Patent Application
20250089550
This application claims priority to Chinese Patent Application No. 202311114556.9 filed on Aug. 31, 2023, the disclosure of which is incorporated herein by reference in its entirety.
The present disclosure relates to compounds for organic electronic devices such as organic light-emitting devices. More particularly, the present disclosure relates to a metal complex comprising a ligand La having a structure of Formula 1 and a ligand Lb having a structure of Formula 2, an organic electroluminescent device comprising the metal complex and a compound composition comprising the metal complex.
Organic electronic devices include, but are not limited to, the following types: organic light-emitting diodes (OLEDs), organic field-effect transistors (O-FETs), organic light-emitting transistors (OLETs), organic photovoltaic devices (OPVs), dye-sensitized solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field-quench devices (OFQDs), light-emitting electrochemical cells (LECs), organic laser diodes and organic plasmon emitting devices.
In 1987, Tang and Van Slyke of Eastman Kodak reported a bilayer organic electroluminescent device, which includes an arylamine hole transporting layer and a tris-8-hydroxyquinolato-aluminum layer as the electron and emitting layer (Applied Physics Letters, 1987, 51 (12): 913-915). Once a bias is applied to the device, green light was emitted from the device. This device laid the foundation for the development of modern organic light-emitting diodes (OLEDs). State-of-the-art OLEDs may include multiple layers such as charge injection and transporting layers, charge and exciton blocking layers, and one or multiple emissive layers between the cathode and anode. Since the OLED is a self-emitting solid state device, it offers tremendous potential for display and lighting applications. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on flexible substrates.
The OLED can be categorized as three different types according to its emitting mechanism. The OLED invented by Tang and van Slyke is a fluorescent OLED. It only utilizes singlet emission. The triplets generated in the device are wasted through nonradiative decay channels. Therefore, the internal quantum efficiency (IQE) of the fluorescent OLED is only 25%. This limitation hindered the commercialization of OLED. In 1997, Forrest and Thompson reported phosphorescent OLED, which uses triplet emission from heavy metal containing complexes as the emitter. As a result, both singlet and triplets can be harvested, achieving 100% IQE. The discovery and development of phosphorescent OLED contributed directly to the commercialization of active-matrix OLED (AMOLED) due to its high efficiency. Recently, Adachi achieved high efficiency through thermally activated delayed fluorescence (TADF) of organic compounds. These emitters have small singlet-triplet gap that makes the transition from triplet back to singlet possible. In the TADF device, the triplet excitons can go through reverse intersystem crossing to generate singlet excitons, resulting in high IQE.
OLEDs can also be classified as small molecule and polymer OLEDs according to the forms of the materials used. A small molecule refers to any organic or organometallic material that is not a polymer. The molecular weight of the small molecule can be large as long as it has well defined structure. Dendrimers with well-defined structures are considered as small molecules. Polymer OLEDs include conjugated polymers and non-conjugated polymers with pendant emitting groups. Small molecule OLED can become the polymer OLED if post polymerization occurred during the fabrication process.
There are various methods for OLED fabrication. Small molecule OLEDs are generally fabricated by vacuum thermal evaporation. Polymer OLEDs are fabricated by solution process such as spin-coating, inkjet printing, and slit printing. If the material can be dissolved or dispersed in a solvent, the small molecule OLED can also be produced by solution process.
The emitting color of the OLED can be achieved by emitter structural design. An OLED may include one emitting layer or a plurality of emitting layers to achieve desired spectrum. In the case of green, yellow, and red OLEDs, phosphorescent emitters have successfully reached commercialization. Blue phosphorescent device still suffers from non-saturated blue color, short device lifetime, and high operating voltage. Commercial full-color OLED displays normally adopt a hybrid strategy, using fluorescent blue and phosphorescent yellow, or red and green. At present, efficiency roll-off of phosphorescent OLEDs at high brightness remains a problem. In addition, it is desirable to have more saturated emitting color, higher efficiency, and longer device lifetime.
From the perspective of electronics, the display principle of the OLED is briefly described as follows: under the action of an applied electric field greater than a certain threshold, holes and electrons are injected from an anode and a cathode respectively into an organic thin-film light-emitting layer sandwiched between the anode and the cathode in the form of currents, the holes and the electrons recombine into excitons, and the radiative recombination occurs to cause light emission. Since an organic light-emitting film has very apparent capacitance characteristics, the capacitance of the organic light-emitting film is a key factor that affects the response time and refresh rate of an OLED display device at a low grayscale.
CN105980519A discloses a compound M(L)n(L′)m, wherein M(L)n has the following structure:
CyD and/or CyC contain two adjacent carbon atoms, the carbon atoms are each substituted with a group R, and the R and the carbon atoms form a ring
Further disclosed are the following specific structures:
This application has taught neither a compound whose ligand L′ is a multi-membered fused aromatic ring structure with a particular substituent nor an effect of the compound 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 and a ligand Lb having a structure of Formula 2 to solve at least part of the preceding problems. When applied to electroluminescent devices, these new metal complexes can obtain more saturated green light emission, a lower efficiency roll-off at high brightness, and a response rate at a low grayscale, increase the refresh rate of the devices, and facilitate an improvement of the overall performance of the devices.
According to an embodiment of the present disclosure, disclosed is a metal complex having a general formula of M(La)m(Lb)n(Lc)q; wherein
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 according to the preceding embodiment.
According to another embodiment of the present disclosure, further disclosed is a compound composition comprising the metal complex according to the preceding embodiment.
The present disclosure aims to provide a series of metal complexes each comprising a ligand La having a structure of Formula 1 and a ligand Lb having a structure of Formula 2 to solve at least part of the preceding problems. When applied to electroluminescent devices, these new metal complexes can obtain more saturated green light emission and a lower efficiency roll-off, providing more options for the application of phosphorescent OLED materials and devices in high-brightness scenarios. Meanwhile, the metal complexes of the present disclosure have lower device capacitance in the devices and better facilitate an increase in the response rate of OLED display devices at a low grayscale and an increase in the refresh rate of the devices.
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 (AES-T). Organic, non-metal containing, donor-acceptor luminescent materials may be able to achieve this. The emission in these materials is generally characterized as a donor-acceptor charge-transfer (CT) type emission. The spatial separation of the HOMO and LUMO in these donor-acceptor type compounds generally results in small AES-T. These states may involve CT states. Generally, donor-acceptor luminescent materials are constructed by connecting an electron donor moiety such as amino- or carbazole-derivatives and an electron acceptor moiety such as N-containing six-membered aromatic rings.
As used herein, unless otherwise specified, the “maximum capacitance” refers to a peak value which the device capacitance can reach as a test voltage increases at a particular frequency, as shown in
Halogen or halide—as used herein includes fluorine, chlorine, bromine, and iodine.
Alkyl—as used herein includes both straight and branched chain alkyl groups. Alkyl may be alkyl having 1 to 20 carbon atoms, preferably alkyl having 1 to 12 carbon atoms, and more preferably alkyl having 1 to 6 carbon atoms. Examples of alkyl groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, a neopentyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 1-pentylhexyl group, a 1-butylpentyl group, a 1-heptyloctyl group, and a 3-methylpentyl group. Of the above, preferred are a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, a neopentyl group, and an n-hexyl group. Additionally, the alkyl group may be optionally substituted.
Cycloalkyl—as used herein includes cyclic alkyl groups. The cycloalkyl groups may be those having 3 to 20 ring carbon atoms, preferably those having 4 to 10 carbon atoms. Examples of cycloalkyl include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcylcohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, and the like. Of the above, preferred are cyclopentyl, cyclohexyl, 4-methylcyclohexyl, and 4,4-dimethylcylcohexyl. Additionally, the cycloalkyl group may be optionally substituted.
Heteroalkyl—as used herein, includes a group formed by replacing one or more carbons in an alkyl chain with a hetero-atom(s) selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a silicon atom, a germanium atom, and a boron atom. Heteroalkyl may be those having 1 to 20 carbon atoms, preferably those having 1 to 10 carbon atoms, and more preferably those having 1 to 6 carbon atoms. Examples of heteroalkyl include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxymethoxymethyl, ethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminomethyl, trimethylgermanylmethyl, trimethylgermanylethyl, trimethylgermanylisopropyl, dimethylethylgermanylmethyl, dimethylisopropylgermanylmethyl, tert-butylmethylgermanylmethyl, triethylgermanylmethyl, triethylgermanylethyl, triisopropylgermanylmethyl, triisopropylgermanylethyl, trimethylsilylmethyl, trimethylsilylethyl, and trimethylsilylisopropyl, triisopropylsilylmethyl, triisopropylsilylethyl. Additionally, the heteroalkyl group may be optionally substituted.
Alkenyl—as used herein includes straight chain, branched chain, and cyclic alkene groups. Alkenyl may be those having 2 to 20 carbon atoms, preferably those having 2 to 10 carbon atoms. Examples of alkenyl include vinyl, 1-propenyl group, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butandienyl, 1-methylvinyl, styryl, 2,2-diphenylvinyl, 1,2-diphenylvinyl, 1-methylallyl, 1,1-dimethylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl, 3-phenylallyl, 3,3-diphenylallyl, 1,2-dimethylallyl, 1-phenyl-1-butenyl, 3-phenyl-1-butenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl, cyclooctatetraenyl, and norbornenyl. Additionally, the alkenyl group may be optionally substituted.
Alkynyl—as used herein includes straight chain alkynyl groups. Alkynyl may be those having 2 to 20 carbon atoms, preferably those having 2 to 10 carbon atoms. Examples of alkynyl groups include ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3,3-dimethyl-1-butynyl, 3-ethyl-3-methyl-1-pentynyl, 3,3-diisopropyl-1-pentynyl, phenylethynyl, phenylpropynyl, etc. Of the above, preferred are ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, and phenylethynyl. Additionally, the alkynyl group may be optionally substituted.
Aryl or an aromatic group—as used herein includes non-condensed and condensed systems. Aryl may be those having 6 to 30 carbon atoms, preferably those having 6 to 20 carbon atoms, and more preferably those having 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene. Examples of non-condensed aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4′-methylbiphenylyl, 4″-t-butyl-p-terphenyl-4-yl, o-cumenyl, m-cumenyl, p-cumenyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesityl, and m-quarterphenyl. Additionally, the aryl group may be optionally substituted.
Heterocyclic groups—as used herein include non-aromatic cyclic groups. Non-aromatic heterocyclic groups include saturated heterocyclic groups having 3 to 20 ring atoms and unsaturated non-aromatic heterocyclic groups having 3 to 20 ring atoms, where at least one ring atom is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, a phosphorus atom, a germanium atom, and a boron atom. Preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms, each of which includes at least one hetero-atom such as nitrogen, oxygen, silicon, or sulfur. Examples of non-aromatic heterocyclic groups include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxolanyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxepinyl, thiepinyl, azepinyl, and tetrahydrosilolyl. Additionally, the heterocyclic group may be optionally substituted.
Heteroaryl—as used herein, includes non-condensed and condensed hetero-aromatic groups having 1 to 5 hetero-atoms, where at least one hetero-atom is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, a phosphorus atom, a germanium atom, and a boron atom. A hetero-aromatic group is also referred to as heteroaryl. Heteroaryl may be those having 3 to 30 carbon atoms, preferably those having 3 to 20 carbon atoms, and more preferably those having 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridoindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.
Alkoxy—as used herein, is represented by —O-alkyl, —O-cycloalkyl, —O-heteroalkyl, or —O-heterocyclic group. Examples and preferred examples of alkyl, cycloalkyl, heteroalkyl, and heterocyclic groups are the same as those described above. Alkoxy groups may be those having 1 to 20 carbon atoms, preferably those having 1 to 6 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy, and ethoxymethyloxy. Additionally, the alkoxy group may be optionally substituted.
Aryloxy—as used herein, is represented by —O-aryl or —O-heteroaryl. Examples and preferred examples of aryl and heteroaryl are the same as those described above. Aryloxy groups may be those having 6 to 30 carbon atoms, preferably those having 6 to 20 carbon atoms. Examples of aryloxy groups include phenoxy and biphenyloxy. Additionally, the aryloxy group may be optionally substituted.
Arylalkyl—as used herein, contemplates alkyl substituted with an aryl group. Arylalkyl may be those having 7 to 30 carbon atoms, preferably those having 7 to 20 carbon atoms, and more preferably those having 7 to 13 carbon atoms. Examples of arylalkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl-t-butyl, alpha-naphthylmethyl, 1-alpha-naphthylethyl, 2-alpha-naphthylethyl, 1-alpha-naphthylisopropyl, 2-alpha-naphthylisopropyl, beta-naphthylmethyl, 1-beta-naphthylethyl, 2-beta-naphthylethyl, 1-beta-naphthylisopropyl, 2-beta-naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl, and 1-chloro-2-phenylisopropyl. Of the above, preferred are benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, and 2-phenylisopropyl. Additionally, the arylalkyl group may be optionally substituted.
Alkylsilyl—as used herein, contemplates a silyl group substituted with an alkyl group. Alkylsilyl groups may be those having 3 to 20 carbon atoms, preferably those having 3 to 10 carbon atoms. Examples of alkylsilyl groups include trimethylsilyl, triethylsilyl, methyldiethylsilyl, ethyldimethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, methyldiisopropylsilyl, dimethylisopropylsilyl, tri-t-butylsilyl, triisobutylsilyl, dimethyl t-butylsilyl, and methyldi-t-butylsilyl. Additionally, the alkylsilyl group may be optionally substituted.
Arylsilyl—as used herein, contemplates a silyl group substituted with an aryl group. Arylsilyl groups may be those having 6 to 30 carbon atoms, preferably those having 8 to 20 carbon atoms. Examples of arylsilyl groups include triphenylsilyl, phenyldibiphenylylsilyl, diphenylbiphenylsilyl, phenyldiethylsilyl, diphenylethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, phenyldiisopropylsilyl, diphenylisopropylsilyl, diphenylbutylsilyl, diphenylisobutylsilyl, diphenyl t-butylsilyl. Additionally, the arylsilyl group may be optionally substituted.
Alkylgermanyl—as used herein contemplates germanyl substituted with an alkyl group. The alkylgermanyl may be those having 3 to 20 carbon atoms, preferably those having 3 to 10 carbon atoms. Examples of alkylgermanyl include trimethylgermanyl, triethylgermanyl, methyldiethylgermanyl, ethyldimethylgermanyl, tripropylgermanyl, tributylgermanyl, triisopropylgermanyl, methyldiisopropylgermanyl, dimethylisopropylgermanyl, tri-t-butylgermanyl, triisobutylgermanyl, dimethyl-t-butylgermanyl, and methyldi-t-butylgermanyl. Additionally, the alkylgermanyl may be optionally substituted.
Arylgermanyl—as used herein contemplates a germanyl substituted with at least one aryl group or heteroaryl group. Arylgermanyl may be those having 6 to 30 carbon atoms, preferably those having 8 to 20 carbon atoms. Examples of arylgermanyl include triphenylgermanyl, phenyldibiphenylylgermanyl, diphenylbiphenylgermanyl, 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, amino, acyl, carbonyl, a carboxylic acid group, an ester group, sulfinyl, sulfonyl, and phosphino may be substituted with one or more moieties selected from the group consisting of deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted heteroalkyl having 1 to 20 carbon atoms, an unsubstituted heterocyclic group having 3 to 20 ring atoms, unsubstituted arylalkyl having 7 to 30 carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted aryloxy having 6 to 30 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, unsubstituted alkynyl having 2 to 20 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted heteroaryl having 3 to 30 carbon atoms, unsubstituted alkylsilyl having 3 to 20 carbon atoms, unsubstituted arylsilyl having 6 to 20 carbon atoms, unsubstituted alkylgermanyl having 3 to 20 carbon atoms, unsubstituted arylgermanyl group having 6 to 20 carbon atoms, unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.
It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or an attached fragment are considered to be equivalent.
In the compounds mentioned in the present disclosure, hydrogen atoms may be partially or fully replaced by deuterium. Other atoms such as carbon and nitrogen can also be replaced by their other stable isotopes. The replacement by other stable isotopes in the compounds may be preferred due to its enhancements of device efficiency and stability.
In the compounds mentioned in the present disclosure, multiple substitution refers to a range that includes a di-substitution, up to the maximum available substitution. When substitution in the compounds mentioned in the present disclosure represents multiple substitution (including di-, tri-, and tetra-substitutions, etc.), that means the substituent may exist at a plurality of available substitution positions on its linking structure, the substituents present at a plurality of available substitution positions may be the same structure or different structures.
In the compounds mentioned in the present disclosure, adjacent substituents in the compounds cannot be joined to form a ring unless otherwise explicitly defined, for example, adjacent substituents can be optionally joined to form a ring. In the compounds mentioned in the present disclosure, the expression that adjacent substituents can be optionally joined to form a ring includes a case where adjacent substituents may be joined to form a ring and a case where adjacent substituents are not joined to form a ring. When adjacent substituents can be optionally joined to form a ring, the ring formed may be monocyclic or polycyclic (including spirocyclic, endocyclic, fusedcyclic, and etc.), as well as alicyclic, heteroalicyclic, aromatic, or heteroaromatic. In such expression, adjacent substituents may refer to substituents bonded to the same atom, substituents bonded to carbon atoms which are directly bonded to each other, or substituents bonded to carbon atoms which are more distant from each other. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms which are directly bonded to each other.
The expression that adjacent substituents can be optionally joined to form a ring is also intended to mean that two substituents bonded to the same carbon atom are joined to each other via a chemical bond to form a ring, which can be exemplified by the following formula:
The expression that adjacent substituents can be optionally joined to form a ring is also intended to mean that two substituents bonded to carbon atoms which are directly bonded to each other are joined to each other via a chemical bond to form a ring, which can be exemplified by the following formula:
The expression that adjacent substituents can be optionally joined to form a ring is also intended to mean that two substituents bonded to a further distant carbon atom are joined to each other via a chemical bond to form a ring, which can be exemplified by the following formula:
Furthermore, the expression that adjacent substituents can be optionally joined to form a ring is also intended to mean that, in the case where one of the two substituents bonded to carbon atoms which are directly bonded to each other represents hydrogen, the second substituent is bonded at a position at which the hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following formula:
According to an embodiment of the present disclosure, disclosed is a metal complex having a general formula of M(La)m(Lb)n(Lc)q; wherein the metal M is selected from a metal with a relative atomic mass greater than 40;
In the present disclosure, when G1 is selected from a single bond, it indicates that the ring Cy is directly joined to the metal M; and when G2 is selected from a single bond, it indicates that X1, X2, X3 or X4 is directly joined to the metal M.
In the present disclosure, when G3 is selected from a single bond, it indicates that the ring Cu is directly joined to the metal M; and when G4 is selected from a single bond, it indicates that the ring Cw is directly joined to the metal M.
In the present disclosure, the expression that “adjacent substituents R, R1 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 R1, and substituents R and R1, 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 Ru, Rw 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 Ru, two substituents Rw, and substituents Ru and R., can be joined to form a ring. Obviously, it is also possible that none of these substituents are joined to form a ring.
In the present disclosure, the expression that “adjacent substituents Ry can be optionally joined to form a ring” is intended to mean that any one or more of groups consisting of adjacent substituents Ry can be optionally joined to form a ring. Obviously, it is also possible that none of these substituents are joined to form a ring.
In the present disclosure, the expression that “adjacent substituents R′, Rx2 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 Rx2, two substituents R′, and substituents Rx2 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.
According to an embodiment of the present disclosure, the ring Cy is, at each occurrence identically or differently, selected from any structure in the group consisting of the following:
represents a position where X1, X2, X3 or X4 is joined.
According to an embodiment of the present disclosure, Lb is, at each occurrence identically or differently, selected from any structure in the group consisting of the following:
In this embodiment, the ring where the substituent Ru is located is the ring Cu and the ring where the substituent Rw is located is the ring Cw.
According to an embodiment of the present disclosure, the metal M is, at each occurrence identically or differently, selected from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir and Pt.
According to an embodiment of the present disclosure, the metal M is, at each occurrence identically or differently, selected from Pt or Jr.
According to an embodiment of the present disclosure, the metal M is, at each occurrence identically or differently, selected from Jr.
According to an embodiment of the present disclosure, G1 and G2 are, at each occurrence identically or differently, selected from a single bond or O.
According to an embodiment of the present disclosure, G1 and G2 are each a single bond.
According to an embodiment of the present disclosure, G3 and G4 are each a single bond.
According to an embodiment of the present disclosure, Le is, at each occurrence identically or differently, selected from any structure in the group consisting of the following:
In the present disclosure, the expression that “adjacent substituents Ra, Rb, Rc, RN1, RC1 and RC2 can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents Ra, two substituents Rb, substituents Ra and Rb, substituents Ra and Rc, substituents Rb and Rc, substituents Ra and RN1, substituents Rb and RN1, substituents Ra and RC1, substituents Ra and RC2, substituents Rb and RC1, substituents Rb and RC2 and substituents RC1 and RC2, can be joined to form a ring. Obviously, it is also possible that none of these substituents are joined to form a ring. For example, adjacent substituents Ra, Rb in
can be optionally joined to form a ring. When Ra is optionally joined to form a ring,
may form a structure of
According to an embodiment of the present disclosure, Le has the following structure:
wherein
According to an embodiment of the present disclosure, Ra and Rb 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 alkylsilyl having 3 to 20 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, the metal complex has a general formula of Ir(La)m(Lb)3-m and a structure represented by Formula 4:
According to an embodiment of the present disclosure, m is selected from 1.
According to an embodiment of the present disclosure, Z is, at each occurrence identically or differently, selected from O or S.
According to an embodiment of the present disclosure, Z is selected from O.
According to an embodiment of the present disclosure, Rn is, at each occurrence identically or differently, 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 heteroaryl having 3 to 30 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, Rn is, at each occurrence identically or differently, 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, Rn is, at each occurrence identically or differently, selected from substituted or unsubstituted alkyl having 1 to 6 carbon atoms.
According to an embodiment of the present disclosure, Rn is, at each occurrence identically or differently, selected from the group consisting of the following:
According to an embodiment of the present disclosure, Y3 to Y6 are, at each occurrence identically or differently, selected from CRy.
According to an embodiment of the present disclosure, Y3 to Y6 are, at each occurrence identically or differently, selected from CRy or N, and at least one of Y3 to Y6 is N. For example, one of Y3 to Y6 is selected from N or two of Y3 to Y6 are selected from N.
According to an embodiment of the present disclosure, Y3 to Y6 are, at each occurrence identically or differently, selected from CRy or N; at least one of Y3 to Y6 is selected from CRy, and the Ry is 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, Y3 to Y6 are, at each occurrence identically or differently, selected from CRy or N; at least one of Y3 to Y6 is selected from CRy, and the Ry is 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, Y3 to Y6 are, at each occurrence identically or differently, selected from CRy or N; at least one of Y3 to Y6 is selected from CRy, and the Ry is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, X3 is selected from CRx1, and the Rx1 is, at each occurrence identically or differently, selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, cyano or a combination thereof.
According to an embodiment of the present disclosure, X3 is selected from CRx1, and the Rx1 is, at each occurrence identically or differently, selected from hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, cyano or a combination thereof.
According to an embodiment of the present disclosure, X5 to X8 are, at each occurrence identically or differently, selected from CRx2.
According to an embodiment of the present disclosure, X5 to X8 are, at each occurrence identically or differently, selected from CRx2 or N, and at least one of X5 to X8 is N. For example, one of X5 to X8 is selected from N or two of X5 to X8 are selected from N.
According to an embodiment of the present disclosure, at least two of X5 to X8 are selected from CRx2, one of the Rx2 is cyano or fluorine, and another one of the Rx2 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 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, at least two of X5 to X8 are selected from CRx2, one of the Rx2 is cyano or fluorine, and another one of the Rx2 is 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, X7 or Xs is CRx2, and the Rx2 is cyano or fluorine.
According to an embodiment of the present disclosure, X7 is CRx2, and the Rx2 is cyano or fluorine.
According to an embodiment of the present disclosure, X7 is CRx2, and the Rx2 is cyano.
According to an embodiment of the present disclosure, X7 is selected from CRx2, and the Rx2 is cyano or fluorine; Xs is selected from CRx2, and the Rx2 is selected from deuterium, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 carbon atoms, substituted or unsubstituted aryl having 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 18 carbon atoms or a combination thereof.
According to an embodiment of the present disclosure, X7 is selected from CRx2, and the Rx2 is cyano or fluorine; Xs is selected from CRx2, and the Rx2 is selected from deuterium, substituted or unsubstituted aryl having 6 to 18 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 18 carbon atoms or a combination thereof.
According to an embodiment of the present disclosure, U3 to U6 contain at least two adjacent C atoms, and the two adjacent C atoms are fused with Formula 3 to form a non-aromatic ring; and/or W3 to W6 contain at least two adjacent C atoms, and the two adjacent C atoms are fused with Formula 3 to form a non-aromatic ring.
According to an embodiment of the present disclosure, W3 to W6 contain at least two adjacent C atoms, and the two adjacent C atoms are fused with Formula 3 to form a non-aromatic ring.
According to an embodiment of the present disclosure, W4 and Ws are selected from C atoms, and the C atoms are fused with Formula 3 to form a non-aromatic ring.
According to an embodiment of the present disclosure, in Formula 3, p1 is selected from 1, 2 or 3 and p2 is selected from 0; A1 and A2 are, at each occurrence identically or differently, selected from CRR; and A3 is, at each occurrence identically or differently, selected from CR1R1, O, S, NR1 or C(═O).
According to an embodiment of the present disclosure, in Formula 3, p1 is selected from 1, 2 or 3 and p2 is selected from 0; A1 and A2 are, at each occurrence identically or differently, selected from CRR; and A3 is, at each occurrence identically or differently, selected from CR1R1.
According to an embodiment of the present disclosure, Formula 3 has a structure represented by Formula 5:
According to an embodiment of the present disclosure, R and R1 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 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, cyano and combinations thereof.
According to an embodiment of the present disclosure, R and R1 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 alkylgermanyl having 3 to 20 carbon atoms, cyano and combinations thereof.
According to an embodiment of the present disclosure, R and R1 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, Ry1 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 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, Rux 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 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, Rx1 and Rx2 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 alkylgermanyl having 3 to 20 carbon atoms, cyano and combinations thereof.
According to an embodiment of the present disclosure, Rx1 and Rx2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 12 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 12 carbon atoms, cyano and combinations thereof.
According to an embodiment of the present disclosure, Rx1 and Rx2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, cyano, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, neopentyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated neopentyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, biphenyl, naphthyl, carbazolyl, pyridyl, trimethylsilyl, trimethylgermanyl and combinations thereof.
According to an embodiment of the present disclosure, Ry is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, cyano and combinations thereof.
According to an embodiment of the present disclosure, Ry is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 12 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 12 carbon atoms, cyano and combinations thereof.
According to an embodiment of the present disclosure, Ry is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, cyano, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, neopentyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated neopentyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridyl, trimethylsilyl, trimethylgermanyl and combinations thereof.
According to an embodiment of the present disclosure, at least one of Y3 to Y6 is selected from CRy, and the Ry is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, at least one of Y3 to Y6 is selected from CRy, and the Ry is selected from the group consisting of: deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, at least one of Y3 to Y6 is selected from CRy, and the Ry is selected from the group consisting of: deuterium, fluorine, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, neopentyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated neopentyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, trimethylsilyl, trimethylgermanyl and combinations thereof.
According to an embodiment of the present disclosure, La is, at each occurrence identically or differently, selected from the group consisting of La1 to La3526. For the specific structures of La1 to La3526, see claim 16.
According to an embodiment of the present disclosure, hydrogens in La1 to La3526 can be partially or fully substituted with deuterium.
According to an embodiment of the present disclosure, Lb is, at each occurrence identically or differently, selected from the group consisting of Lb1 to Lb294. For the specific structures of Lb1 to Lb294, see claim 17.
According to an embodiment of the present disclosure, hydrogens in Lb1 to Lb294 can be partially or fully substituted with deuterium.
According to an embodiment of the present disclosure, Lc is, at each occurrence identically or differently, selected from the group consisting of Lc1 to Lc142. For the specific structures of Lc1 to Lc142, see claim 18.
According to an embodiment of the present disclosure, hydrogens in Lc1 to Lc18, Lc20 to Lc26 and Lc31 to Lc142 can be partially or fully substituted with deuterium.
According to an embodiment of the present disclosure, the metal complex has a structure of Ir(La)(Lb)2 or Ir(La)2(Lb), wherein La is, at each occurrence identically or differently, selected from one or two of the group consisting of La1 to La3526, and Lb is, at each occurrence identically or differently, selected from one or two of the group consisting of Lb1 to Lb294.
According to an embodiment of the present disclosure, the metal complex has a structure of Ir(La)(Lb)(Lc), wherein La is, at each occurrence identically or differently, selected from one of the group consisting of La1 to La3526, Lb is, at each occurrence identically or differently, selected from one of the group consisting of Lb1 to Lb294, and Le is, at each occurrence identically or differently, selected from one of the group consisting of Lc1 to Lc142.
According to an embodiment of the present disclosure, the metal complex is selected from the group consisting of Metal Complex 1 to Metal Complex 5544. For the specific structures of Metal Complex 1 to Metal Complex 5544, see claim 19.
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 according to any one of the preceding embodiments.
According to an embodiment of the present disclosure, the organic layer comprising the metal complex is a light-emitting layer.
According to an embodiment of the present disclosure, the light-emitting layer further comprises a first host compound.
According to an embodiment of the present disclosure, the light-emitting layer further comprises a first host compound and a second host compound.
According to an embodiment of the present disclosure, the first host compound and/or the second host compound comprise at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, aza-dibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene and combinations thereof.
According to an embodiment of the present disclosure, the first host compound has a structure represented by Formula X-1 or Formula X-2:
In this embodiment, the expression that “adjacent substituents Rg, Rv and Rt can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents Rv, two substituents Rt, two substituents Rg, substituents Rv and Rt, substituents Rv and Rg, and substituents Rg and Rt, can be joined to form a ring. Obviously, it is also possible that none of these substituents are joined to form a ring.
According to an embodiment of the present disclosure, the first host compound has a structure represented by one of Formula X-a to Formula X-p:
According to an embodiment of the present disclosure, the first host compound is selected from the group consisting of the following compounds:
According to an embodiment of the present disclosure, the second host compound has a structure represented by Formula 6:
In the present disclosure, the expression that “adjacent substituents Re, RQ and Rq can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents Re, two substituents RQ, two substituents Rq, and two substituents RQ and Rq, can be joined to form a ring. Obviously, it is also possible that none of these substituents are joined to form a ring.
According to an embodiment of the present disclosure, the second host compound is selected from the group consisting of the following compounds:
According to an embodiment of the present disclosure, the metal complex is doped in the first host compound and the second host compound, and the weight of the metal complex accounts for 1% to 30% of the total weight of the light-emitting layer.
According to an embodiment of the present disclosure, the metal complex is doped in the first host compound and the second host compound, and the weight of the metal complex accounts for 3% to 13% of the total weight of the light-emitting layer.
According to an embodiment of the present disclosure, the organic electroluminescent device further comprises a hole injection layer. The hole injection layer may be a functional layer comprising a single material or a functional layer comprising multiple materials, wherein the comprised multiple materials are most commonly used as hole transporting materials doped with a certain proportion of p-type conductive doping material. Common p-type doping materials are as follows:
According to an embodiment of the present disclosure, further disclosed is a compound composition comprising the metal complex according to any one of the preceding embodiments.
Combination with Other Materials
The materials described in the present disclosure for a particular layer in an organic light-emitting device can be used in combination with various other materials present in the device. The combinations of these materials are described in more detail in U.S. Pat. Pub. No. 20160359122 at paragraphs 0132-0161, which is incorporated by reference herein in its entirety. The materials described or referred to the disclosure are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
The materials described herein as useful for a particular layer in an organic light-emitting device may be used in combination with a variety of other materials present in the device. For example, dopants disclosed herein may be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The combination of these materials is described in detail in paragraphs 0080-0101 of U.S. Pat. Pub. No. 20150349273, which is incorporated by reference herein in its entirety. The materials described or referred to the disclosure are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
In the embodiments of material synthesis, all reactions were performed under nitrogen protection unless otherwise stated. All reaction solvents were anhydrous and used as received from commercial sources. Synthetic products were structurally confirmed and tested for properties using one or more conventional equipment in the art (including, but not limited to, nuclear magnetic resonance instrument produced by BRUKER, liquid chromatograph produced by SHIMADZU, liquid chromatograph-mass spectrometry produced by SHIMADZU, gas chromatograph-mass 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.
Under nitrogen protection, 6-bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene (15.0 g, 56.1 mmol), bis(pinacolato)diboron (18.5 g, 72.3 mmol), Pd(dppf)Cl2 (1.4 g, 1.9 mmol), potassium acetate (13.8 g, 140.3 mmol) and N,N-dimethylformamide (DMF, 100 mL) were added in sequence to a dry 250 mL round-bottom flask and reacted overnight at 100° C. After the reaction was completed, the system was washed with a large amount of water and extracted with ethyl acetate, and the organic phase was concentrated to obtain a crude product, Intermediate 1, which was directly used in the next step.
Under nitrogen protection, Intermediate 1 in the above step, 2-chloro-5-t-butylpyridine (9.5 g, 56.1 mmol), Pd(PPh3)4 (2.0 g, 1.7 mmol), sodium carbonate (14.9 g, 140.3 mmol) and 1,4-dioxane:water (3:1, 160 mL) were added in sequence to a dry 250 mL round-bottom flask and reacted overnight at 100° C. After the reaction was completed, the system was extracted with ethyl acetate and purified through column chromatography to obtain Intermediate 2 (8.1 g, 25.2 mmol, with a yield of 45%).
Under nitrogen protection, Intermediate 2 (8.1 g, 25.2 mmol), iridium trichloride trihydrate (3.0 g, 8.5 mmol), 2-Ethoxyethanol (30 mL) and water (10 mL) were added in sequence to a dry 250 mL round-bottom flask, reacted for 24 h at 130° C. and filtered. A solid was collected, dried and dissolved in dichloromethane (100 mL). Silver trifluoromethanesulfonate (1.8 g, 7.0 mmol) and methanol (5 mL) were added and stirred overnight at room temperature. After the reaction was completed, the system was filtered and the filtrate was concentrated under reduced pressure to obtain Intermediate 3 as a yellow solid (6.0 g, 5.7 mmol, with a yield of 67%).
Intermediate 3 (1.3 g, 1.25 mmol), Intermediate 4 (0.55 g, 1.35 mmol), 2-ethoxyethanol (15 mL) and DMF (15 mL) were added in sequence to a dry 100 mL round-bottom flask and heated to react for 5 days at 100° C. under N2 protection. After the reaction was cooled, the system was concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 2810 as a yellow solid (0.8 g, with a yield of 52%). The product was confirmed as the target product with a molecular weight of 1239.6.
Intermediate 3 (1.0 g, 0.96 mmol), Intermediate 5 (0.6 g, 1.0 mmol), 2-ethoxyethanol (15 mL) and DMF (15 mL) were added in sequence to a dry 100 mL round-bottom flask and heated to react for 5 days at 100° C. under N2 protection. After the reaction was cooled, the system was concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 2832 as a yellow solid (0.5 g, with a yield of 36%). The product was confirmed as the target product with a molecular weight of 1435.8.
Intermediate 6 (2.5 g, 2.7 mmol), Intermediate 7 (1.5 g, 3.0 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL) were added in sequence to a dry 250 mL round-bottom flask and heated to react for 5 days at 100° C. under N2 protection. The system was concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 1640 as a yellow solid (1.8 g, with a yield of 55%). The product was confirmed as the target product with a molecular weight of 1219.6.
Those skilled in the art will appreciate that the above preparation methods are merely exemplary. Those skilled in the art can obtain other compound structures of the present disclosure through the modifications of the preparation methods.
A glass substrate having an indium tin oxide (ITO) anode with a thickness of 80 nm (with a sheet resistance of 14-20 Ω/sq and an emissive area of 0.04 cm2) was cleaned and treated with oxygen plasma and UV ozone. After the treatment, the substrate was dried in a glovebox to remove moisture. Then, the substrate was mounted on a substrate holder and placed in a vacuum chamber. The organic layers specified below were sequentially deposited through vacuum thermal evaporation on the ITO anode at a rate of 0.2-2 Angstroms per second and a vacuum degree of about 10−8 Torr. Compound HT doped with Compound PD was used as a hole injection layer (HIL). Compound HT was used as a hole transporting layer (HTL). Compound PH-1 was used as an electron blocking layer (EBL). Metal Complex 2810 of the present disclosure was doped in Compound PH-1 and Compound H-40, all of which were co-deposited for use as an emissive layer (EML). On the EML, Compound H-2 was used as a hole blocking layer (HBL). On the HBL, Compound ET and 8-hydroxyquinolinolato-lithium (Liq) were co-deposited for use as an electron transporting layer (ETL). Finally, 8-hydroxyquinolinolato-lithium (Liq) was deposited for use as an electron injection layer with a thickness of 1 nm and Al was deposited for use as a cathode with a thickness of 120 nm. The device was transferred back to the glovebox and encapsulated with a glass lid and a moisture getter to complete the device.
Device Comparative Example 1 was implemented in the same manner as Device Example 1 except that in the EML, Metal Complex 2810 was replaced with Compound GD1.
Detailed structures and thicknesses of layers of the devices are shown in the following table. A layer using more than one material is obtained by doping different compounds at their weight ratio as recorded.
The materials used in the devices have the following structures:
The current-voltage-luminance (IVL) characteristics of the devices were measured. The CIE data, maximum emission wavelength λmax, full width at half maximum (FWHM), current efficiency (CE) and external quantum efficiency (EQE) of each device were measured at 1000 cd/m2 and the current efficiency (CE) and external quantum efficiency (EQE) of each device were measured at 11500 cd/m2. Capacitance testing was performed on the devices by using an impedance analyzer (Keysight E4990A). A direct current bias voltage of −4 V to 5 V was applied to the electrodes at two ends of the device, and a sinusoidal alternating current voltage signal of 100 mV was superimposed at the same time. The testing was performed at alternating current voltages with a frequency of 500 Hz, separately. The C-V curve of the device was measured to obtain the maximum capacitance (Cmax). The data are recorded and shown in Table 2.
As can be seen from the data in Table 2, the spectrum of Example 1 was blue-shifted by 9 nm compared with that of Comparative Example 1; at 1000 cd/m2, the CE of Example 1 was consistent with that of Comparative Example 1 and the EQE of Example 1 was slightly lower than that of Comparative Example 1; at a high luminance of 11500 cd/m2, the CE and EQE of Example 1 were higher than those of Comparative Example 1. Moreover, the maximum capacitance of Example 1 was 0.31 nF lower than that of Comparative Example 1. The above data indicate that the example having the features of the present disclosure has more saturated green light emission and a lower efficiency roll-off than Comparative Example 1, providing more options for the application of phosphorescent OLED materials and devices in high-brightness scenarios; meanwhile, the example having the features of the present disclosure has lower device capacitance than the Comparative Example and better facilitates an increase in the response rate of OLED display devices at a low grayscale and an increase in the refresh rate of the device.
Device Example 2 was implemented in the same manner as Device Example 1 except that in the EML, Metal Complex 2810 was replaced with Metal Complex 2832 of the present disclosure, where the ratio of Compound PH-1, Compound H-40 and Metal Complex 2832 was 47:47:6.
Device Comparative Example 2 was implemented in the same manner as Device Example 2 except that in the EML, Metal Complex 2832 was replaced with Compound GD2.
Detailed structures and thicknesses of layers of the devices are shown in the following table. A layer using more than one material is obtained by doping different compounds at their weight ratio as recorded.
The new materials used in the devices have the following structures:
The IVL characteristics of the devices were measured. The CIE data, maximum emission wavelength λmax, full width at half maximum (FWHM), current efficiency (CE) and external quantum efficiency (EQE) of each device were measured at 1000 cd/m2 and the current efficiency (CE) and external quantum efficiency (EQE) of each device were measured at 11500 cd/m2. Capacitance testing was performed on the devices by using an impedance analyzer (Keysight E4990A). A direct current bias voltage of −4 V to 5 V was applied to the electrodes at two ends of the device, and a sinusoidal alternating current voltage signal of 100 mV was superimposed at the same time. The testing was performed at alternating current voltages with a frequency of 500 Hz, separately. The C-V curve of the device was measured to obtain the maximum capacitance (Cmax). The data are recorded and shown in Table 4.
As can be seen from the data in Table 4, the spectrum of Example 2 was blue-shifted by 1 nm compared with that of Comparative Example 2; at 1000 cd/m2, the CE of Example 2 was consistent with that of Comparative Example 2 and the EQE of Example 2 was slightly lower than that of Comparative Example 2; at a high luminance of 11500 cd/m2, the CE of Example 2 was consistent with that of Comparative Example 2 and the EQE of Example 2 was slightly higher than that of Comparative Example 2. Moreover, the maximum capacitance of Example 2 was 1.57 nF lower than that of Comparative Example 2. The above data indicate that the example having the features of the present disclosure has more saturated green light emission and a lower efficiency roll-off than Comparative Example 2, providing more options for the application of the phosphorescent OLED materials and devices in the high-brightness scenarios; meanwhile, the example having the features of the present disclosure has lower device capacitance than the Comparative Example and better facilitates an increase in the response rate of the OLED display devices at a low grayscale and an increase in the refresh rate of the device.
The above results indicate that the metal complex of the present disclosure comprising the ligand La having the structure of Formula 1 and the ligand Lb having the structure of Formula 2 can obtain the more saturated green light emission, the lower efficiency roll-off and the lower device capacitance. The metal complex better facilitates the application of OLED materials and devices in the high-brightness scenarios, an increase in the response rate of the OLED display devices at a low grayscale and an increase in the refresh rate of the device. The metal complex of the present disclosure facilitates an improvement of the overall performance of the device and has great advantages and a broad prospect in industrial applications.
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 |
|---|---|---|---|
| 202311114556.9 | Aug 2023 | CN | national |
