Patent Application
20240109926
This application claims priority to Chinese Patent Application No. 202211022393.7 filed on Aug. 25, 2022, Chinese Patent Application No. 202310280294.7 filed on Mar. 22, 2023, and Chinese Patent Application No. 202310859895.3 filed on Jul. 13, 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 light-emitting devices. More particularly, the present disclosure relates to a metal complex comprising a ligand La having a structure of Formula 1, an organic electroluminescent device comprising the metal complex and a 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.
At present, full-color displays are widely applied to our work and life, such as a display of a mobile phone, a display of a computer and an advertising display in a shopping mall. The displays are mainly used for displaying texts, graphics, animations, videos and other information, and imaging display is performed by pixel units of the displays. Each pixel unit displays full-color pictures of different colors by controlling RGB subpixels and is composed of one or more RGB subpixels. The color reproduction generally refers to a color that can be exhibited by RGB subpixels in the display. BT.2020 is a current color gamut requirement with the highest color reproduction. The higher the BT.2020 coverage of the full-color display, the higher the color reproduction of the full-color display. Although the color gamut specification of BT.2020 is higher, the three primary colors of BT.2020 are too saturated, which is difficult for general devices to achieve. The color coordinates of the red, green and blue primary colors are required to be (0.708, 0.292), (0.131, 0.046) and (0.170, 0.797) in BT. 2020, respectively. At present, both a red light device and a blue light device in a commonly used display panel can basically meet the color gamut requirement. However, the display panel is mainly limited by the performance of a green light device. At present, the green light device does not meet the color gamut requirement, and a color coordinate of the green light device needs to be adjusted to be close to the requirement of BT.2020.
CN111655705A has disclosed a metal complex having the following structure:
where R5 is selected from groups such as halogen, a nitrile group, a nitro group, . . . and substituted or unsubstituted alkyl having 3 to 30 carbon atoms, and CN111655705A has further disclosed the following specific structures:
The application does not disclose or teach other particular substituents which are present at particular positions while a quaternary carbon atom is present at a position of Rs in the metal complex and an effect of the metal complex on device performance.
The present disclosure aims to provide a series of metal complexes each comprising a ligand La having a structure of Formula 1 to solve at least part of the above-mentioned problems, where the ligand La has a (6-5-6)-multi-membered fused cyclic structural unit and comprises particular substituents R1 and Rn. These new metal complexes are applied to electroluminescent devices so that very excellent device performance can be obtained, the luminescence performance of the devices can be significantly improved, more saturated luminescence can be obtained and a BT.2020 requirement for commercial application is met.
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 La has a structure represented by Formula 1:
According to another embodiment of the present disclosure, further disclosed is an organic electroluminescent device, which comprises an anode, a cathode and an organic layer disposed between the anode and the cathode, wherein at least one layer of the organic layer comprises the metal complex in the preceding embodiment.
According to another embodiment of the present disclosure, further disclosed is a composition, which comprises the metal complex in the preceding embodiment.
The present disclosure discloses the series of metal complexes each comprising the ligand La having the structure of Formula 1 to solve at least part of the above-mentioned problems, where the ligand La has the (6-5-6)-multi-membered fused cyclic structural unit and comprises the particular substituents R1 and Rn. These new compounds are applied to the electroluminescent devices so that very excellent device performance can be obtained, full widths at half maximum of emission spectra can be further reduced while high performance of the devices can be maintained, the luminescence saturation of the devices can be improved and the devices can have high efficiency under a condition of being closer to a BT.2020 commercial luminescence requirement.
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.
As used herein, the term “color coordinates” refers to the corresponding coordinates in the CIE 1931 color space.
A structure of a typical top-emitting OLED device is shown in
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 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.
Definition of Terms of Substituents
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 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 a 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, a substituted hydroxyl group, a substituted sulfanyl 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, hydroxyl group, sulfanyl 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 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 La has a structure represented by Formula 1:
In the present disclosure, the expression that “adjacent substituents R can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents R, can be joined to form a ring. Obviously, it is also possible that none of these substituents are joined to form a ring.
In the present disclosure, the expression that “adjacent substituents R′ and Rx can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents R′, two substituents Rx, and substituents R′ and Rx, can be joined to form a ring. Obviously, it is also possible that none of these substituents are joined to form a ring.
In the present disclosure, the expression that “adjacent substituents R2, R3 and R4 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 R2 and R3, substituents R2 and R4, and substituents R4 and R3, 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,
in Formula 1 is, at each occurrence identically or differently, selected from any one of the following structures:
represents a position where X1, X2 or X3 is joined.
According to an embodiment of the present disclosure, the metal complex has a general formula of M(La)m(Lb)n(Lc)q;
According to an embodiment of the present disclosure, Lb and Lc are, at each occurrence identically or differently, selected from a structure represented by any one of the group consisting of:
In the present disclosure, the expression that “adjacent substituents Ra, Rb, Rc, RN1, RC1 and RC2 can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents Ra, two substituents Rb, substituents Ra and Rb, substituents Ra and Rc, substituents Rb and Rc, substituents Ra and RN1, substituents Rb and RN1, substituents Ra and RC1, substituents Ra and RC2, substituents Rb and RC1, substituents Rb and RC2, and substituents RC1 and RC2, can be joined to form a ring. Obviously, it is also possible that none of these substituents are joined to form a ring. For example, adjacent substituents Ra and Rb in
can be optionally joined to form a ring. When Ra is optionally joined to form a ring,
may form a structure of
According to an embodiment of the present disclosure, 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 Ir.
According to an embodiment of the present disclosure, G1 and G2 are selected from a single bond.
According to an embodiment of the present disclosure, Y1 is selected from C.
According to an embodiment of the present disclosure, the metal complex has a general formula structure of Ir(La)m(Lb)3-m, and the structure is represented by Formula 3:
In the present disclosure, the expression that “adjacent substituents Ru can be optionally joined to form a ring” is intended to mean that any one or more of groups of adjacent substituents, such as two substituents Ru, 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, Z is 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, L is selected from the group consisting of: a single bond, substituted or unsubstituted alkylene having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkylene having 4 to 10 carbon atoms, substituted or unsubstituted arylene having 6 to 12 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, L is selected from a single bond and substituted or unsubstituted methylene.
According to an embodiment of the present disclosure, R2, R3 and R4 are, 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, a cyano group and combinations thereof.
According to an embodiment of the present disclosure, R2, R3 and R4 are, at each occurrence identically or differently, selected from the group consisting of: fluorine, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, a cyano group and combinations thereof.
According to an embodiment of the present disclosure, R2, R3 and R4 are, at each occurrence identically or differently, selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms.
According to an embodiment of the present disclosure, R2, R3 and R4 are, 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, X3 to X6 are, at each occurrence identically or differently, selected from CRx.
According to an embodiment of the present disclosure, X3 to X6 are, at each occurrence identically or differently, selected from CRx or N, and at least one of X3 to X6 is N. For example, one of X3 to X6 is selected from N, or two of X3 to X6 are selected from N.
According to an embodiment of the present disclosure, X6 is selected from N.
According to an embodiment of the present disclosure, Y3 to Y6 are, at each occurrence identically or differently, selected from CR.
According to an embodiment of the present disclosure, Y3 to Y6 are, at each occurrence identically or differently, selected from CR 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, Rx and R are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, a cyano group and combinations thereof.
According to an embodiment of the present disclosure, Rx and R 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, a cyano group and combinations thereof.
According to an embodiment of the present disclosure, Rx and R are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, a cyano group, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, 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 R 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 R 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, Y3 to Y6 are, at each occurrence identically or differently, selected from CR, and R 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 alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanyl having 3 to 20 carbon atoms, a cyano group and combinations thereof.
According to an embodiment of the present disclosure, Y3 to Y6 are, at each occurrence identically or differently, selected from CR, and R 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 and combinations thereof.
According to an embodiment of the present disclosure, at least one of X3 to X6 is selected from CRx, and Rx is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted 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 one of X3 to X6 is selected from CRx, and Rx is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, a cyano group and combinations thereof.
According to an embodiment of the present disclosure, at least one of X3 to X6 is selected from CRx, and Rx is selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms or a combination thereof.
According to an embodiment of the present disclosure, X6 is selected from CRx, and Rx is selected from 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 or a combination thereof.
According to an embodiment of the present disclosure, X6 is selected from CRx, and Rx is selected from substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms or a combination thereof.
According to an embodiment of the present disclosure, X6 is selected from CRx, and Rx is selected from substituted or unsubstituted aryl having 6 to 18 carbon atoms.
According to an embodiment of the present disclosure, X6 is selected from CRx, and Rx is selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted phenanthryl, substituted or substituted anthryl or a combination thereof.
According to an embodiment of the present disclosure, at least one R is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 12 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, at least one R 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, Rn is, at each occurrence identically or differently, selected from the group consisting of:
wherein optionally, hydrogens in the above Rn can be partially or fully substituted with deuterium.
According to an embodiment of the present disclosure, U1 to U8 are, at each occurrence identically or differently, selected from CRu.
According to an embodiment of the present disclosure, U1 to U8 are, at each occurrence identically or differently, selected from CRu or N, and at least one of U1 to Us is selected from N. For example, one of U1 to U8 is selected from N, or two of U1 to U8 are selected from N.
According to an embodiment of the present disclosure, Ru is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group and combinations thereof.
According to an embodiment of the present disclosure, Ru is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, 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 and combinations thereof.
According to an embodiment of the present disclosure, Ru is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl having 6 to 12 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, Ru is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, a cyano group, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, 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 or at least two of U1 to U8 are selected from CRu, Ru is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms or a combination thereof, and the total number of carbon atoms in all of Ru is at least 4.
According to an embodiment of the present disclosure, at least one or at least two of Us to U8 are selected from CRu, Ru is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms or a combination thereof, and the total number of carbon atoms in all of Ru is at least 4.
According to an embodiment of the present disclosure, at least one or at least two of U1 to U4 are selected from CRu, Ru is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms or a combination thereof, and the total number of carbon atoms in all of Ru is at least 4.
According to an embodiment of the present disclosure, U6 or U7 is selected from CRu, and Ru is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms or a combination thereof.
According to an embodiment of the present disclosure, U6 or U7 is selected from CRu, and Ru is selected from substituted or unsubstituted alkyl having 4 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 4 to 20 ring carbon atoms or a combination thereof.
According to an embodiment of the present disclosure, at least one of U1 to U4 is selected from CRu, at least one of Y3 to Y6 is selected from CR, Ru and R are selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms or a combination thereof, and the total number of carbon atoms in Ru and R is greater than or equal to 2.
According to an embodiment of the present disclosure, at least one of U5 to U8 is selected from CRu, at least one of Y3 to Y6 is selected from CR, Ru and R are selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms or a combination thereof, and the total number of carbon atoms in Ru and R is greater than or equal to 2.
According to an embodiment of the present disclosure, at least one of U1 to U4 is selected from CRu, at least one of U5 to U8 is selected from CRu, Ru is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms or a combination thereof, and the total number of carbon atoms in Ru is greater than or equal to 2.
According to an embodiment of the present disclosure, R′ is, at each occurrence identically or differently, selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms or substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms.
According to an embodiment of the present disclosure, R′ is methyl or deuterated methyl.
According to an embodiment of the present disclosure, La is, at each occurrence identically or differently, selected from the group consisting of La1 to La3530, wherein the specific structures of La1 to La3530 are referred to claim 15.
According to an embodiment of the present disclosure, hydrogens in La1 to La3530 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 Lb151, wherein the specific structures of Lb1 to Lb151 are referred to claim 16.
According to an embodiment of the present disclosure, hydrogens in Lb1 to Lb18, Lb20 to Lb26 and Lb31 to Lb151 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:
According to an embodiment of the present disclosure, the metal complex has a structure of Ir(La)3, IrLa(Lb)2, Ir(La)2Lb, Ir(La)2Lc, IrLa(Lc)2 or IrLaLbLc, wherein the ligand La is, at each occurrence identically or differently, selected from any one, any two or any three of the group consisting of La1 to La3530, the ligand Lb is, at each occurrence identically or differently, selected from any one or any two of the group consisting of Lb1 to Lb151, and the ligand Lc is, at each occurrence identically or differently, selected from any one or any two of the group consisting of Lc1 to Lc50.
According to an embodiment of the present disclosure, the metal complex is selected from the group consisting of Metal Complex 1 to Metal Complex 3806, wherein the specific structures of Metal Complex 1 to Metal Complex 3806 are referred to claim 17.
According to an embodiment of the present disclosure, further disclosed is an organic electroluminescent device, which comprises an anode, a cathode and an organic layer disposed between the anode and the cathode, wherein at least one layer of the organic layer comprises the metal complex in any one of the preceding embodiments.
According to an embodiment of the present disclosure, in the organic electroluminescent device, the organic layer comprising the metal complex is a light-emitting layer.
According to an embodiment of the present disclosure, the organic electroluminescent device emits green light.
According to an embodiment of the present disclosure, the organic electroluminescent device emits white light.
According to an embodiment of the present disclosure, in the organic electroluminescent device, the light-emitting layer further comprises a first host compound.
According to an embodiment of the present disclosure, in the organic electroluminescent device, the light-emitting layer further comprises a first host compound and a second host compound.
According to an embodiment of the present disclosure, in the electroluminescent device, 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, wherein the second host compound has a structure represented by Formula 5:
Herein, the expression that “adjacent substituents Re, RQ, 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 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, in the electroluminescent device, the metal complex is doped in the first host compound and the second host compound, and the weight of the metal complex accounts for 1% to 30% of the total weight of the emissive layer.
According to an embodiment of the present disclosure, in the electroluminescent device, the metal complex is doped in the first host compound and the second host compound, and the weight of the metal complex accounts for 3% to 13% of the total weight of the emissive layer.
According to an embodiment of the present disclosure, the organic electroluminescent device further comprises a hole injection layer. The hole injection layer may be a functional layer containing a single material or a functional layer containing multiple materials, wherein the contained multiple materials which are the most commonly used are hole transport materials doped with a certain proportion of p-type conductive doping material. Common p-type doped materials are as follows:
According to another embodiment of the present disclosure, further disclosed is a composition, which comprises a metal complex whose specific structure is as shown in any one of the preceding embodiments.
Combination with Other Materials
The materials described in the present disclosure for a particular layer in an organic light-emitting device can be used in combination with various other materials present in the device. The combinations of these materials are described in more detail in U.S. Pat. App. 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. App. 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.
Intermediate 1 (1.8 g, 2.2 mmol), Intermediate 2 (1.0 g, 2.4 mmol), 2-ethoxyethanol (30 mL) and dimethylformamide (DMF) (30 mL) were sequentially added to a dry 250 mL round-bottom flask and heated to react for 144 h at 100° C. under N2 protection. The reaction was cooled and filtered through Celite. The reaction was washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 1345 as a yellow solid (1.3 g, 1.2 mmol, with a yield of 55%). The product was confirmed as the target product with a molecular weight of 1019.4 and a melting point of 407° C.
Intermediate 3 (0.7 g, 0.8 mmol), Intermediate 4 (0.4 g, 1.0 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL) were sequentially added to a dry 250 mL round-bottom flask and heated to react for 144 h at 100° C. under N2 protection. The reaction was cooled and filtered through Celite. The reaction was washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 2252 as a yellow solid (0.4 g, 0.3 mmol, with a yield of 38%). The product was confirmed as the target product with a molecular weight of 1131.5.
Intermediate 1 (2.8 g, 3.4 mmol), Intermediate 5 (2.0 g, 4.7 mmol), 2-ethoxyethanol (40 mL) and DMF (40 mL) were sequentially added to a dry 250 mL round-bottom flask and heated to react for 144 h at 100° C. under N2 protection. The reaction was cooled and filtered through Celite. The reaction was washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 1583 as a yellow solid (1.6 g, 1.6 mmol, with a yield of 47%). The product was confirmed as the target product with a molecular weight of 1033.4 and a melting point of 354° C.
Intermediate 1 (1.2 g, 1.5 mmol), Intermediate 6 (0.9 g, 1.8 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL) were sequentially added to a dry 250 mL round-bottom flask and heated to react for 144 h at 100° C. under N2 protection. The reaction was cooled and filtered through Celite. The reaction was washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 1493 as a yellow solid (0.72 g, 0.65 mmol, with a yield of 43%). The product was confirmed as the target product with a molecular weight of 1106.4 and a melting point of 363° C.
Intermediate 7 (2.6 g, 2.8 mmol), Intermediate 2 (1.7 g, 4.2 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL) were sequentially added to a dry 250 mL round-bottom flask and heated to react for 144 h at 100° C. under N2 protection. The reaction was cooled and filtered through Celite. The reaction was washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 2262 as a yellow solid (2.0 g, 1.8 mmol, with a yield of 63%). The product was confirmed as the target product with a molecular weight of 1131.5 and a melting point of 388° C.
Intermediate 8 (1.4 g, 1.8 mmol), Intermediate 2 (1.0 g, 2.5 mmol), 2-ethoxyethanol (25 mL) and DMF (25 mL) were sequentially added to a dry 250 mL round-bottom flask and heated to react for 144 h at 100° C. under N2 protection. The reaction was cooled and filtered through Celite. The reaction was washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 2164 as a yellow solid (0.6 g, 0.6 mmol, with a yield of 34%). The product was confirmed as the target product with a molecular weight of 975.4 and a melting point of 451° C.
Intermediate 7 (1.2 g, 1.3 mmol), Intermediate 9 (1.0 g, 2.0 mmol), 2-ethoxyethanol (20 mL) and DMF (20 mL) were sequentially added to a dry 250 mL round-bottom flask and heated to react for 144 h at 100° C. under N2 protection. The reaction was concentrated under reduced pressure and filtered through Celite. The reaction was washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected and purified through column chromatography to obtain Metal Complex 2394 as a yellow solid (1.1 g, 0.9 mmol, with a yield of 70%). The product was confirmed as the target product with a molecular weight of 1215.5 and a melting point of 426° C.
Intermediate 8 (1.3 g, 1.7 mmol), Intermediate 10 (1.0 g, 2.0 mmol), 2-ethoxyethanol (20 mL) and DMF (20 mL) were sequentially added to a dry 250 mL round-bottom flask and heated to react for 144 h at 100° C. under N2 protection. The reaction was cooled and filtered through Celite. The reaction was washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 2955 as a yellow solid (0.6 g, 0.6 mmol, with a yield of 33%). The product was confirmed as the target product with a molecular weight of 1083.5 and a melting point of 379° C.
Intermediate 11 (3.0 g, 3.6 mmol), Intermediate 12 (2.5 g, 5.0 mmol), 2-ethoxyethanol (50 mL) and DMF (50 mL) were sequentially added to a dry 250 mL round-bottom flask and heated to react for 144 h at 100° C. under N2 protection. The reaction was cooled and filtered through Celite. The reaction was washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 982 as a yellow solid (2.0 g, 1.8 mmol, with a yield of 49%). The product was confirmed as the target product with a molecular weight of 1139.5 and a melting point of 364° C.
Intermediate 7 (2.7 g, 3.3 mmol), Intermediate 13 (2.5 g, 4.9 mmol), 2-ethoxyethanol (50 mL) and DMF (50 mL) were sequentially added to a dry 250 mL round-bottom flask and heated to react for 144 h at 100° C. under N2 protection. The reaction was cooled and filtered through Celite. The reaction was washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 3671 as a yellow solid (1.6 g, 1.3 mmol, with a yield of 39%). The product was confirmed as the target product with a molecular weight of 1279.6 and a melting point of 385° C.
Intermediate 7 (4.8 g, 5.1 mmol), Intermediate 14 (4.0 g, 6.6 mmol), 2-ethoxyethanol (80 mL) and DMF (80 mL) were sequentially added to a dry 250 mL round-bottom flask and heated to react for 144 h at 100° C. under N2 protection. The reaction was cooled and filtered through Celite. The reaction was washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 2526 as a yellow solid (5.2 g, 3.9 mmol, with a yield of 76%). The product was confirmed as the target product with a molecular weight of 1327.7 and a melting point of 383° C.
Intermediate 7 (5.1 g, 5.4 mmol), Intermediate 15 (3.6 g, 6.0 mmol), 2-ethoxyethanol (50 mL) and DMF (50 mL) were sequentially added to a dry 250 mL round-bottom flask and heated to react for 96 h at 100° C. under N2 protection. The reaction was cooled and filtered through Celite. The reaction was washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 2657 as a yellow solid (6.0 g, 4.7 mmol, with a yield of 87%). The product was confirmed as the target product with a molecular weight of 1327.7 and a melting point of 422° C.
Intermediate 1 (0.7 g, 0.8 mmol), Intermediate 16 (0.5 g, 1.0 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL) were sequentially added to a dry 250 mL round-bottom flask and heated to react for 144 h at 100° C. under N2 protection. The reaction was cooled and filtered through Celite. The reaction was washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 1371 as a yellow solid (0.28 g, 0.25 mmol, with a yield of 31%). The product was confirmed as the target product with a molecular weight of 1090.4 and a melting point of 421° C.
Intermediate 7 (1.8 g, 1.9 mmol), Intermediate 16 (1.3 g, 2.7 mmol), 2-ethoxyethanol (40 mL) and DMF (40 mL) were sequentially added to a dry 250 mL round-bottom flask and heated to react for 144 h at 100° C. under N2 protection. The reaction was cooled and filtered through Celite. The reaction was washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 2393 as a yellow solid (1.4 g, 1.2 mmol, with a yield of 63%). The product was confirmed as the target product with a molecular weight of 1202.5 and a melting point of 350° C.
Intermediate 7 (1.5 g, 1.6 mmol), Intermediate 6 (1.1 g, 2.2 mmol), 2-ethoxyethanol (40 mL) and DMF (40 mL) were sequentially added to a dry 250 mL round-bottom flask and heated to react for 144 h at 100° C. under N2 protection. The reaction was cooled and filtered through Celite. The reaction was washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 2921 as a yellow solid (1.3 g, 1.1 mmol, with a yield of 69%). The product was confirmed as the target product with a molecular weight of 1218.6 and a melting point of 387° C.
Intermediate 18 (1.7 g, 1.8 mmol), Intermediate 19 (1.0 g, 2.4 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL) were sequentially added to a dry 250 mL round-bottom flask and heated to react for 144 h at 100° C. under N2 protection. The reaction was cooled and filtered through Celite. The reaction was washed twice with methanol and n-hexane separately. Yellow solids on the Celite were dissolved with dichloromethane. The organic phases were collected, concentrated under reduced pressure and purified through column chromatography to obtain Metal Complex 2249 as a yellow solid (0.9 g, 0.8 mmol, with a yield of 44%). The product was confirmed as the target product with a molecular weight of 1156.5 and a melting point of 439° C.
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.
Firstly, a glass substrate having an indium tin oxide (ITO) anode with a thickness of 80 nm was cleaned and then treated with oxygen plasma and UV ozone. After the treatment, the substrate was dried in a glovebox to remove moisture. Then, the substrate was mounted on a substrate holder and placed in a vacuum chamber. Organic layers specified below were sequentially deposited through vacuum thermal evaporation on the ITO anode at a rate of 0.2 to 2 Angstroms per second and a vacuum degree of about 10−6 torr. Compound HI was used as a hole injection layer (HIL). Compound HT was used as a hole transporting layer (HTL). Compound PH-23 was used as an electron blocking layer (EBL). Metal Complex 1345 of the present disclosure was doped in Compound PH-23 and Compound H-40, all of which were co-deposited for use as an emissive layer (EML). On the EML, Compound 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.
The implementation mode in Device Example 2 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 1345 of the present disclosure was replaced with Metal Complex 1583.
The implementation mode in Device Comparative Example 1 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 1345 of the present disclosure was replaced with Compound GD1.
The implementation mode in Device Comparative Example 2 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 1345 of the present disclosure was replaced with Compound GD2.
The implementation mode in Device Comparative Example 3 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 1345 of the present disclosure was replaced with Compound GD3.
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 TVL characteristics of the devices were measured. The CIE data, maximum emission wavelength (λmax), full width at half maximum (FWHM), drive voltage (V), current efficiency (CE) and external quantum efficiency (EQE) of the devices were measured at a constant current of 10 mA/cm2. The data are recorded and shown in Table 2.
Examples 1 and 2 differ from Comparative Examples 1 and 2 respectively only in the presence or absence of a Rn group represented by Formula 2 of the present disclosure in the luminescent material. It can be seen from the data in Table 2 that compared with Comparative Examples 1 and 2, respectively, in Examples 1 and 2, the drive voltage was maintained substantially the same or slightly reduced and both the current efficiency and the external quantum efficiency were maintained substantially the same or slightly improved. However, unexpectedly, compared with the full widths at half maximum in Comparative Examples 1 and 2 that have been considered relatively narrow, the full widths at half maximum in Examples 1 and 2 were further narrowed. Compared with Comparative Example 1, the full widths at half maximum in Examples 1 and 2 were narrowed by 5.5 nm and 3.2 nm, respectively, and compared with Comparative Example 2, the full widths at half maximum in Examples 1 and 2 were narrowed by 4.4 nm and 2.1 nm, respectively. It is to be emphasized that the full widths at half maximum in Comparative Examples 1 and 2 have reached a relative high level in the industry, and it is very rare to further reduce the full widths at half maximum on the premise that the device efficiency and the voltages are maintained substantially comparable. Such a result is unexpected. With a narrower full width at half maximum, a higher color purity can be obtained, which is closer to a requirement of the industry for the luminescence performance of a green light material, indicating that with the metal complex provided in the present disclosure, a device with more excellent performance can be obtained.
Although the metal complex GD3 used in Comparative Example 3 has the substituent Rn of the present disclosure, the metal complex GD3 does not have the substituent R1 of the present application. From the data in Table 2, compared with Comparative Example 3, in Examples 1 and 2, the full widths at half maximum were narrowed by 28.2 nm and 25.9 nm, respectively, the EQE was improved by 20.5% and 19.7%, respectively, and the CE was improved by 24.2% and 23.3%, respectively.
Moreover, it can also be seen from the data in Table 2 that Examples 1 and 2 were blue-shifted by 9 nm compared with Comparative Example 1, but red-shifted by 2 nm compared with Comparative Example 2. Such a result is completely different from the result disclosed in CN111655705A and is an unpredictable result for those skilled in the art.
From the above, it can be seen that in the present application, the metal complex comprising both the substituents R1 and Rn can reduce the full width at half maximum in the case where excellent device efficiency is maintained, which is conducive to providing a high-performance device with more saturated luminescence.
The implementation mode in Device Example 3 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 1345 of the present disclosure was replaced with Metal Complex 2252.
The implementation mode in Device Comparative Example 4 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 1345 of the present disclosure was replaced with Compound GD4.
Detailed structures and thicknesses of layers of the devices are shown in the following table. A layer using more than one material is obtained by doping different compounds at their weight ratio as recorded.
The new metal complexes used in the devices have the following structures:
The TVL characteristics of the devices were measured. The CIE data, maximum emission wavelength (λmax), full width at half maximum (FWHM), drive voltage (V), current efficiency (CE) and external quantum efficiency (EQE) of the devices were measured at 10 mA/cm2. The data are recorded and shown in Table 4.
Example 3 differs from Comparative Example 4 only in the presence or absence of a Rn group represented by Formula 2 of the present disclosure in the luminescent material. It can be seen from the data in Table 4 that although the device voltage was improved by 0.2 V and the efficiency was reduced by 5.3%, Example 3 still reached a relatively high level of greater than 23%. More importantly, the emission wavelength in Example 3 was blue-shifted by 10 nm compared with that in Comparative Example 4, and the full width at half maximum in Example 3 was narrowed by 6.1 nm compared with that in Comparative Example 4. A more blue emission wavelength and a narrower full width at half maximum in Example 3 compared with those in Comparative Example 4 can enable the device to have a wider color gamut and a higher color purity, which is closer to a requirement of the industry for the luminescence performance of a green light material, indicating that with the metal complex provided in the present disclosure, a device with more excellent performance can be obtained.
The implementation mode in Device Example 4 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 1345 of the present disclosure was replaced with Metal Complex 1493.
The implementation mode in Device Comparative Example 5 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 1345 of the present disclosure was replaced with Compound GD5.
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 metal complexes 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), drive voltage (V), current efficiency (CE) and external quantum efficiency (EQE) of the devices were measured at a constant current of 10 mA/cm2. The data are recorded and shown in Table 6.
Example 4 differs from Comparative Example 5 only in the presence or absence of a Rn group represented by Formula 2 of the present disclosure in the luminescent material. It can be seen from the data in Table 6 that compared with Comparative Example 5, in Example 4, the drive voltage was reduced by 0.12 V, the current efficiency was slightly reduced, the external quantum efficiency was slightly improved, the emission wavelength was blue-shifted by 10 nm and the full width at half maximum was narrowed by 3.4 nm. Again, it indicates that the metal complex of the present disclosure can have a wider color gamut and a higher color purity on the premise that excellent device performance is maintained, which is closer to a requirement of the industry for the luminescence performance of a green light material, indicating that with the metal complex provided in the present disclosure, a device with more excellent performance can be obtained.
Examples of top-emitting devices: To study the device performance of the metal complex most approaching the BT.2020 luminescence requirement, the microcavities of the following top-emitting devices were all adjusted to CIEx=0.170, and the device performance at this time was recorded. As mentioned above about the top-emitting device, due to different refractive indexes of different metal complexes, the top-emitting devices comprising these different metal complexes may have slightly different microcavity lengths, that is, the HTLs have slightly different thicknesses.
Firstly, a 0.7 mm thick glass substrate was pre-patterned with ITO 75 Å/Ag 1500 Å/ITO 150 Å as an anode, where 150 Å ITO deposited on Ag had a hole injection function. Then, the substrate was dried in a glovebox to remove moisture, mounted on a holder and transferred into a vacuum chamber. Organic layers specified below were sequentially deposited through vacuum thermal evaporation on the anode at a rate of 0.01 to 10 Å/s and a vacuum degree of about 10−6 torr. Compound HT and Compound PD were co-deposited as a hole injection layer (HIL, 97:3, 100 Å). On the HIL, Compound HT was deposited as a hole transporting layer (HTL) (where the HTL also served as a microcavity adjustment layer, and the microcavity was adjusted within a range of 1000 to 1500 Å). On the HTL, Compound PH-23 was deposited as an electron blocking layer (EBL, 50 Å). Then, Metal Complex 1493, Compound PH-1, and Compound H-40 of the present disclosure were co-deposited as an emissive layer (EML, 4:48:48, 400 Å). Compound H-2 was deposited as a hole blocking layer (HBL, 50 Å). Compound ET and Liq were co-deposited as an electron transporting layer (ETL, 40:60, 350 Å). A metal Yb was deposited as an electron injection layer (EIL, 10 Å). Metals Ag and Mg were co-deposited at a ratio of 9:1 as a cathode (140 Å). Compound CP (a material with a refractive index of about 2.01 at 530 nm) was deposited as a capping layer with a thickness of 800 Å. The device was transferred back to the glovebox and encapsulated with a glass lid in a nitrogen atmosphere to complete the device. In this example, when the microcavity was adjusted to about 1340 Å, CIEx of the device was 0.170, and CE0.170 in this case was obtained.
The implementation mode in Device Example 6 was the same as that in Device Example 5, except that in the emissive layer, Metal Complex 1493 of the present disclosure was replaced with Metal Complex 1345 of the present disclosure. In this example, when the microcavity was adjusted to about 1370 Å, CIEx of the device was 0.170, and CE0.170 in this case was obtained.
The implementation mode in Device Comparative Example 6 was the same as that in Device Example 5, except that in the emissive layer, Metal Complex 1493 of the present disclosure was replaced with Metal Complex GD5 of the present disclosure. In this example, when the microcavity was adjusted to about 1410 Å, CIEx of the device was 0.170, and CE0.170 in this case was obtained.
The implementation mode in Device Comparative Example 7 was the same as that in Device Example 5, except that in the emissive layer, Metal Complex 1493 of the present disclosure was replaced with Metal Complex GD2 of the present disclosure. In this example, when the microcavity was adjusted to about 1370 Å, CIEx of the device was 0.170, and CEA)70 in this case was obtained.
Structures and thicknesses of part 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 at a constant current of 10 mA/cm2. The corresponding color coordinate, current efficiency (CE0.170) and external quantum efficiency (EQE0.170) of the devices are recorded when x=0.170 in the color coordinate CIE (x, y) of the devices. The data are recorded and shown in Table 8.
It can be seen from the data in Table 8 that when CIEx=0.170 in the color coordinates CIE (x, y) in Example 5 and Comparative Example 6, both the color coordinates in Example 5 and Comparative Example 6 were close to the green coordinate CIE (0.170, 0.797) in BT.2020, that is, both Example 5 and Comparative Example 6 had a relatively saturated green light emission. However, in this case, compared with Comparative Example 6, the current efficiency and the external quantum efficiency in Example 5 were improved by 16.3% and 16.4%, respectively, both of which are significantly improved. It indicates that the technical solution provided in the present disclosure is used so that a device with more excellent performance and close to the BT.2020 luminescence requirement can be obtained and excellent device performance can be maintained under the luminescence requirement.
Similarly, when CIEx=0.170 in the color coordinates CIE (x, y) in Example 6 and Comparative Example 7, both the color coordinates in Example 6 and Comparative Example 7 were close to the green coordinate CIE (0.170, 0.797) in BT.2020, that is, both Example 6 and Comparative Example 7 had a relatively saturated green light emission. However, in this case, compared with Comparative Example 7, both the current efficiency and the external quantum efficiency in Example 6 were improved by about 5%. It indicates that the technical solution provided in the present disclosure is used so that a device with more excellent performance and close to the BT.2020 luminescence requirement can be obtained and excellent device performance can be maintained under the luminescence requirement.
The implementation mode in Device Example 7 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 1345 of the present disclosure was replaced with Metal Complex 2262.
The implementation mode in Device Example 8 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 1345 of the present disclosure was replaced with Metal Complex 2164.
The implementation mode in Device Example 9 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 1345 of the present disclosure was replaced with Metal Complex 2394.
The implementation mode in Device Example 10 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 1345 of the present disclosure was replaced with Metal Complex 2955.
The implementation mode in Device Example 11 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 1345 of the present disclosure was replaced with Metal Complex 982.
The implementation mode in Device Example 12 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 1345 of the present disclosure was replaced with Metal Complex 3671.
The implementation mode in Device Example 13 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 1345 of the present disclosure was replaced with Metal Complex 2526, and in the HIL, Compound HI was replaced with Compound HT:Compound PD=97:3.
The implementation mode in Device Example 14 was the same as that in Device Example 13, except that in the emissive layer (EML), Metal Complex 2526 of the present disclosure was replaced with Metal Complex 2657.
The implementation mode in Device Example 15 was the same as that in Device Example 1, except that in the emissive layer (EML), Metal Complex 1345 of the present disclosure was replaced with Metal Complex 1371.
The implementation mode in Device Example 16 was the same as that in Device Example 13, except that in the emissive layer (EML), Metal Complex 2526 of the present disclosure was replaced with Metal Complex 2393.
The implementation mode in Device Example 17 was the same as that in Device Example 13, except that in the emissive layer (EML), Metal Complex 2526 of the present disclosure was replaced with Metal Complex 2921.
The implementation mode in Device Example 18 was the same as that in Device Example 13, except that in the emissive layer (EML), Metal Complex 2526 of the present disclosure was replaced with Metal Complex 2249.
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), drive voltage (V), current efficiency (CE) and external quantum efficiency (EQE) of the devices were measured at a constant current of 10 mA/cm2. The data are recorded and shown in Table 10.
As can be seen from the data in Table 10, the luminescent materials used in Examples 7 to 18 each comprised the ligand La having a structure of Formula 1 of the present application. The devices of Examples 7 to 18 all had a deep green light emission, a narrow full width at half maximum and external quantum efficiency (EQE) of 24% or more at a deep green emission wavelength, reaching a relatively high level in the art, where Examples 10, 12 to 14 and 17 all reached external quantum efficiency (EQE) of 25.5% or more, and in particular, Examples 13 and 14 even reached surprising external quantum efficiency (EQE) of 27.02% and 27.25%, respectively. It also indicates that in the present application, the metal complexes each comprising the ligand La having the structure of Formula 1 comprising different substituents can all obtain excellent device performance. Moreover, in the present application, the ligand La having the structure of Formula 1 matched with different ligands Le can also obtain excellent device performance.
The above results indicate that in the present application, the metal complex comprising the ligand La having the structure of Formula 1 comprising specific substituents R1 and Rn is applied to an organic electroluminescent device so that a full width at half maximum of an emission spectrum can be further reduced while high performance of the device can be maintained, the luminescence saturation of the device can be improved and the device can have high efficiency under a condition of being closer to a BT.2020 commercial luminescence requirement. Therefore, in the present application, the metal complex comprising the ligand La having the structure of Formula 1 comprising specific substituents R1 and Rn is a high-performance luminescent material with a commercial application prospect.
It is to be understood that various embodiments described herein are merely examples and not intended to limit the scope of the present disclosure. Therefore, it is apparent to the persons skilled in the art that the present disclosure as claimed may include variations of specific embodiments and preferred embodiments described herein. Many of materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the present disclosure. It is to be understood that various theories as to why the present disclosure works are not intended to be limitative.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202211022393.7 | Aug 2022 | CN | national |
| 202310280294.7 | Mar 2023 | CN | national |
| 202310859895.3 | Jul 2023 | CN | national |
