These advantages highlight the uniqueness of the present disclosure and the commercial application potential as a red light-emitting material.
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 from 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 |
|---|---|---|---|
| 202210755442.1 | Jun 2022 | CN | national |
| 202310421323.7 | Apr 2023 | CN | national |
