Patent Application
20220109118
This application claims priority to Chinese Patent Application No. CN 202010362117.X filed on Apr. 30, 2020, Chinese Patent Application No. CN 202011219604.7 filed on Nov. 9, 2020, and Chinese Patent Application No. CN 202110348602.6 filed on Apr. 1, 2021, the disclosures of which are incorporated herein by reference in their entirety.
The present disclosure relates to compounds used in organic electronic devices such as organic light-emitting devices. More particularly, the present disclosure relates to a metal complex with a polycyclic ligand and an electroluminescent device and a compound composition including 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 comprises 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 comprise 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 comprise one emitting layer or a plurality of emitting layers to achieve desired spectrum. In the case of green, yellow, and red OLEDs, phosphorescent emitters have successfully reached commercialization. Blue phosphorescent device still suffers from non-saturated blue color, short device lifetime, and high operating voltage. Commercial full-color OLED displays normally adopt a hybrid strategy, using fluorescent blue and phosphorescent yellow, or red and green. At present, efficiency roll-off of phosphorescent OLEDs at high brightness remains a problem. In addition, it is desirable to have more saturated emitting color, higher efficiency, and longer device lifetime.
Phosphorescent metal complexes can be used as phosphorescent doping materials of light-emitting layers and applied to the field of organic electroluminescence lighting or display.
CN110698518A discloses a metal complex with a structure of
wherein X is N or P. One of many structures disclosed is
This disclosure has discussed the improvement in performance of materials due to bridge connection via an N or P atom. However, it does not notice the performance improvement brought by the further introduction of a fused ring system at a specific position of a specific ring.
CN110790797A discloses a metal complex with a structure of
One of many structures disclosed is
This disclosure has discussed the improvement in performance of materials due to bridge connection via an O or S atom. However, it does not notice the performance improvement brought by the further introduction of a fused ring system at a specific position of a specific ring.
The currently developed metal complexes still have various deficiencies in performance when used in electroluminescent devices. To meet the increasing requirements of the industry such as lower voltage, higher device efficiency, light-emitting color within a particular wavelength range, more saturated light-emitting color, and longer device lifetime, the research and development related to metal complexes still needs to be deepened.
The present disclosure aims to provide a series of metal complexes having a polycyclic ligand(s) to solve at least part of the above-mentioned problems. The metal complexes can be used as light-emitting materials in organic electroluminescent devices. While maintaining a very narrow full width at half maximum (FWHM), these novel metal complexes can better adjust the light-emitting colors of the devices, reduce the driving voltages of the devices or maintain the driving voltages of the devices at low voltage levels, improve the efficiency of the devices, and greatly increase the lifetimes of the devices. These novel metal complexes can provide better device performance.
According to an embodiment of the present disclosure, disclosed is a metal complex including a ligand La having a structure represented by Formula 1:
According to another embodiment of the present disclosure, further disclosed is an electroluminescent device including an anode, a cathode and an organic layer disposed between the anode and the cathode, wherein the organic layer includes a metal complex including a ligand La having a structure represented by Formula 1:
According to another embodiment of the present disclosure, further disclosed is a compound composition including the metal complex described in the preceding embodiments.
The novel metal complexes having a polycyclic ligand(s), as disclosed by the present disclosure, may be used as light-emitting materials in electroluminescent devices. While maintaining a very narrow FWHM, these novel metal complexes can better adjust the light-emitting colors of the devices, reduce the driving voltages of the devices or maintain the driving voltages of the devices at low voltage levels, improve the efficiency of the devices, and greatly increase the lifetimes of the devices. These novel metal complexes can provide better device performance.
OLEDs can be fabricated on various types of substrates such as glass, plastic, and metal foil.
More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference herein in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference herein in its entirety. Examples of host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference herein in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference herein in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference herein in their entireties, disclose examples of cathodes including composite cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers are described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference herein in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference herein in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference herein in its entirety.
The layered structure described above is provided by wav 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 comprise 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 rate is fast enough to minimize the non-radiative decay from the triplet state, the fraction of back populated singlet excited states can potentially reach 75%. The total singlet fraction can be 100%, far exceeding 25% of the spin statistics limit for electrically generated excitons.
E-type delayed fluorescence characteristics can be found in an exciplex system or in a single compound. Without being bound by theory, it is believed that E-type delayed fluorescence requires the luminescent material to have a small singlet-triplet energy gap (AES-T). Organic, non-metal containing, donor-acceptor luminescent materials may be able to achieve this. The emission in these materials is generally characterized as a donor-acceptor charge-transfer (CT) type emission. The spatial separation of the HOMO and LUMO in these donor-acceptor type compounds generally results in small AES-T. These states may involve CT states. Generally, donor-acceptor luminescent materials are constructed by connecting an electron donor moiety such as amino- or carbazole-derivatives and an electron acceptor moiety such as N-containing six-membered aromatic rings.
Definition of Terms of Substituents
Halogen or halide—as used herein includes fluorine, chlorine, bromine, and iodine.
Alkyl—contemplates both straight and branched chain alkyl groups. The alkyl group may be an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, neopentyl group, 1-methyl pentyl group, 2-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group, and 3-methylpentyl group. Additionally, the alkyl group may be optionally substituted. The carbons in the alkyl chain can be replaced by other hetero atoms. Of the above, preferred are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, and neopentyl group.
Cycloalkyl—as used herein contemplates cyclic alkyl groups. Preferred cycloalkyl groups are those containing 4 to 10 ring carbon atoms and include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like. Additionally, the cycloalkyl group may be optionally substituted. The carbons in the ring can be replaced by other hetero atoms.
Alkenyl—as used herein contemplates both straight and branched chain alkene groups. Preferred alkenyl groups are those containing 2 to 15 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butanedienyl group, 1-methyl vinyl group, styryl group, 2,2-diphenylvinyl group, 1,2-diphenylvinyl group, 1-methylallyl group, 1,1-dimethylallyl group, 2-methylallyl group, 1-phenylallyl group, 2-phenylallyl group, 3-phenylallyl group, 3,3-diphenylallyl group, 1,2-dimethylallyl group, 1-phenyl 1-butenyl group, and 3-phenyl-1-butenyl group. Additionally, the alkenyl group may be optionally substituted.
Alkynyl—as used herein contemplates both straight and branched chain alkyne groups. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. Additionally, the alkynyl group may be optionally substituted.
Aryl or aromatic group—as used herein includes noncondensed and condensed systems. Preferred aryl groups are those containing six to sixty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Examples of the aryl group include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may be optionally substituted. Examples of the non-condensed aryl group include phenyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, p-t-butylphenyl group, p-(2-phenylpropyl)phenyl group, 4′-methylbiphenylyl group, 4″-t-butyl p-terphenyl-4-yl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, 2,3-xylyl group, 3,4-xylyl group, 2,5-xylyl group, mesityl group, and m-quarterphenyl group.
Heterocyclic group or heterocycle—as used herein includes aromatic and non-aromatic cyclic groups. Hetero-aromatic also means heteroaryl. Preferred non-aromatic heterocyclic groups are those containing 3 to 7 ring atoms which include at least one hetero atom such as nitrogen, oxygen, and sulfur. The heterocyclic group can also be an aromatic heterocyclic group having at least one heteroatom selected from nitrogen atom, oxygen atom, sulfur atom, and selenium atom.
Heteroaryl—as used herein includes non condensed and condensed hetero-aromatic groups that may include from one to five heteroatoms. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, 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, phenoxazine, 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—it is represented by —O-Alkyl. Examples and preferred examples thereof are the same as those described above. Examples of the alkoxy group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, and hexyloxy group. The alkoxy group having 3 or more carbon atoms may be linear, cyclic or branched.
Aryloxy—it is represented by —O-Aryl or —O-heteroaryl. Examples and preferred examples thereof are the same as those described above. Examples of the aryloxy group having 6 to 40 carbon atoms include phenoxy group and biphenyloxy group.
Arylalkyl—as used herein contemplates an alkyl group that has an aryl substituent. Additionally, the arylalkyl group may be optionally substituted. Examples of the arylalkyl group include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl group, alpha-naphthylmethyl group, 1-alpha-naphthylethyl group, 2-alpha-naphthylethyl group, 1-alpha-naphthylisopropyl group, 2-alpha-naphthylisopropyl group, beta-naphthylmethyl group, 1-beta-naphthylethyl group, 2-beta-naphthylethyl group, 1-beta-naphthylisopropyl group, 2-beta-naphthylisopropyl group, p-methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group, p-aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy-2-phenylisopropyl group, and 1-chloro-2-phenylisopropyl group. Of the above, preferred are benzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, and 2-phenylisopropyl group.
The term “aza” in azadibenzofuran, aza-dibenzothiophene, etc. means that one or more of the 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 analogues 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 arylalkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted amine, substituted acyl, substituted carbonyl, substituted carboxylic acid group, substituted ester group, substituted sulfinyl, substituted sulfonyl and substituted phosphino is used, it means that any group of alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, alkenyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amine, acyl, carbonyl, carboxylic acid group, ester group, sulfinyl, sulfonyl and phosphino may be substituted with one or more groups selected from the group consisting of deuterium, a halogen, an unsubstituted alkyl group having 1 to 20 carbon atoms, an unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, an unsubstituted heteroalkyl group having 1 to 20 carbon atoms, an unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted alkoxy group having 1 to 20 carbon atoms, an unsubstituted aryloxy group having 6 to 30 carbon atoms, an unsubstituted alkenyl group having 2 to 20 carbon atoms, an unsubstituted aryl group having 6 to 30 carbon atoms, an unsubstituted heteroaryl group having 3 to 30 carbon atoms, an unsubstituted alkylsilyl group having 3 to 20 carbon atoms, an unsubstituted arylsilyl group having 6 to 20 carbon atoms, an unsubstituted amino group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a sulfanyl group, a sulfinyl group, a sulfonyl group and 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 wav s of designating a substituent or attached fragment are considered to be equivalent.
In the compounds mentioned in the present disclosure, the hydrogen atoms can be partially or fully replaced by deuterium. Other atoms such as carbon and nitrogen can also be replaced by their other stable isotopes. The replacement by other stable isotopes in the compounds may be preferred due to its enhancements of device efficiency and stability.
In the compounds mentioned in the present disclosure, multiple substitutions refer to a range that includes a double substitution, up to the maximum available substitutions. When a substitution in the compounds mentioned in the present disclosure represents multiple substitutions (including di, tri, 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 connect 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, adjacent substituents can be optionally joined to form a ring, including both the case where adjacent substituents can be joined to form a ring, and the 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, 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:
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 including a ligand La having a structure represented by Formula 1:
In the present disclosure, the expression that adjacent substituents Ri, Rx, Ry, R and 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 Ri, two substituents Rii, two substituents Ry, two substituents Rx, substituents Ri and Rx, substituents R and Ry, and substituents Rii and R, can be joined to form a ring. Obviously, these substituents may not be joined to form a ring.
According to an embodiment of the present disclosure, wherein the metal complex optionally contains other ligand(s) which is(are) optionally joined to the La to form a tridentate ligand, a tetradentate ligand, a pentadentate ligand or a hexadentate ligand.
According to an embodiment of the present disclosure, wherein the ring A and the ring B are each independently selected from a five-membered unsaturated carbocyclic ring, an aromatic ring having 6 to 18 carbon atoms, or a heteroaromatic ring having 3 to 18 carbon atoms.
According to an embodiment of the present disclosure, wherein the ring A or the ring B is each independently selected from a five-membered unsaturated carbocyclic ring, an aromatic ring having 6 to 18 carbon atoms, or a heteroaromatic ring having 3 to 18 carbon atoms.
According to an embodiment of the present disclosure, wherein the ring A and the ring B are each independently selected from a five-membered unsaturated carbocyclic ring, an aromatic ring having 6 to 10 carbon atoms, or a heteroaromatic ring having 3 to 10 carbon atoms.
According to an embodiment of the present disclosure, wherein the ring A or the ring B is each independently selected from a five-membered unsaturated carbocyclic ring, an aromatic ring having 6 to 10 carbon atoms, or a heteroaromatic ring having 3 to 10 carbon atoms.
According to an embodiment of the present disclosure, wherein the La is selected from a structure represented by any one of Formula 2 to Formula 19 and Formula 22 to Formula 23;
In the present disclosure, the expression that adjacent substituents R, Rx, Ry, Ri, Rii and Riii 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 Ri, two substituents Rii, two substituents Rx, two substituents Ry, two substituents Riii, substituents Ri and Rx, substituents Rii and Riii, substituents R and Ry, substituents Ry and Riii, and substituents R and Riii, can be joined to form a ring. Obviously, these substituents may not be joined to form a ring.
According to an embodiment of the present disclosure, wherein, La is selected from a structure represented by Formula 2, Formula 9, Formula 11 or Formula 12.
According to an embodiment of the present disclosure, wherein, La is selected from a structure represented by Formula 2.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 19 and Formula 22 to Formula 23, at least one of X1 to Xn and/or A1 to Am is selected from N, wherein the Xn corresponds to one with the largest number of X1 to X7 in any one of Formula 2 to Formula 19 and Formula 22 to Formula 23, and the Am corresponds to one with the largest number of A1 to A6 in any one of Formula 2 to Formula 19 and Formula 22 to Formula 23. For example, in the case of Formula 2, the Xn corresponds to one with the largest number of X1 to X7 in Formula 2, that is X5; and the Am corresponds to one with the largest number of A1 to A6 in Formula 2, that is A4. That is, in Formula 2, at least one of X1 to X5 and/or A1 to A4 is selected from N. In another example, in the case of Formula 12, the Xn corresponds to one with the largest number of X1 to X7 in Formula 12, that is X3; and the Am corresponds to one with the largest number of A1 to A6 in Formula 12, that is A4. That is, in Formula 12, at least one of X1 to X3 and/or A1 to A4 is selected from N.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 19 and Formula 22 to Formula 23, at least one of X1 to Xn is selected from N, wherein the Xn corresponds to one with the largest number of X1 to X7 in any one of Formula 2 to Formula 19 and Formula 22 to Formula 23.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 19 and Formula 22 to Formula 23, X2 is N.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 19 and Formula 22 to Formula 23, X1 and X2 are each independently selected from CRx; X3 to X7 are each independently selected from CRi; A1 to A6 are each independently selected from CRii; and adjacent substituents Rx, Ri, Rii can be optionally joined to form a ring.
In this embodiment, the expression that adjacent substituents Rx, Ri, Ra can be optionally joined to form a ring is intended to mean that any one or more of groups of adjacent substituents, such as two substituents Ri, two substituents Rii, two substituents Rx, and substituents Ri and Rx, can be joined to form a ring. Obviously, these substituents may not be joined to form a ring.
According to an embodiment of the present disclosure, in Formula 2 to Formula 19 and Formula 22 to Formula 23, X1 and X2 are each independently selected from CRx; X3 to X7 are each independently selected from CRii and A1 to A6 are each independently selected from CRii; and the Rx, Ri and Rii are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, a cyano group and combinations thereof; and adjacent substituents Rx, Ri, Rii can be optionally joined to form a ring.
According to an embodiment of the present disclosure, in Formula 2 to Formula 19 and Formula 22 to Formula 23, X1 and X2 are each independently selected from CRx; X3 to X7 are each independently selected from CRi; and A1 to A6 are each independently selected from CRii; and at least two of the Rx, Ri and Rii are, at each occurrence identically or differently, selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, a cyano group and combinations thereof; and adjacent substituents Rx, Ri, Rii can be optionally joined to form a ring.
In this embodiment, the expression that at least two of the Rx, Ri and Rii are, at each occurrence identically or differently, selected from the group of substituents is intended to mean that at least two substituents in the group consisting of two substituents Rx, all substituents Ri and all substituents Rii are, at each occurrence identically or differently, selected from the group of substituents.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 19 and Formula 22 to Formula 23, X1 and X2 are each independently selected from CRx; X3 to X7 are each independently selected from CRi; and A1 to A6 are each independently selected from CRii; and at least three of the Rx, Ri and Rii are, at each occurrence identically or differently, selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, a cyano group and combinations thereof; and adjacent substituents Rx, Ri, Rii can be optionally joined to form a ring.
In this embodiment, the expression that at least three of the Rx, Ri and Rii are, at each occurrence identically or differently, selected from the group of substituents is intended to mean that at least three substituents in the group consisting of two substituents Rx, all substituents Ri and all substituents Rii are, at each occurrence identically or differently, selected from the group of substituents.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 11 and Formula 22 to Formula 23, X4 and X5 are each independently selected from CRi; and in Formula 12 to Formula 19, X3 is selected from CRi.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 11 and Formula 22 to Formula 23, X4 or X5 is selected from CRi; and in Formula 12 to Formula 19, X3 is selected from CRi.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 11 and Formula 22 to Formula 23, X4 and X5 are each independently selected from CRi; and in Formula 12 to Formula 19, X3 is selected from CRi; and the Ri is, at each occurrence identically or differently, selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, a cyano group or a combination thereof.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 11 and Formula 22 to Formula 23, X4 or X5 is selected from CRi, and in Formula 12 to Formula 19, X3 is selected from CRi; and the Ri is, at each occurrence identically or differently, selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, a cyano group or a combination thereof.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 11 and Formula 22 to Formula 23, X4 and X5 are each independently selected from CRi; and in Formula 12 to Formula 19, X3 is selected from CRii and the Ri is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, methyl, ethyl, isopropyl, isobutyl, t-butyl, neopentyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, norbornyl, adamantyl, trimethylsilyl, isopropyldimethylsilyl, phenyldimethylsilyl, trifluoromethyl, cyano, phenyl and combinations thereof.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 11 and Formula 22 to Formula 23, X4 or X5 is selected from CRii and in Formula 12 to Formula 19, X3 is selected from CRii and the Ri is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, fluorine, methyl, ethyl, isopropyl, isobutyl, t-butyl, neopentyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, norbornyl, adamantyl, trimethylsilyl, isopropyldimethylsilyl, phenyldimethylsilyl, trifluoromethyl, cyano, phenyl and combinations thereof.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 19 and Formula 22 to Formula 23, R is selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms or a combination thereof.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 19 and Formula 22 to Formula 23, R is selected from hydrogen, deuterium, fluorine, methyl, ethyl, isopropyl, isobutyl, t-butyl, neopentyl, cyclopentyl, cyclopentylmethyl, deuterated methyl, deuterated ethyl, deuterated isopropyl, deuterated t-butyl, deuterated neopentyl, deuterated cyclopentyl, deuterated cyclopentylmethyl, deuterated cyclohexyl, trimethylsilyl or a combination thereof.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 19 and Formula 22 to Formula 23, Y is selected from O or S.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 19 and Formula 22 to Formula 23, Y is selected from O.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 19 and Formula 22 to Formula 23, X1 and X2 are each independently selected from CRx.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 19 and Formula 22 to Formula 23, X1 and X2 are each independently selected from CRx; and the Rx is, at each occurrence identically or differently, selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms or a combination thereof.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 19 and Formula 22 to Formula 23, X1 is selected from CRx and X2 is N.
According to an embodiment of the present disclosure, wherein, in Formula 2 to Formula 19 and Formula 22 to Formula 23, X1 is selected from CRx and X2 is N; and the Rx is, at each occurrence identically or differently, selected from hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms or a combination thereof.
According to an embodiment of the present disclosure, wherein, the ligand La has a structure represented by Formula 20 or Formula 21:
According to an embodiment of the present disclosure, the ligand La has a structure represented by Formula 20 or Formula 21:
According to an embodiment of the present disclosure, wherein, the ligand La has a structure represented by Formula 20 or Formula 21:
According to an embodiment of the present disclosure, wherein, the ligand La has a structure represented by Formula 20 or Formula 21:
According to an embodiment of the present disclosure, wherein, the ligand La has a structure represented by Formula 20 or Formula 21:
According to an embodiment of the present disclosure, wherein, in Formula 20 and Formula 21, one (for example, Rii1 or Rii2 or Rii3) or two (for example, Rii1 and Rii2, or Rii2 and Rii3, or Rii1 and Rii3) of Rii1, Rii2 and Rii3 are, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, wherein, in Formula 20 and Formula 21, at least one of Rx1, Rx2, Ri1, Ri2, Ri3, Rii1, Rii2, Rii3, Rii4 and R is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 3 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms and combinations thereof.
In this embodiment, the expression that at least one of Rx1, Rx2, Ri1, Ri2, Ri3, Rii1, Rii2, Rii3, Rii4 and R is, at each occurrence identically or differently, selected from the group of substituents is intended to mean that: at least one of Rx1 and Rx2 is, at each occurrence identically or differently, selected from the group of substituents, and/or at least one of Rii, Ru and R13 is, at each occurrence identically or differently, selected from the group of substituents, and/or at least one of Rii1, Rii2, Rii3 and Rii4 is, at each occurrence identically or differently, selected from the group of substituents, and/or R is selected from the group of substituents.
According to an embodiment of the present disclosure, wherein, in Formula 20 and Formula 21, at least one of Ri2, Ri3, Rii1, Rii2, Rii3 and R is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 3 to carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms and combinations thereof.
In this embodiment, the expression that at least one of Ri2, Ri3, Rii1, Rii2, Rii3 and R is, at each occurrence identically or differently, selected from the group of substituents is intended to mean that: at least one of Ri2 and Ri3 is, at each occurrence identically or differently, selected from the group of substituents, and/or at least one of Rii1, Rii2 and Rii3 is, at each occurrence identically or differently, selected from the group of substituents, and/or R is selected from the group of substituents.
According to an embodiment of the present disclosure, wherein, in Formula 20 and Formula 21, at least one of Rx1, Rx2, Ri1, Ri2, Ri3, Rii1, Rii2, Rii3, Rii4 and R is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 3 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms and combinations thereof.
In this embodiment, the expression that at least one of Rx1, Rx2, Ri1, Ri2, Ri3, Rii1, Rii2, Rii3, Rii4 and R is, at each occurrence identically or differently, selected from the group of substituents is intended to mean that: at least one of Rx1 and Rx2 is, at each occurrence identically or differently, selected from the group of substituents, and/or at least one of Rii, Ru and R13 is, at each occurrence identically or differently, selected from the group of substituents, and/or at least one of Rii1, Rii2, Rii3 and Rii4 is, at each occurrence identically or differently, selected from the group of substituents, and/or R is selected from the group of substituents.
According to an embodiment of the present disclosure, wherein, La is, at each occurrence identically or differently, selected from the group consisting of La1 to La1706, wherein the specific structures of the La1 to La1706 are referred to claim 14.
According to an embodiment of the present disclosure, wherein, La is, at each occurrence identically or differently, selected from the group consisting of La1 to La1803, wherein the specific structures of the La1 to La1803 are referred to claim 14.
According to an embodiment of the present disclosure, wherein, La is, at each occurrence identically or differently, selected from the group consisting of La1 to La1931, wherein the specific structures of the La1 to La1931 are referred to claim 14.
According to an embodiment of the present disclosure, wherein, hydrogens in structures of the La1 to La1931 may be partially or fully substituted by deuterium.
According to an embodiment of the present disclosure, wherein, the metal complex has a structure of M(La)m(Lb)n(Lc)q;
In this embodiment, the expression that adjacent substituents Ra, Rb, Rc, RN1, RN2, RC1 and RC2 can be optionally joined to form a ring is intended to mean that any one or more of groups of adjacent substituents, such as two substituents Ra, two substituents Rb, two substituents Rc, substituents Ra and Rb, substituents Ra and Rc, substituents Rb and Rc, substituents Ra and RN1, substituents Rb and RN1, substituents Ra and RC1, substituents Rb and RC2, substituents Rb and RC1, substituents Rb and RC2, substituents Ra and RN2, substituents Rb and RN2, and substituents RC1 and RC2, may be joined to form a ring. Obviously, these substituents may not be joined to form a ring.
In this embodiment, the expression that La, Lb and Lc can be optionally joined to form a multi-dentate ligand is intended to mean that any two or three of La, Lb and Lc can be joined to form a tetradentate ligand or a hexadentate ligand. Obviously, it is possible that La, Lb and Lc are not joined, so that no multi-dentate ligand is formed.
According to an embodiment of the present disclosure, wherein, the metal M is selected from Ir, Rh, Re, Os, Pt, Au or Cu.
According to an embodiment of the present disclosure, wherein, the metal M is selected from Ir, Pt or Os.
According to an embodiment of the present disclosure, wherein, the metal M is Ir.
According to an embodiment of the present disclosure, wherein, Lb is, at each occurrence identically or differently, selected from the following structure:
According to an embodiment of the present disclosure, wherein, Lb is, at each occurrence identically or differently, selected from the following structure:
According to an embodiment of the present disclosure, wherein, Lb is, at each occurrence identically or differently, selected from the following structure:
According to an embodiment of the present disclosure, wherein, Lb is, at each occurrence identically or differently, selected from the following structure:
According to an embodiment of the present disclosure, wherein, Lb is, at each occurrence identically or differently, selected from the group consisting of Lb1 to Lb322, and Lc is, at each occurrence identically or differently, selected from the group consisting of Lc1 to Lc231. The specific structures of the Lb1 to Lb322 and the Lc to Lc231 are referred to claim 18.
According to an embodiment of the present disclosure, wherein, the metal complex has a structure of Ir(La)2(Lb) or Ir(La)2(Lc) or Ir(La)(Lc)2;
According to an embodiment of the present disclosure, wherein, the metal complex has a structure of Ir(La)2(Lb) or Ir(La)2(Lc) or Ir(La)(Lc)2;
According to an embodiment of the present disclosure, wherein, the metal complex has a structure of Ir(La)2(Lb) or Ir(La)2(Lc) or Ir(La)(Lc)2;
According to an embodiment of the present disclosure, wherein, the metal complex is selected from the group consisting of Compound 1 to Compound 260, wherein the specific structures of the Compound 1 to Compound 260 are referred to claim 19.
According to an embodiment of the present disclosure, wherein, the metal complex is selected from the group consisting of Compound 1 to Compound 290, wherein the specific structures of the Compound 1 to Compound 290 are referred to claim 19.
According to an embodiment of the present disclosure, wherein, the metal complex is selected from the group consisting of Compound 1 to compound 312, wherein the specific structures of the Compound 1 to Compound 312 are referred to claim 19.
According to an embodiment of the present disclosure, an electroluminescent device is further disclosed, comprising:
According to an embodiment of the present disclosure, in the electroluminescent device, the organic layer is a light-emitting layer and the metal complex is a light-emitting material.
According to an embodiment of the present disclosure, the electroluminescent device emits red light.
According to an embodiment of the present disclosure, the electroluminescent device emits white light.
According to an embodiment of the present disclosure, in the electroluminescent device, the organic layer is a light-emitting layer, wherein the light-emitting layer further includes at least one host material.
According to an embodiment of the present disclosure, in the electroluminescent device, the at least one host material includes 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 another embodiment of the present disclosure, further disclosed is a compound composition which includes a metal complex whose specific structure is as shown in any one of the embodiments described above.
Combination with Other Materials
The materials described in the present disclosure for a particular layer in an organic light emitting device can be used in combination with various other materials present in the device. The combinations of these materials are described in more detail in U.S. Pat. App. No. 20160359122 at paragraphs 0132-0161, which is incorporated by reference herein in its entirety. The materials described or referred to the disclosure are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The combination of these materials is described in detail in paragraphs 0080-0101 of U.S. Pat. App. No. 20150349273, which is incorporated by reference herein in its entirety. The materials described or referred to the disclosure are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
In the embodiments of material synthesis, all reactions were performed under nitrogen protection unless otherwise stated. All reaction solvents were anhydrous and used as received from commercial sources. Synthetic products were structurally confirmed and tested for properties using one or more conventional equipment in the art (including, but not limited to, nuclear magnetic resonance instrument produced by BRUKER, liquid chromatograph produced by SHIMADZU, liquid chromatograph-mass spectrometry produced by SHIMADZU, gas chromatograph-mass spectrometry produced by SHIMADZU, differential Scanning calorimeters produced by SHIMADZU, fluorescence spectrophotometer produced by SHANGHAI LENGGUANG TECH., electrochemical workstation produced by WUHAN CORRTEST, and sublimation apparatus produced by ANHUI BEQ, etc.) by methods well known to the persons skilled in the art. In the embodiments of the device, the characteristics of the device were also tested using conventional equipment in the art (including, but not limited to, evaporator produced by ANGSTROM ENGINEERING, optical testing system produced by SUZHOU FATAR, life testing system produced by SUZHOU FATAR, and ellipsometer produced by BEIJING ELLITOP, etc.) by methods well known to the persons skilled in the art. As the persons skilled in the art are aware of the above-mentioned equipment use, test methods and other related contents, the inherent data of the sample can be obtained with certainty and without influence, so the above related contents are not further described in this present disclosure.
The method for preparing a compound in the present disclosure is not limited herein. Typically, the following compounds are used as examples without limitations, and synthesis routes and preparation methods thereof are described below.
5 g (24.03 mmol) of Raw material 1 was dissolved in 50 mL of DCM, and 5.39 g (1.3 eq, 31.24 mmol) of meta-chloroperoxybenzoic acid (m-CPBA) was added at room temperature and stirred for 24 h. After TLC showed that the raw material disappeared, the solvents were removed in vacuo to obtain crude Intermediate 2 which was directly used in the next step.
Intermediate 2 obtained in step 1 was dissolved in 24 mL of phosphorus oxychloride, warmed to 100° C., stirred for 3 h, and cooled to 0° C. An aqueous solution of NaOH was slowly added dropwise until the pH was 9 and the system was extracted three times with DCM (50 mL*3). The organic phases were combined, washed with a saturated aqueous solution of sodium chloride, and dried over anhydrous magnesium sulfate, and the solvents were removed in vacuo. The residue was purified through column chromatography (PE:EA=30:1) to obtain 1.98 g of Intermediate 3 with a yield of 34% over two steps.
3 g (18.96 mmol) of Intermediate 4 was dissolved in 30 mL of anhydrous tetrahydrofuran and cooled to −78° C. n-BuLi (1 M, 22.75 mL) (1.2 eq, 22.75 mmol) was slowly added dropwise under a nitrogen atmosphere. After addition, the system was warmed to room temperature and stirred for 1 h. The system was cooled to −78° C. and 4.63 g (1.3 eq, 24.65 mmol) of 1,2-dibromoethane was slowly added dropwise. After addition, the system was warmed to room temperature and stirred overnight. The reaction was quenched with saturated ammonium chloride and extracted three times with EA (40 mL*3). The organic phases were combined, washed with a saturated aqueous solution of sodium chloride, and dried over anhydrous magnesium sulfate, and the solvents were removed in vacuo. The residue was purified through column chromatography (PE:EA=100:1) to obtain 3.82 g of Intermediate 5 with a yield of 85%.
2.5 g (10.57 mmol) of Intermediate 5, 0.387 g (0.05 eq, 0.53 mmol) of PdCh(dppf), 1.56 g (1.5 eq, 15.85 mmol) of AcOK, 3.22 g (1.2 eq, 12.68 mmol) of bis(pinacolato)diboron (B2Pin2) were dissolved in 30 mL of 1,4-dioxane, heated to 80° C., and stirred overnight. The system was cooled to room temperature, the solvents were removed in vacuo, and the residue was purified through column chromatography (PE:EA=20:1) to obtain 2.21 g of Intermediate as a white solid with a yield of 74%.
3.93 g (1.2 eq, 13.85 mmol) of Intermediate 6, 2.78 g (1 eq, 11.54 mmol) of Intermediate 3, 0.387 g (0.05 eq, 0.58 mmol) of Pd(PPh3)4, 1.83 g (1.5 eq, 17.31 mmol) of Na2CO3 were dissolved in 30 mL of 1,4-dioxane and 10 mL of water, heated to 90° C., and stirred overnight. The system was cooled to room temperature, the solvents were removed in vacuo, and the residue was purified through column chromatography (PE:EA=50:1) to obtain 3 g of Intermediate 7 as a white solid with a yield of 72%.
3.03 g (8.32 mmol) of Intermediate 7 was dissolved in 30 mL of DCM and cooled to 0° C. BBr3 was slowly added dropwise under a nitrogen atmosphere and stirred for 2 h. The reaction was quenched with an aqueous solution of NaHCO3 and extracted with DCM (60 mL*3). The organic phases were combined, washed with a saturated aqueous solution of sodium chloride, and dried over anhydrous magnesium sulfate, and the solvents were removed in vacuo. The residue was purified through column chromatography (PE:EA=4:1) to obtain 1.17 g of Intermediate 8 with a yield of 40%.
1.2 g (1 eq, 3.33 mmol) of Intermediate 8, 24 mg (0.05 eq, 0.17 mmol) of CuBr, and 2.82 g (4 eq, 13.3 mmol) of were dissolved in 15 mL of DMF, heat to 90° C., and stirred overnight. The system was cooled to room temperature and diluted with water to precipitate out a product. The product was filtered through Celite and washed with 1 L of DCM to obtain 0.81 g of Intermediate 9 with a yield of 90%. The obtained yellow solid Intermediate 9 was recrystallized from toluene. The obtained solid Intermediate 9 had a purity of 99.7%.
1.2 g (3 eq, 4.45 mmol) of Intermediate 9 was dissolved in 24 mL of 2-ethoxyethanol and 8 mL of water at room temperature, 523 mg (1 eq, 1.48 mmol) of IrCl3.3H2O were added, and the system was purged with nitrogen three times at room temperature, heated to 130° C., refluxed for 24 h at 130° C., and cooled to room temperature. The system was filtered to obtain solids, and the solids were washed with ethanol until the washing liquid was colorless and suction-filtered for about 15 min until ethanol on the solids completely disappeared, to obtain 1.13 g of an iridium dimer as a red solid with a yield of 99%. The iridium dimer was directly used in the next step without further purification.
1.13 g (1 eq, 0.74 mmol) of the iridium dimer obtained in step 8 was added to a 100 mL round-bottom flask, 510 mg (5 eq, 3.7 mmol) of K2CO3 and 0.74 g (4 eq, 2.96 mmol) of 3,7-diethyl-3-methyl-4,6-nonanedione were added, and the system was purged with nitrogen three times at room temperature, stirred under nitrogen protection for 24 h, and filtered through Celite. The solids were washed with ethanol until the washing liquid was colorless and suction-filtered for about 15 min to remove ethanol adsorbed to the solids. Under vacuum filtration, the red solids on the Celite were dissolved in 200 mL of dichloromethane. 20 mL of ethanol was added to the flask, and dichloromethane was removed in vacuo. A product was precipitated from the remaining ethanol and filtered, and ethanol adsorbed to the solids was removed completely through suction filtration. The solids were purified through silica gel column chromatography (PE:DCM=10:1). The obtained crude solids were dissolved in 200 mL of dichloromethane. 20 mL of ethanol was added, and dichloromethane was removed in vacuo. A product was precipitated from the remaining ethanol and filtered, and ethanol adsorbed to the solids was removed completely through suction filtration to obtain Compound 81 as a red solid (with a mass of 1.13 g and a yield of 80%). The purity of Compound 81 was 99.6%. The product was confirmed as the target product with a molecular weight of 954.3.
Intermediate 10 (7.6 g, 35.1 mmol) was dissolved in 70 mL of ultra-dry tetrahydrofuran, the reaction solution was cooled to 0° C., and a solution of n-butyl lithium (15.5 mL, 38.7 mmol) was added dropwise thereto under nitrogen protection. After the dropwise addition, the reaction was maintained at this temperature for 1 h, isopropyl pinacol borate (iPrOBpin) (8.49 g, 45.6 mmol) was added thereto, and after addition, the reaction was warmed to room temperature for 2 h. Then, the reaction was quenched with a saturated solution of ammonium chloride. Ethyl acetate was added to the reaction, liquids were separated, and the aqueous phase was extracted with ethyl acetate. The organic phases were combined, dried, and subjected to rotary evaporation to dryness to obtain a crude product. The crude product was isolated through silica gel column chromatography (using an eluent of ethyl acetate:petroleum ether=1:50, v/v) to obtain the target product Intermediate 11 as a colorless oily liquid (4.7 g, with a yield of 39.1%).
Intermediate 12 (3.19 g, 13.7 mmol), Intermediate 11 (4.7 g, 13.7 mmol), tetrakis(triphenylphosphine)palladium (0.8 g, 0.69 mmol), sodium carbonate (2.18 g, 20.55 mmol), 1,4-dioxane (60 mL), and water (15 mL) were added to a 250 mL round-bottom flask. Then, the reaction was heated to 80° C. under nitrogen protection and stirred overnight. After TLC showed that the reaction was completed, the system was cooled to room temperature. Ethyl acetate was added to the reaction, liquids were separated, and the aqueous phase was extracted with ethyl acetate. The organic phases were combined, dried, and subjected to rotary evaporation to dryness to obtain a crude product. The crude product was isolated through silica gel column chromatography (using an eluent of ethyl acetate:petroleum ether=1:10, v/v) to obtain the target product Intermediate 13 as a white solid (3.5 g, with a yield of 73.0%).
Intermediate 13 (4.1 g, 10 mmol) was dissolved in 20 mL of ethanol, and then 20 mL of 2 M HCl were added thereto, and then the reaction was heated to reflux and stirred overnight. After TLC showed that the reaction was completed, the system was cooled to room temperature. Then, a saturated solution of sodium carbonate was added to adjust the pH to neutrality. A large amount of yellow solids were precipitated from the solution. The solids were filtered, washed with water several times, and suction-filtered to obtain the target product Intermediate 14 as a yellow solid (3.3 g, with a yield of 93.2%).
Intermediate 14 (3.3 g, 9.3 mmol), cuprous bromide (133 mg, 0.9 mmol), 2,2,6,6-tetramethylheptanedione (1.37 g, 7.44 mmol), cesium carbonate (7.6 g, 23.25 mmol), and DMF (90 mL) were heated to 135° C. and reacted overnight under nitrogen protection. After TLC showed that the reaction was completed, the system was cooled to room temperature. 200 mL of water were added to the solution until a large amount of yellow solids were precipitated from the solution. The solids were filtered, washed with water several times, and suction-filtered to obtain the target product Intermediate 15 as a yellow solid (3.10 g, with a yield of 96%).
Intermediate 15 (3.42 g, 10.8 mmol), isobutylboronic acid (2.2 g, 21.6 mmol), palladium acetate (121 mg, 0.54 mmol), Sphos (443 mg, 1.08 mmol), potassium phosphate trihydrate (8.63 g, 32.4 mmol), and toluene (80 mL) were heated to reflux and reacted overnight under nitrogen protection. After TLC showed that the reaction was completed, the system was cooled to room temperature. The solution was poured into a funnel filled with Celite and filtered. The filtrate was collected and subjected to rotary evaporation to dryness to obtain a crude product. The crude product was isolated through silica gel column chromatography (using an eluent of ethyl acetate:petroleum ether=1:30, v/v) to obtain the target product Intermediate 16 as a yellow solid (1.8 g, with a yield of 49.4%).
A mixture of Intermediate 16 (1.8 g, 5.3 mmol), iridium trichloride trihydrate (628 mg, 1.78 mmol), 2-ethoxy ethanol (21 mL), and water (7 mL) was refluxed under a nitrogen atmosphere for 24 h. The system was cooled to room temperature and subjected to rotary evaporation to carefully remove water in the solution, so that a solution of an iridium dimer in ethoxyethanol was obtained, which was used in the next step without further purification.
The solution of iridium dimer, 3,7-diethyl-3-methylnonane-4,6-dione (663 mg, 2.67 mmol), and potassium carbonate (1.23 g, 8.9 mmol) were added to a 100 mL round-bottom flask and reacted at 60° C. for 24 h under nitrogen protection. Then, the solution was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain 1.1 g of Compound 83 with a yield of 57%. The product was further purified through column chromatography. The structure of the compound was confirmed through NMR and LC-MS as the target product with a molecular weight of 1094.5.
Intermediate 17 (2.93 g, 12.54 mmol), Intermediate 11 (3.9 g, 11.4 mmol), Pd(dppf)Cl2 (439 mg, 0.6 mmol), and K2CO3 (4.73 g, 34.2 mmol) were mixed in dioxane/water (42 mL/14 mL), purged with nitrogen, and reacted overnight at room temperature. The solution was filtered through Celite and extracted with EA three times. The organic phases were combined, concentrated, and subjected to column chromatography to obtain Intermediate 18 (3 g with a yield of 63.7%).
Intermediate 18 (3.8 g, 9.2 mmol) was added to a mixed solution of 12 N HCl (7.6 mL) and MeOH (20 mL) and reacted at 54° C. for 2 h. After TLC detected that the reaction was completed, the system was cooled to room temperature, added with a saturated solution of NaHCO3 to adjust the pH to about 7-8, and extracted with EA three times. The organic phases were combined, washed with a saturated aqueous solution of sodium chloride, and concentrated to obtain a crude product of Intermediate 19, which was directly used in the next step without further purification. The crude product of Intermediate 19 (2.6 g, 7.2 mmol), CuBr (103 mg, 0.72 mmol), 2,2,6,6-tetramethyl-3,5-heptanedione (1.06 g, 5.76 mmol), and Cs2CO3 (5.87 g, 18 mmol) were mixed in DMF (72 mL), purged with nitrogen, reacted overnight, and cooled to room temperature. The product was filtered out. The filter cake was washed with an appropriate amount of DMF, washed with EtOH and PE, and dried to obtain Intermediate 20 (1.85 g with a yield of 63% over two steps).
Intermediate 20 (1.85 g, 5.82 mmol), isobutylboronic acid (1.19 g, 11.64 mmol), Pd(OAc)2 (65 mg, 0.29 mmol), Sphos (238 mg, 0.58 mmol), and K3PO4.3H2O (4.66 g, 17.5 mmol) were mixed in toluene (58 mL) and refluxed at 120° C. under nitrogen protection. After HPLC detected that Intermediate 21 was converted completely, the reaction solution was cooled to room temperature, filtered through Celite, concentrated, and subjected to column chromatography to obtain Intermediate 21 (1.3 g of yellow solids with a yield of 66%).
Intermediate 21 (825 mg, 2.42 mmol), IrCl3.3H2O (286 mg, 0.81 mmol), ethoxyethanol (11.5 mL), and water (3.5 mL) were added to a 100 mL single-necked flask, purged with nitrogen, and refluxed at 130° C. for 24 h. After the reaction was cooled to room temperature, the resulting precipitate was filtered out and the filter cake was washed with ethanol and dried. The resulting iridium dimer, 3,7-diethyl-1,1,1-trifluorononane-4,6-dione (319 mg, 1.2 mmol), K2CO3 (560 mg, 4.05 mmol), and ethoxyethanol (13 mL) were mixed in a 100 mL single-necked flask, purged with nitrogen, and reacted overnight at room temperature. After TLC detected that the reaction was completed, stirring was stopped. The reaction solution was filtered through Celite. The filter cake was washed with an appropriate amount of EtOH. The crude product was washed with DCM into a 250 mL eggplant-shaped flask. EtOH (about 5 mL) was added to the crude product, and DCM was removed through rotary evaporation at room temperature until solids were precipitated. The solids were filtered and washed with an appropriate amount of EtOH to obtain Compound 64 (80 mg with a yield of 8.7%). The product was confirmed as the target product with a molecular weight of 1136.4.
A mixture of Intermediate 22 (0.76 g, 1.92 mmol), iridium trichloride trihydrate (226 mg, 0.64 mmol), 2-ethoxyethanol (7.5 mL), and water (2.5 mL) was refluxed under a nitrogen atmosphere for 24 h. The system was cooled to room temperature and subjected to rotary evaporation to carefully remove water in the solution, so that a solution of an iridium dimer in ethoxyethanol was obtained, which was directly used in the next step without further purification.
The solution of iridium dimer in ethoxyethanol obtained in the previous step, 3,7-diethyl-3-methylnonane-4,6-dione (450 mg, 1.84 mmol), and potassium carbonate (0.64 g, 4.45 mmol) were added to a 25 mL round-bottom flask and reacted at 50° C. for 24 h under nitrogen protection. Then, the solution was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain 550 mg of Compound 93 with a yield of 71%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1206.6.
Intermediate 23 (2.1 g, 5.56 mmol), iridium trichloride trihydrate (494 mg, 1.4 mmol), ethoxyethanol (18 mL), and water (6 mL) were added to a 250 mL single-necked flask, purged with nitrogen, and refluxed at 130° C. for 24 h. After the reaction was cooled to room temperature, the resulting precipitate was filtered out and the filter cake was washed with ethanol and dried to obtain an iridium dimer which was directly used in the next step without further purification.
The obtained iridium dimer, 3,7-diethyl-3,7-dimethyl-4,6-nonanedione (421 mg, 1.75 mmol), potassium carbonate (1.94 mg, 14 mmol), and ethoxyethanol (24 mL) were mixed in a 100 mL single-necked flask, purged with nitrogen, and reacted overnight at 55° C. After TLC detected that the reaction was completed, stirring was stopped. The reaction solution was filtered through Celite, the filter cake was washed with an appropriate amount of ethanol, and the crude product was washed with dichloromethane into a 250 mL eggplant-shaped flask. Ethanol (about 5 mL) was added, and dichloromethane was removed through rotary evaporation at room temperature until solids were precipitated. The solids were filtered out, washed with an appropriate amount of ethanol, dried, dissolved in dichloromethane, concentrated, and subjected to column chromatography to obtain Compound 117 as a red solid (1 g with a yield of 60%). The purity of the compound was 99.4%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1192.6.
A mixture of Intermediate 24 (1.37 g, 3.73 mmol), iridium trichloride trihydrate (329 mg, 0.93 mmol), 2-ethoxyethanol (12 mL), and water (4 mL) was refluxed under a nitrogen atmosphere for 24 h. The solution was cooled to room temperature and filtered to obtain an iridium dimer as a red solid which was directly used in the next step without further purification.
The iridium dimer obtained in the previous step, 3,7-diethyl-3,7-dimethylnonane-4,6-dione (430 mg, 1.79 mmol), and potassium carbonate (0.62 g, 4.48 mmol) were added to a 50 mL round-bottom flask and reacted at 50° C. for 24 h under nitrogen protection. Then, the system was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain 810 mg of Compound 116 with a yield of 82.2%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1164.5.
A mixture of Intermediate 25 (0.76 g, 1.92 mmol), iridium trichloride trihydrate (226 mg, 0.64 mmol), 2-ethoxyethanol (7.5 mL), and water (2.5 mL) was refluxed under a nitrogen atmosphere for 24 h. The system was cooled to room temperature and subjected to rotary evaporation to carefully remove water in the solution, so that a solution of an iridium dimer in ethoxyethanol was obtained, which was directly used in the next step without further purification.
The solution of iridium dimer in ethoxyethanol obtained in the previous step, 3,7-diethyl-3,7-dimethylnonane-4,6-dione (450 mg, 1.84 mmol), and potassium carbonate (0.64 g, 4.45 mmol) were added to a 25 mL round-bottom flask and reacted at 50° C. for 24 h under nitrogen protection. Then, the system was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated, but not to dryness. The solution was filtered to obtain 1.75 g of Compound 261 with a yield of 96%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1220.6.
A mixture of Intermediate 26 (0.76 g, 1.92 mmol), iridium trichloride trihydrate (226 mg, 0.64 mmol), 2-ethoxyethanol (7.5 mL), and water (2.5 mL) was refluxed under a nitrogen atmosphere for 24 h. The system was cooled to room temperature and subjected to rotary evaporation to carefully remove water in the solution, so that a solution of an iridium dimer in ethoxyethanol was obtained, which was directly used in the next step without further purification.
The solution of the iridium dimer in ethoxyethanol obtained in the previous step, 3,7-diethyl-1,1,1-trifluorononane-4,6-dione (450 mg, 1.84 mmol), and potassium carbonate (0.64 g, 4.45 mmol) were added to a 25 mL round-bottom flask and reacted at 50° C. for 24 h under nitrogen protection. Then, the system was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain 1.35 g of Compound 262 with a purity of 98.86% and a yield of 92%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1246.5.
Intermediate 27 (800 mg, 2.1 mmol), iridium trichloride trihydrate (250 mg, 0.7 mmol), ethoxyethanol (7.5 mL), and water (2.5 mL) were added to a 100 mL single-necked flask, purged with nitrogen, and refluxed at 130° C. for 24 h. After the reaction was cooled, the solution was concentrated and the solvents were removed through rotary evaporation to obtain an iridium dimer which was directly used in the next step without further purification.
The iridium dimer obtained in the previous step was added with 3,7-diethyl-3,7-dimethylnonane-4,6-dione (337 mg, 1.4 mmol), potassium carbonate (967 mg, 7 mmol), and ethoxyethanol (14 mL), purged with nitrogen, and reacted at room temperature for 48 h. The reaction solution was filtered through Celite. The filter cake was washed with an appropriate amount of ethanol. The crude product was washed with dichloromethane into a 250 mL eggplant-shaped flask. Ethanol (about 5 mL) was added to the crude product, and dichloromethane was removed through rotary evaporation at room temperature until solids were precipitated. The solids were filtered out, washed with an appropriate amount of ethanol, dried, dissolved in dichloromethane, concentrated, and purified through column chromatography to obtain Compound 264 (570 mg). The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1192.6.
A mixture of Intermediate 28 (0.46 g, 1.28 mmol), iridium trichloride trihydrate (130 mg, 0.37 mmol), 2-ethoxyethanol (4.5 mL), and water (1.5 mL) was refluxed under a nitrogen atmosphere for 24 h. The solution was cooled to room temperature and Altered to obtain an iridium dimer as a red solid which was directly used in the next step without further purification.
The iridium dimer obtained in the previous step, 3,7-diethyl-3,7-dimethylnonane-4,6-dione (133 mg, 0.55 mmol), and potassium carbonate (0.25 g, 1.84 mmol) were added to a 50 mL round-bottom flask and reacted at 40° C. for 24 h under nitrogen protection. Then, the system was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain 300 mg of Compound 263 with a yield of 73.7%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1164.5.
A mixture of Intermediate 29 (1.45 g, 3.42 mmol), iridium trichloride trihydrate (346 mg, 0.98 mmol), 2-ethoxyethanol (12 mL), and water (4 mL) was refluxed under a nitrogen atmosphere for 24 h. The solution was cooled to room temperature and filtered to obtain an iridium dimer as a red solid which was directly used in the next step without further purification.
The iridium dimer (0.67 g, 0.31 mmol) obtained in the previous step, 3,7-diethyl-3-methylnonane-4,6-dione (0.21 g, 0.94 mmol), and potassium carbonate (0.43 g, 3.1 mmol) were dissolved in 9 mL of ethoxyethanol and reacted at 40° C. for 24 h under nitrogen protection. Then, the system was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain 370 mg of Compound 266 with a yield of 47.3%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1262.6.
The iridium dimer (0.67 g, 0.31 mmol), Intermediate 30 (0.21 g, 0.94 mmol), and potassium carbonate (0.43 g, 3.1 mmol) were dissolved in 9 mL of ethoxyethanol and reacted at 40° C. for 24 h under nitrogen protection. Then, the system was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain 370 mg of Compound 265 with a yield of 47.3%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1302.6.
A mixture of Intermediate 31 (0.6 g, 1.68 mmol), iridium trichloride trihydrate (198 mg, 0.56 mmol), 2-ethoxyethanol (7.5 mL), and water (2.5 mL) was refluxed under a nitrogen atmosphere for 24 h. The solution was cooled to room temperature and filtered to obtain an iridium dimer as a red solid which was directly used in the next step without further purification.
The iridium dimer obtained in the previous step, 3,7-diethyl-3,7-dimethylnonane-4,6-dione (270 mg, 1.12 mmol), and potassium carbonate (0.77 g, 5.6 mmol) were added to a 25 mL round-bottom flask and reacted at 50° C. for 24 h under nitrogen protection. Then, the system was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain a crude product with a purity of 91.6% (0.4 g). The product was further purified through column chromatography to obtain the final product Compound 267 (0.3 g) with a yield of 47%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1136.5.
A mixture of Intermediate 32 (1.5 g, 4.2 mmol), iridium trichloride trihydrate (427 mg, 1.2 mmol), 2-ethoxyethanol (12 mL), and water (4 mL) was refluxed under a nitrogen atmosphere for 24 h. The solution was cooled to room temperature and filtered to obtain an iridium dimer as a red solid which was directly used in the next step without further purification.
The iridium dimer obtained in the previous step, 3,7-diethyl-3,7-dimethylnonane-4,6-dione (580 mg, 2.4 mmol), and potassium carbonate (0.83 g, 6.04 mmol) were dissolved in 16 mL of ethoxyethanol and reacted at 40° C. for 24 h under nitrogen protection. Then, the system was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain 940 mg of Compound 269 with a yield of 66%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1166.5.
A mixture of Intermediate 33 (1.2 g, 2.93 mmol), iridium trichloride trihydrate (427 mg, 1.2 mmol), 2-ethoxyethanol (12 mL), and water (4 mL) was refluxed under a nitrogen atmosphere for 24 h. The solution was cooled to room temperature and filtered to obtain an iridium dimer as a red solid which was directly used in the next step without further purification.
The iridium dimer (0.67 g, 0.31 mmol) obtained in the previous step, Intermediate 34 (414 mg, 1.76 mmol), and sodium hydroxide (176 mg, 4.4 mmol) were dissolved in 16 mL of ethoxyethanol and reacted at 40° C. for 24 h under nitrogen protection. Then, the system was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain 410 mg of Compound 288 with a yield of 27.4%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1248.6.
A mixture of Intermediate 35 (1.3 g, 3.54 mmol), iridium trichloride trihydrate (204 mg, 0.58 mmol), 2-ethoxyethanol (18 mL), and water (6 mL) was refluxed under a nitrogen atmosphere for 24 h. The solution was cooled to room temperature and filtered to obtain an iridium dimer as a red solid which was directly used in the next step without further purification.
The iridium dimer obtained in the previous step, 3,7-diethyl-3,7-dimethylnonane-4,6-dione (0.21 g, 0.87 mmol), and potassium carbonate (0.40 g, 2.9 mmol) were added to a 100 mL round-bottom flask and reacted at 50° C. for 24 h under nitrogen protection. Then, the system was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain a crude product (0.7 g). The crude product was further purified through column chromatography to obtain Compound 273 (0.6 g) with a yield of 91%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1136.5.
A mixture of Intermediate 36 (1.77 g, 3.87 mmol), iridium trichloride trihydrate (390 mg, 1.11 mmol), 2-ethoxyethanol (24 mL), and water (8 mL) was refluxed under a nitrogen atmosphere for 24 h. The solution was cooled to room temperature and filtered to obtain an iridium dimer as a red solid which was directly used in the next step without further purification.
The iridium dimer obtained in the previous step, 3,7-diethyl-3,7-dimethylnonane-4,6-dione (0.4 g, 1.66 mmol), and potassium carbonate (0.77 mg, 5.6 mmol) were added to a 100 mL round-bottom flask and reacted at 50° C. for 48 h under nitrogen protection. Then, the system was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain a crude product (0.7 g). The crude product was further purified through column chromatography to obtain Compound 282 (0.25 g) with a yield of 17%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1344.6.
The iridium dimer (0.94 g, 0.45 mmol), 3,7-diethyl-3,7-dimethylnonane-4,6-dione (0.32 g, 1.34 mmol), and potassium carbonate (0.62 mg, 4.45 mmol) were dissolved in 25 mL of ethoxyethanol and reacted at 40° C. for 24 h under nitrogen protection. Then, the system was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain 0.87 g of Compound 287 with a yield of 78%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1248.6.
Intermediate 37 (2.68 g, 8.69 mmol) and TMEDA (1.31 g, 11.3 mmol) were dissolved in 80 mL of ultra-dry THF. The reaction system was cooled to 0° C. and then n-butyl lithium (4.2 mL, 10.43 mmol, 2.5 M) was slowly added. After reacting for 1 h at this temperature, isopropyl pinacol borate (2.102 g, 11.3 mmol) was added and reacted overnight. After TLC showed that the reaction was completed, saturated ammonium chloride was added to quench the reaction. The solution was extracted with EA, dried, and filtered, and the solvent was removed through rotary evaporation to obtain a crude product. The crude product was purified through silica gel column chromatography to obtain Intermediate 38 (3.86 g, 82%).
A mixture of Intermediate 12 (1.95 g, 8.4 mmol), Intermediate 38 (3.85 g, 8.4 mmol), Pd(PPh3)4 (0.48 g, 0.42 mmol), sodium carbonate (1.34 g, 12.6 mmol), and 1,4-dioxane/water (32 mL/8 mL) was heated to reflux and reacted overnight under nitrogen protection. After TLC showed that the reaction was completed, the system was cooled to room temperature. Water was added to the reaction system. The organic phase was extracted with EA, dried, and filtered, and the solvent was removed through rotary evaporation to obtain Intermediate 39 (3.1 g with a yield of 70%).
Intermediate 39 (3.1 g, 5.91 mmol) was dissolved in 15 mL of ethanol. Then, the reaction system was slowly added with 15 mL of HCl (2N), heated to reflux, and reacted for 2 h. After TLC showed that the reaction was completed, the reaction system was cooled to room temperature, neutralized to be neutral by adding a solution of sodium bicarbonate, and filtered to obtain a crude solid product. The crude solid product was purified through column chromatography to obtain Intermediate 40 (2.75 g with a yield of 99.78%).
Intermediate 40 (2.75 g, 5.9 mmol), cuprous bromide (86 mg, 0.6 mmol), 2,2,6,6-tetramethylheptanedione (0.88 g, 4.8 mmol), cesium carbonate (4.89 g, IS mmol), and DMF (60 mL) were heated to 135° C. and reacted overnight under nitrogen protection. After TLC showed that the reaction was completed, the system was cooled to room temperature. Water was added thereto until a large amount of yellow solids were precipitated from the solution. The solids were filtered, washed with water several times, and suction-filtered to obtain Intermediate 41 as a yellow solid (2.54 g with a yield of 99.8%).
Intermediate 41 (2.54 g, 5.91 mmol), neopentylboronic acid (1.37 g, 11.83 mmol), Pd2(dba)3 (135 mg, 0.15 mmol), Sphos (243 mg, 0.59 mmol), K3PO4.3H2O (4.72 g, 17.7 mmol) and toluene (30 mL) were mixed. The system was purged with nitrogen three times, heated to reflux, and reacted overnight. After TLC detected that the reaction was completed, the system was cooled to room temperature, and the solvent was removed through rotary evaporation to obtain a crude product. The crude product was purified through column chromatography to obtain Intermediate 42 (1.8 g with a yield of 65%).
A mixture of Intermediate 42 (1.4 g, 3.0 mmol), iridium trichloride trihydrate (0.35 g, 1.0 mmol), 2-ethoxyethanol (12 mL), and water (4 mL) was refluxed under a nitrogen atmosphere for 24 h. The solution was cooled to room temperature and filtered to obtain an iridium dimer as a red solid which was directly used in the next step without further purification.
The iridium dimer obtained in the previous step, 3,7-diethyl-1,1,1-trifluorononane-4,6-dione (0.39 g, 1.5 mmol), and potassium carbonate (0.69 g, 5.00 mmol) were dissolved in 16 mL of ethoxyethanol and reacted at 50° C. for 24 h under nitrogen protection. Then, the system was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain 0.71 g of Compound 291 with a yield of 41.2%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1386.7.
A mixture of Intermediate 43 (1.4 g, 2.92 mmol), iridium trichloride trihydrate (0.34 g, 0.97 mmol), 2-ethoxyethanol (12 mL), and water (4 mL) was refluxed under a nitrogen atmosphere for 24 h. The solution was cooled to room temperature and filtered to obtain an iridium dimer as a red solid which was directly used in the next step without further purification.
The iridium dimer obtained in the previous step, 3,7-diethyl-1,1,1-trifluorononane-4,6-dione (0.38 g, 1.5 mmol), and potassium carbonate (0.67 g, 4.85 mmol) were dissolved in 16 mL of ethoxyethanol and reacted at 50° C. for 24 h under nitrogen protection. Then, the system was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain 0.67 g of Compound 292 with a yield of 49%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1414.7.
The iridium dimer (1.01 g, 0.97 mmol), 3,3,7-triethylnonane-4,6-dione (0.4 g, 1.5 mmol), and potassium carbonate (0.72 g, 4.85 mmol) were dissolved in 16 mL of ethoxyethanol and reacted at 50° C. for 24 h under nitrogen protection. Then, the system was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain 0.62 g of Compound 293 with a yield of 45%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1388.8.
Step 1: Synthesis of an Iridium Dimer
A mixture of Intermediate 44 (0.68 g, 1.60 mmol), iridium trichloride trihydrate (0.16 g, 0.45 mmol), 2-ethoxyethanol (6 mL), and water (2 mL) was refluxed under a nitrogen atmosphere for 24 h. The solution was cooled to room temperature and filtered to obtain an iridium dimer as a red solid which was directly used in the next step without further purification.
The iridium dimer obtained in the previous step, 3,7-diethyl-3,7-dimethylnonane-4,6-dione (0.22 g, 0.9 mmol), and potassium carbonate (0.62 g, 4.5 mmol) were dissolved in 16 mL of ethoxyethanol and reacted at 50° C. for 24 h under nitrogen protection. Then, the system was poured into a funnel filled with Celite to be filtered and washed with ethanol. The resulting solid was added with dichloromethane and the filtrate was collected. Then ethanol was added and the resulting solution was concentrated but not to dryness. The solution was filtered to obtain 0.42 g of Compound 294 with a yield of 73%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1276.7.
A mixture of Intermediate 45 (2.03 g, 4.93 mmol), iridium trichloride trihydrate (0.48 g, 1.37 mmol), 2-ethoxyethanol (33 mL), and water (11 mL) was refluxed under a nitrogen atmosphere for 24 h. The solution was cooled to room temperature and filtered to obtain an iridium dimer as a red solid which was directly used in the next step without further purification.
The iridium dimer obtained in the previous step, 3,7-diethyl-1,1,1-trifluorononane-4,6-dione (0.53 g, 2 mmol), and potassium carbonate (0.95 g, 6.85 mmol) were mixed in ethoxy ethanol (23 mL), purged with nitrogen, and reacted at room temperature for 48 h. The reaction solution was filtered through Celite. The filter cake was washed with an appropriate amount of EtOH. The crude product was washed with DCM into a 250 mL eggplant-shaped flask. EtOH (about 10 mL) was added thereto, and DCM was removed through rotary evaporation at room temperature until solids were precipitated. The solids were filtered and washed with an appropriate amount of EtOH to obtain a crude product. The crude product was purified through column chromatography to obtain 0.1 g of Compound 295 with a yield of 5.7%. The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 1278.5.
Intermediate 46 (0.15 g, 0.526 mmol) was dissolved in 9 mL of 2-ethoxyethanol and 3 mL of water at room temperature, IrCl3.3H2O (62 mg, 0.175 mmol) was added, and the system was heated to 160° C. in an autoclave, refluxed for 24 h at this temperature, and cooled to room temperature. The solution was filtered. The solids were washed with ethanol until the washing liquid was colorless and then suction-filtered to obtain an iridium dimer as a red solid which was directly used in the next step without being purified.
The iridium dimer (0.25 g, 0.157 mmol) obtained in the previous step was added to a 100 mL round-bottom flask, K2CO3 (217 mg, 1.57 mmol) and 3,7-diethyl-3-methylnonane-4,6-dione (142 mg, 0.629 mmol) were added, and 5 mL of 2-ethoxyethanol and 5 mL of DCM were added. The system was purged three times at room temperature, heated to 40° C., and stirred for 24 h under nitrogen protection. DCM was removed in vacuo. The system was filtered through Celite. The solids were washed with ethanol until the washing liquid was colorless and then suction-filtered to remove ethanol. Under vacuum filtration, the red solids on the Celite were dissolved in 200 mL of dichloromethane. 20 mL of ethanol was added, and dichloromethane was removed in vacuo to precipitate out a solid which was filtered to obtain Compound 280 as a red solid (195 mg, 0.20 mmol, with a yield of 63.7%). The structure of the compound was confirmed through LC-MS as the target product with a molecular weight of 986.3.
A mixture of Intermediate 12 (1.63 g, 7.0 mmol), Intermediate 47 (3.9 g, 7.4 mmol), Pd(PPh3)4 (0.4 g, 0.35 mmol), sodium carbonate (1.11 g, 10.5 mmol) and 1,4-dioxane/water (28 mL/7 mL) was heated under nitrogen protection to reflux overnight. After TLC showed that the reaction was complete, the system was cooled to room temperature. Water was added to the reaction system. The organic phase was extracted with EA, dried and filtered. The solvent was removed via rotary-evaporation to obtain Intermediate 48 (3.2 g, 76% yield).
Intermediate 48 (3.2 g, 5.33 mmol) was dissolved in 15 mL of ethanol. 15 mL of HCl (2N) was then slowly added to the reaction system, followed by heating to reflux and reacting for 2 h. After TLC showed that the reaction was complete, the system was cooled to room temperature, neutralized by adding sodium bicarbonate solution to neutral, filtered to obtain a solid crude which was purified by column chromatography to obtain Intermediate 49 (2.65 g, 94.5% yield).
Intermediate 49 (2.65 g, 5.0 mmol), cuprous bromide (72 mg, 0.5 mmol), 2,2,6,6-tetramethylheptanedione (0.74 g, 4.0 mmol), cesium carbonate (4.07 g, 12.5 mmol) and DMF (50 mL) were heated to 135° C. under nitrogen protection and reacted overnight. After TLC showed that the reaction was complete, the system was cooled to room temperature. Water was added to the system to precipitate out a large amount of yellow solids which was filtered, washed with water several times and suction-filtered to obtain Intermediate 50 as a yellow solid (2.26 g, 92.4% yield).
Intermediate 50 (2.26 g, 4.62 mmol), neopentylboronic acid (1.07 g, 9.23 mmol), Pd2(dba)3 (106 mg, 0.12 mmol), Sphos (190 mg, 0.46 mmol), K3PO4.3H2O (3.69 g, 13.9 mmol) and toluene (30 mL) were mixed. The system was purged with nitrogen three times, heated to reflux, and reacted overnight. After TLC showed that the reaction was complete, the system was cooled to room temperature. The solvent was removed through rotary-evaporation to obtain a crude product, which was purified by column chromatography to obtain Intermediate 51 (1.8 g, 74% yield). The structure of this intermediate was confirmed as the target structure by LC-MS with the molecular weight of 525.3.
Starting from Intermediate 51, a compound of the present disclosure comprising the ligand La1931 can be obtained by the person skilled in the art by referring to the methods in the prior art or by following the methods of Synthesis Examples 1-24.
Those skilled in the art will appreciate that the above preparation methods are merely illustrative. Those skilled in the art can obtain other compound structures of the present disclosure through the modifications of the preparation methods.
First, a glass substrate having an Indium Tin Oxide (ITO) anode with a thickness of 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. Next, 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 Angstroms per second at a vacuum degree of about 10−8 torr. Compound HI was used as a hole injection layer (HIL) with a thickness of 100 Å. Compound HT was used as a hole transporting layer (HTL) with a thickness of 400 Å. Compound EB1 was used as an electron blocking layer (EBL) with a thickness of 50 Å. Compound 81 of the present disclosure was doped in a host compound RH to be used as an emissive layer (EML, 2:98) with a thickness of 400 Å. Compound HB was used as a hole blocking layer (HBL) with a thickness of 50 Å. On the HBL, Compound ET and 8-hydroxyquinolinolato-lithium (Liq) were co-deposited as an electron transporting layer (ETL) with a thickness of 350 Å. Finally, Liq with a thickness of 1 nm was deposited as an electron injection layer, and A1 with a thickness of 120 nm was deposited as a cathode. The device was transferred back to the glovebox and encapsulated with a glass lid and a moisture getter to complete the device.
The preparation method in Device Example 2 was the same as that in Device Example 1, except that Compound 81 of the present disclosure was replaced with Compound 83 of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 3 was the same as that in Device Example 1, except that Compound 81 of the present disclosure was replaced with Compound 64 of the present disclosure in the emissive layer (EML), and Compound 64 of the present disclosure was doped with Compound RH at a ratio of 3:97, and Compound EB1 was replaced with Compound EB2 in the electron blocking layer (EBL).
The preparation method in Device Example 4 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound 93 of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 5 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound 117 of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 6 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound 116 of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 7 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound 261 of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 8 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound 262 of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 9 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound 264 of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 10 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 11 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 12 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 13 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 14 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 15 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 16 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 17 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 18 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 19 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 20 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound of the present disclosure in the emissive layer (EML).
The preparation method in Device Example 21 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound of the present disclosure in the emissive layer (EML).
The preparation method in Device Comparative Example 1 was the same as that in Device Example 1, except that Compound 81 of the present disclosure was replaced with Compound RD in the emissive layer (EML).
The preparation method in Device Comparative Example 2 was the same as that in Device Example 3, except that Compound 64 of the present disclosure was replaced with Compound RD in the emissive layer (EML).
The structures and thicknesses of partial layers of the devices are shown in the following table. The layers using more than one material were obtained by doping different compounds at weight ratios as recorded.
The structures of the materials used in the devices are shown as follows:
Current-voltage-luminance (IVL) and lifetime characteristics of the devices were measured at different current densities and voltages. Table 2 shows the CIE data, driving voltage (V), maximum emission wavelength (λmax), full width at half maximum (FWHM), and external quantum efficiency (EQE) of Device Example 1, Device Example 2, and Device Comparative Example 1 measured at a constant current of IS mA/cm2 and the lifetime (LT97) measured at a constant current of 80 mA/cm2.
Discussion
From the data shown in Table 2, it can be seen that the FWHMs of Comparative Example 1 and Examples 1 and 2 were all around 30 nm, which are very remarkable. But, Comparative Example 1 had a maximum emission wavelength of 566 nm. Examples 1 and 2, however, achieved a large red shift of the maximum emission wavelength by designing the molecular structure of a light-emitting dopant, so that the emission wavelengths were between nm and 620 nm, which satisfies the requirement on different red emission wavelength bands. At a constant current of IS mA/cm2, Examples 1 and 2 were superior to Comparative Example 1 in terms of the voltage and the external quantum efficiency. Especially, the external quantum efficiency of Example 2 was 36% higher than that of Comparative Example 1. According to the data on the lifetime LT97 of Comparative Example 1 and Examples 1 and 2 at a constant current of 80 mA/cm2, the lifetime of Comparative Example 1 under this condition was 2 hours, the lifetime of Example 1 was 30 hours, and the lifetime of Example 2 was 105 hours. Therefore, it can be seen that the compounds disclosed by the present disclosure can greatly improve the lifetime of an electroluminescent device. From the preceding data analysis, it can be seen that while maintaining a very narrow FWHM, the Examples can effectively adjust the emission wavelength to meet the requirement on red light emission, reduce the voltage, improve the EQE, and most importantly, greatly improve the lifetime, thereby providing excellent performance.
Table 3 shows the CIE data, driving voltage (V), maximum emission wavelength (λmax), full width at half maximum (FWHM), and lifetime (LT97) of Device Example 3 measured at a constant current of 15 mA/cm2.
Discussion
From the data shown in Table 3, it can be seen that Example 3 achieved an emission wavelength of 633 nm by adjusting the molecular structure, which is in a deep red region. At a constant current of 15 mA/cm2, Example 3 had a very narrow FWHM of 39 nm and a relatively low driving voltage of 3.78 V.
Table 4 shows the CIE data, driving voltage (V), maximum emission wavelength (λmax), full width at half maximum (FWHM), and external quantum efficiency (EQE) of Device Comparative Example 2, and Device Examples 4 to 21 measured at a constant current of 15 mA/cm2 and the lifetime (LT97) at a constant current of 80 mA/cm2.
Discussion
From the device data in Table 4, it can also be seen that Examples 4 to 13, where the compounds of the present disclosure were used as a dopant in the light-emitting layer, all achieved a large red shift of the maximum emission wavelength of the devices. The emission wavelengths of Examples 4 to 13 were between 614 nm and 623 nm and can meet the requirement on different red emission wavelength bands. While the maximum emission wavelength of Comparative Example 2 where Comparative Compound RD was used was only nm and cannot meet the requirement on the light-emitting colors of red light-emitting devices at all. In addition, though the FWHMs and voltages of Examples 4 to 13 were basically the same as or slightly worse than those of Comparative Example 2 at a constant current of 15 mA/cm2, it should be noted that the FWHMs of Examples 4 to 13, that were less than 36 nm, are still at high levels in the industry and the voltages of Examples 4 to 13 are also still relatively low in the industry. On the other hand, the external quantum efficiency of all Examples 4 to 13 was further improved compared to the very high external quantum efficiency of Comparative Example 2. Most importantly, the lifetimes LT97 of Examples 4 to 13 at a constant current of 80 mA/cm2 were all greatly improved (at least about 20 fold and up to about 50 fold) relative to the lifetime of Comparative Example 2 (which was only 3 hours under this condition and cannot meet the requirement at all). All the above comparisons prove again that the compounds disclosed by the present disclosure have very excellent performance.
From the device data in Table 4, it can also be seen that Examples 14 to 21, where the compounds of the present disclosure were used as a dopant in the light-emitting layer, all achieved a large red shift of the maximum emission wavelength of the devices. The emission wavelengths of Examples 14 to 21 were between 607 nm and 625 nm and can meet the requirement on different red emission wavelength bands. While the maximum emission wavelength of Comparative Example 2 where Comparative Compound RD was used was only nm and cannot meet the requirement on the light-emitting colors of red light-emitting devices at all. In addition, though the FWHMs and voltages of Examples 14 to 21 were basically the same as or slightly worse than those of Comparative Example 2 at a constant current of 15 mA/cm2, it should be noted that the FWHMs of Examples 14 to 21, that were less than 34 nm, are still at high levels in the industry and the voltages of Examples 14 to 21 are also still relatively low in the industry. On the other hand, the external quantum efficiency of all Examples 14 to 21 was further improved compared to the very high external quantum efficiency of Comparative Example 2. Most importantly, the lifetimes LT97 of Examples 14 to 21 at a constant current of 80 mA/cm2 were all greatly improved (at least about 9 fold and up to about fold) relative to the lifetime of Comparative Example 2 (which was only 3 hours under this condition and cannot meet the requirement at all). All the above comparisons prove again that the compounds disclosed by the present disclosure have very excellent performance.
In summary, while maintaining a very narrow FWHM, the compounds disclosed by the present disclosure can effectively adjust the emission wavelength to meet the requirement on red light emission, reduce the voltage or maintain the voltage at a low level, improve the EQE, and most importantly, greatly improve the lifetime, thereby providing excellent performance.
According to our researches on OLED red light-emitting materials, when the substituent R in the structure of Formula I is not a hydrogen atom, the emission spectrum of the materials can be well adjusted and the external quantum efficiency of the materials can be improved:
However, according to our repeated researches, a ligand with the structure of Formula II cannot be successfully coordinated with a metal to form a metal complex:
Surprisingly, if the substituent R in Formula I is designed, through structural design, as a part of a fused ring, then (1) a ligand with a corresponding structure, such as Formula 1 disclosed by the present disclosure, can be successfully coordinated with a metal to form a metal complex; (2) as shown by the results of researches on devices using the related compounds, metal complexes having such structure disclosed by the present disclosure, when used as light-emitting materials in electroluminescent devices, all exhibit excellent device performance, and they can effectively adjust the emission wavelength to meet the requirement on red light emission, obtain a very narrow FWHM, reduce the voltage or maintain a low voltage, improve the EQE, and most importantly, greatly increase the lifetime. These results further highlight the uniqueness and importance of the present disclosure.
It should be understood that various embodiments described herein are merely embodiments and not intended to limit the scope of the present disclosure. Therefore, it is apparent to those skilled in the art that the present disclosure as claimed may include variations of specific embodiments and preferred embodiments described herein. Many of the materials and structures described herein may be replaced with other materials and structures without departing from the spirit of the present disclosure. It should be understood that various theories as to why the present disclosure works are not intended to be limitative.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202010362117.X | Apr 2020 | CN | national |
| 202011219604.7 | Nov 2020 | CN | national |
| 202110348602.6 | Apr 2021 | CN | national |
