Patent Application
20220402877
The present disclosure relates to electronic devices, for example, electroluminescent devices. In particular, the present disclosure relates to an electroluminescent device containing a novel material combination of a first compound having a structure of H-L-E and a second compound having a general formula of M(La)m(Lb)n(Lc)q in an organic layer.
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.
To develop phosphorescent OLEDs, appropriate host materials are to be selected for use in conjunction with phosphorescent light-emitting materials, which is an important and extensive research direction.
KR1020150077220A has disclosed a compound with a general formula of
Specific examples include
Although this application claims the synthesis of these two compounds, the characterization data of the key intermediate
provided by this application does not match the structure of this compound. Therefore, whether these two compounds have been obtained remains uncertain. Additionally, this application has only mentioned the use in conjunction with the following light-emitting materials:
This application pays no attention to the coordination of host materials and light-emitting materials and has not disclosed or taught the use of the disclosed host materials in conjunction with light-emitting materials of other structures.
US20180337340A1 has disclosed an organic electroluminescent compound and an organic electroluminescent device containing the same. The organic electroluminescent device includes an organic layer containing one or more hosts, where a first host is an organic optical compound having the following structure:
However, the disclosed compounds have to include a structural unit of quinazoline or quinoxaline. Additionally, this application uses a combination of such a host compound and a phosphorescent light-emitting compound,
in a comparative device example. It is believed that the compound formed through carbazole fused to an aza seven-membered ring structural unit and linked to a triazine structural unit is not suitable as phosphorescent host materials. Inventors of this application have not discovered that excellent performance can be obtained by rationally selecting a novel material combination of a host compound having triazine or similar structures and a suitable phosphorescent light-emitting compound. The teaching in the comparative example of this application goes against the present application in essence.
However, the device performance of a combination of a host material and a phosphorescent light-emitting material reported so far can still be improved. To meet the increasing requirements of the industry, it is an efficient research and development means to select a combination of a suitable host material and the phosphorescent light-emitting material and the novel material combination still needs to be further researched and developed.
The present disclosure aims to provide an electroluminescent device having a novel material combination to solve at least part of the above-mentioned problems. The electroluminescent device adopts a novel material combination consisting of a first compound having a structure of H-L-E and a second compound having a general formula of M(La)m(Lb)n(Lc)q. The novel material combination may be used in a light-emitting layer of the electroluminescent device. The novel material combination can enable the electroluminescent device to obtain a lower voltage, higher efficiency and an ultra-long lifetime and can provide better device performance.
According to an embodiment of the present disclosure, 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 at least includes a first compound and a second compound;
the first compound has a structure of H-L-E;
H has a structure represented by Formula 1:
in Formula 1, A1, A2 and A3 are, at each occurrence identically or differently, selected from N or CR, and the ring A, the ring B and the ring C are, at each occurrence identically or differently, selected from a carbocyclic ring having 5 to 18 carbon atoms or a heterocyclic ring having 3 to 18 carbon atoms;
Rf represents, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
E has a structure represented by Formula 2:
in Formula 2, at least one of Z1 to Z5 is N, and the rest of Z1 to Z5 are each independently selected from CRz;
L is selected from a single bond, substituted or unsubstituted arylene having 6 to 30 carbon atoms, substituted or unsubstituted heteroarylene having 3 to 30 carbon atoms or a combination thereof;
R, Rf and Rz are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
adjacent substituents R, Rf can be optionally joined to form a ring;
the second compound is a metal complex having a general formula of M(La)m(Lb)n(Lc)q;
wherein the M is selected from a metal with a relative atomic mass greater than 40;
La, Lb and Lc are a first ligand, a second ligand and a third ligand coordinated to the M, respectively; La, Lb and Lc can be optionally joined to form a multidentate ligand;
La, Lb and Lc may be the same or different; m is 1, 2 or 3, n is 0, 1 or 2, q is 0 or 1, and m+n+q equals to the oxidation state of the M; when m is greater than or equal to 2, the multiple La may be the same or different; when n is equal to 2, the two Lb may be the same or different;
La has a structure represented by Formula 3:
wherein,
the ring D is selected from a five-membered heteroaromatic ring or a six-membered heteroaromatic ring;
the ring E is selected from a five-membered unsaturated carbocyclic ring, a benzene ring, a five-membered heteroaromatic ring or a six-membered heteroaromatic ring;
the ring D and the ring E are fused via Ya and Yb;
Ya and Yb are, at each occurrence identically or differently, selected from C or N;
Rd and Re represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
X1 to X4 are, at each occurrence identically or differently, selected from CRx or N;
Rd, Re and Rx are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
adjacent substituents Rd, Re, Rx can be optionally joined to form a ring;
Lb and Lc are each independently selected from any one of the following structures:
Ra, Rb and Rc represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
Xb is selected from the group consisting of: O, S, Se, NRN1 and CRC1RC2;
Xc and Xd are each independently selected from the group consisting of: O, S, Se and NRN2;
Ra, Rb, Rc, RN1, RN2, RC1 and RC2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
in structures of Lb and Lc, adjacent substituents Ra, Rb, Rc, RN1, RN2, RC1 and RC2 can be optionally joined to form a ring;
and, the following case is not comprised: the first compound is
while the second compound is
According to another embodiment of the present disclosure, further disclosed is a display assembly comprising the electroluminescent device described above.
According to another embodiment of the present disclosure, further disclosed is a compound combination comprising a first compound and a second compound;
the first compound has a structure of H-L-E;
H has a structure represented by Formula 1:
in Formula 1, A1, A2 and A3 are, at each occurrence identically or differently, selected from N or CR, and the ring A, the ring B and the ring C are, at each occurrence identically or differently, selected from a carbocyclic ring having 5 to 18 carbon atoms or a heterocyclic ring having 3 to 18 carbon atoms;
Rf represents, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
E has a structure represented by Formula 2:
in Formula 2, at least one of Z1 to Z5 is N, and the rest of Z1 to Z5 are each independently selected from CRz;
L is selected from a single bond, substituted or unsubstituted arylene having 6 to 30 carbon atoms, substituted or unsubstituted heteroarylene having 3 to 30 carbon atoms or a combination thereof;
R, Rf and Rz are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
adjacent substituents R, Rf can be optionally joined to form a ring;
the second compound is a metal complex having a general formula of M(La)m(Lb)n(Lc)q;
wherein the M is selected from a metal with a relative atomic mass greater than 40;
La, Lb and Lc are a first ligand, a second ligand and a third ligand coordinated to the M, respectively; La, Lb and Lc can be optionally joined to form a multidentate ligand;
La, Lb and Lc may be the same or different; m is 1, 2 or 3, n is 0, 1 or 2, q is 0 or 1, and m+n+q equals to the oxidation state of the M; when m is greater than or equal to 2, the multiple La may be the same or different; when n is equal to 2, the two Lb may be the same or different;
La has a structure represented by Formula 3:
wherein,
the ring D is selected from a five-membered heteroaromatic ring or a six-membered heteroaromatic ring;
the ring E is selected from a five-membered unsaturated carbocyclic ring, a benzene ring, a five-membered heteroaromatic ring or a six-membered heteroaromatic ring;
the ring D and the ring E are fused via Ya and Yb;
Ya and Yb are, at each occurrence identically or differently, selected from C or N;
Rd and Re represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
X1 to X4 are, at each occurrence identically or differently, selected from CRx or N;
Rd, Re and Rx are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
adjacent substituents Rd, Re, Rx can be optionally joined to form a ring;
Lb and Lc are each independently selected from any one of the following structures:
Ra, Rb and Rc represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
Xb is selected from the group consisting of: O, S, Se, NRN1 and CRC1RC2;
Xc and Xd are each independently selected from the group consisting of: O, S, Se and NRN2;
Ra, Rb, Rc, RN1, RN2, RC1 and RC2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
in structures of Lb and Lc, adjacent substituents Ra, Rb, Rc, RN1, RN2, RC1 and RC2 can be optionally joined to form a ring;
and, the following case is not comprised: the first compound is
while the second compound is
The present disclosure discloses a novel electroluminescent device. The electroluminescent device adopts the novel material combination consisting of the first compound having the structure of H-L-E and the second compound having the general formula of M(La)m(Lb)n(Lc)q. The novel material combination may be used in the light-emitting layer of the electroluminescent device. The novel material combination can enable the novel electroluminescent device to obtain the lower voltage, the higher efficiency and the ultra-long lifetime and can provide the 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 way of non-limiting examples. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely. It may also include other layers not specifically described. Within each layer, a single material or a mixture of multiple materials can be used to achieve optimum performance. Any functional layer may include several sublayers. For example, the emissive layer may have two layers of different emitting materials to achieve desired emission spectrum.
In one embodiment, an OLED may be described as having an “organic layer” disposed between a cathode and an anode. This organic layer may 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 ΔES-T. These states may involve CT states. Generally, donor-acceptor luminescent materials are constructed by connecting an electron donor moiety such as amino- or carbazole-derivatives and an electron acceptor moiety such as N-containing six-membered aromatic rings.
Halogen or halide—as used herein includes fluorine, chlorine, bromine, and iodine.
Alkyl—as used herein includes both straight and branched chain alkyl groups. Alkyl may be alkyl having 1 to 20 carbon atoms, preferably alkyl having 1 to 12 carbon atoms, and more preferably alkyl having 1 to 6 carbon atoms. Examples of alkyl groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, a neopentyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 1-pentylhexyl group, a 1-butylpentyl group, a 1-heptyloctyl group, and a 3-methylpentyl group. Additionally, the alkyl may be optionally substituted. Of the above, preferred are a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, a neopentyl group, and an n-hexyl group. Additionally, the alkyl group may be optionally substituted.
Cycloalkyl—as used herein includes cyclic alkyl groups. The cycloalkyl groups may be those having 3 to 20 ring carbon atoms, preferably those having 4 to 10 carbon atoms. Examples of cycloalkyl include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcylcohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, and the like. Of the above, preferred are cyclopentyl, cyclohexyl, 4-methylcyclohexyl, and 4,4-dimethylcylcohexyl. Additionally, the cycloalkyl group may be optionally substituted.
Heteroalkyl—as used herein, includes a group formed by replacing one or more carbons in an alkyl chain with a hetero-atom(s) selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a phosphorus atom, a silicon atom, a germanium atom, and a boron atom. Heteroalkyl may be those having 1 to 20 carbon atoms, preferably those having 1 to 10 carbon atoms, and more preferably those having 1 to 6 carbon atoms. Examples of heteroalkyl include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxymethoxymethyl, ethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminomethyl, trimethylsilyl, dimethylethylsilyl, dimethylisopropylsilyl, t-butyldimethylsilyl, triethylsilyl, triisopropylsilyl, trimethylsilylmethyl, trimethylsilylethyl, and trimethylsilylisopropyl. Additionally, the heteroalkyl group may be optionally substituted.
Alkenyl—as used herein includes straight chain, branched chain, and cyclic alkene groups. Alkenyl may be those having 2 to 20 carbon atoms, preferably those having 2 to 10 carbon atoms. Examples of alkenyl include vinyl, propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butandienyl, 1-methylvinyl, styryl, 2,2-diphenylvinyl, 1,2-diphenylvinyl, 1-methylallyl, 1,1-dimethylallyl, 2-methylallyl, 1-phenylallyl, 2-phenylallyl, 3-phenylallyl, 3,3-diphenylallyl, 1,2-dimethylallyl, 1-phenyl-1-butenyl, 3-phenyl-1-butenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl, cyclooctatetraenyl, and norbornenyl. Additionally, the alkenyl group may be optionally substituted.
Alkynyl—as used herein includes straight chain alkynyl groups. Alkynyl may be those having 2 to 20 carbon atoms, preferably those having 2 to 10 carbon atoms. Examples of alkynyl groups include ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3,3-dimethyl-1-butynyl, 3-ethyl-3-methyl-1-pentynyl, 3,3-diisopropyl-1-pentynyl, phenylethynyl, phenylpropynyl, etc. Of the above, preferred are ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, and phenylethynyl. Additionally, the alkynyl group may be optionally substituted.
Aryl or an aromatic group—as used herein includes non-condensed and condensed systems. Aryl may be those having 6 to 30 carbon atoms, preferably those having 6 to 20 carbon atoms, and more preferably those having 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl may be optionally substituted. Examples of non-condensed aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p-tolyl, p-(2-phenylpropyl)phenyl, 4′-methylbiphenylyl, 4″-t-butyl-p-terphenyl-4-yl, o-cumenyl, m-cumenyl, p-cumenyl, 2,3-xylyl, 3,4-xylyl, 2,5-xylyl, mesityl, and m-quarterphenyl. Additionally, the aryl group may be optionally substituted.
Heterocyclic groups or heterocycle—as used herein include non-aromatic cyclic groups. Non-aromatic heterocyclic groups include saturated heterocyclic groups having 3 to 20 ring atoms and unsaturated non-aromatic heterocyclic groups having 3 to 20 ring atoms, where at least one ring atom is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, a phosphorus atom, a germanium atom, and a boron atom. Preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms, each of which includes at least one hetero-atom such as nitrogen, oxygen, silicon, or sulfur. Examples of non-aromatic heterocyclic groups include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxolanyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxepinyl, thiepinyl, azepinyl, and tetrahydrosilolyl. Additionally, the heterocyclic group may be optionally substituted.
Heteroaryl—as used herein, includes non-condensed and condensed hetero-aromatic groups having 1 to 5 hetero-atoms, wherein at least one hetero-atom is selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, a selenium atom, a silicon atom, a phosphorus atom, a germanium atom, and a boron atom. A hetero-aromatic group is also referred to as heteroaryl. Heteroaryl may be those having 3 to 30 carbon atoms, preferably those having 3 to 20 carbon atoms, and more preferably those having 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridoindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indenoazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.
Alkoxy—as used herein, is represented by —O-alkyl, —O-cycloalkyl, —O-heteroalkyl, or —O-heterocyclic group. Examples and preferred examples of alkyl, cycloalkyl, heteroalkyl, and heterocyclic groups are the same as those described above. Alkoxy groups may be those having 1 to 20 carbon atoms, preferably those having 1 to 6 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy, and ethoxymethyloxy. Additionally, the alkoxy group may be optionally substituted.
Aryloxy—as used herein, is represented by —O-aryl or —O-heteroaryl. Examples and preferred examples of aryl and heteroaryl are the same as those described above. Aryloxy groups may be those having 6 to 30 carbon atoms, preferably those having 6 to 20 carbon atoms. Examples of aryloxy groups include phenoxy and biphenyloxy. Additionally, the aryloxy group may be optionally substituted.
Arylalkyl—as used herein, contemplates alkyl substituted with an aryl group. Arylalkyl may be those having 7 to 30 carbon atoms, preferably those having 7 to 20 carbon atoms, and more preferably those having 7 to 13 carbon atoms. Examples of arylalkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl-t-butyl, alpha-naphthylmethyl, 1-alpha-naphthylethyl, 2-alpha-naphthylethyl, 1-alpha-naphthylisopropyl, 2-alpha-naphthylisopropyl, beta-naphthylmethyl, 1-beta-naphthylethyl, 2-beta-naphthylethyl, 1-beta-naphthylisopropyl, 2-beta-naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl, and 1-chloro-2-phenylisopropyl. Of the above, preferred are benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenyl ethyl, 1-phenylisopropyl, and 2-phenylisopropyl. Additionally, the arylalkyl group may be optionally substituted.
Alkylsilyl—as used herein, contemplates a silyl group substituted with an alkyl group. Alkylsilyl groups may be those having 3 to 20 carbon atoms, preferably those having 3 to 10 carbon atoms. Examples of alkylsilyl groups include trimethylsilyl, triethylsilyl, methyldiethylsilyl, ethyldimethylsilyl, tripropylsilyl, tributylsilyl, triisopropylsilyl, methyldiisopropylsilyl, dimethylisopropylsilyl, tri-t-butylsilyl, triisobutylsilyl, dimethyl t-butylsilyl, and methyl di-t-butylsilyl. Additionally, the alkylsilyl group may be optionally substituted.
Arylsilyl—as used herein, contemplates a silyl group substituted with at least one aryl group. Arylsilyl groups may be those having 6 to 30 carbon atoms, preferably those having 8 to 20 carbon atoms. Examples of arylsilyl groups include triphenylsilyl, phenyldibiphenylylsilyl, diphenylbiphenylsilyl, phenyldiethylsilyl, diphenylethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, phenyldiisopropylsilyl, diphenylisopropylsilyl, diphenylbutylsilyl, diphenylisobutylsilyl, diphenyl t-butylsilyl, tri-t-butylsilyl, dimethyl t-butylsilyl, methyl di-t-butylsilyl. Additionally, the arylsilyl group may be optionally substituted.
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, a substituted heterocyclic group, substituted arylalkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted amino, substituted acyl, substituted carbonyl, a substituted carboxylic acid group, a substituted ester group, substituted sulfinyl, substituted sulfonyl and substituted phosphino is used, it means that any group of alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, alkenyl, alkynyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amino, 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, 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 heterocyclic group having 3 to 20 ring 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 alkynyl 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 cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof.
It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or 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 sub stituents 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 an electroluminescent device comprising:
an anode,
a cathode, and
an organic layer disposed between the anode and the cathode, wherein the organic layer at least comprises a first compound and a second compound;
the first compound has a structure of H-L-E;
H has a structure represented by Formula 1:
in Formula 1, A1, A2 and A3 are, at each occurrence identically or differently, selected from N or CR, and the ring A, the ring B and the ring C are, at each occurrence identically or differently, selected from a carbocyclic ring having 5 to 18 carbon atoms or a heterocyclic ring having 3 to 18 carbon atoms;
Rf represents, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
E has a structure represented by Formula 2:
in Formula 2, at least one of Z1 to Z5 is N, and the rest of Z1 to Z5 are each independently selected from CRz;
wherein L is selected from a single bond, substituted or unsubstituted arylene having 6 to 30 carbon atoms, substituted or unsubstituted heteroarylene having 3 to 30 carbon atoms or a combination thereof;
R, Rf and Rz are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
adjacent substituents R, Rf can be optionally joined to form a ring;
the second compound is a metal complex having a general formula of M(La)m(Lb)n(Lc)q;
the M is selected from a metal with a relative atomic mass greater than 40;
La, Lb and Lc are a first ligand, a second ligand and a third ligand coordinated to the M, respectively; La, Lb and Lc can be optionally joined to form a multidentate ligand; for example, any two of La, Lb and Lc may be joined to form a tetradentate ligand; in another example, La, Lb and Lc may be joined to each other to form a hexadentate ligand; in another example, none of La, Lb and Lc are joined so that no multidentate ligand is formed;
La, Lb and Lc may be the same or different; m is 1, 2 or 3, n is 0, 1 or 2, q is 0 or 1, and m+n+q equals to the oxidation state of the M; when m is greater than or equal to 2, the multiple La may be the same or different; when n is equal to 2, the two Lb may be the same or different;
La has a structure represented by Formula 3:
wherein,
the ring D is selected from a five-membered heteroaromatic ring or a six-membered heteroaromatic ring;
the ring E is selected from a five-membered unsaturated carbocyclic ring, a benzene ring, a five-membered heteroaromatic ring or a six-membered heteroaromatic ring;
the ring D and the ring E are fused via Ya and Yb;
Ya and Yb are, at each occurrence identically or differently, selected from C or N;
Rd and Re represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
X1 to X4 are, at each occurrence identically or differently, selected from CRx or N;
Rd, Re and Rx are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
adjacent substituents Rd, Re, Rx can be optionally joined to form a ring;
Lb and Lc are each independently selected from any one of the following structures:
Ra, Rb and Rc represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
Xb is selected from the group consisting of: O, S, Se, NRN1 and CRC1RC2;
Xc and Xd are each independently selected from the group consisting of: O, S, Se and NRN2;
Ra, Rb, Rc, RN1, RN2, RC1 and RC2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
in structures of Lb and Lc, adjacent substituents Ra, Rb, Rc, RN1, RN2, RC1 and RC2 can be optionally joined to form a ring;
and, the following case is not comprised: the first compound is
while the second compound is
In the present disclosure, the expression that adjacent substituents R, Rf can be optionally joined to form a ring is intended to mean that in the presence of substituents R and Rf, any one or more of groups of adjacent substituents, such as adjacent substituents R, adjacent substituents Rf, and substituents R and Rf, can be joined to form a ring. Obviously, in the presence of substituents R and Rf, it is possible that none of these groups of substituents are joined to form a ring.
In the present disclosure, the expression that adjacent substituents Rd, Re, Rx can be optionally joined to form a ring is intended to mean that in the presence of substituents Rd, Re and Rx, any one or more of groups of adjacent substituents, such as adjacent substituents Rd, adjacent substituents Re, adjacent substituents Rx, adjacent substituents Rd and Re, adjacent substituents Rd and Rx, and adjacent substituents Re and Rx, can be joined to form a ring. Obviously, in the presence of substituents Rd, Re and Rx, it is possible that none of these groups of substituents are joined to form a ring.
In the present disclosure, the expression that in the structures of Lb and Lc, 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 Ra and Rb, substituents Ra and Rc, substituents Rb and Rc, substituents Ra and RN1, substituents Rb and RN1, substituents Ra and RC1, substituents Ra and RC2, substituents Rb and RC1, substituents Rb and RC2, substituents Ra and RN2, substituents Rb and RN2, and substituents RC1 and RC2, may be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
According to an embodiment of the present disclosure, wherein in Formula 1, the ring A, the ring B and the ring C are, at each occurrence identically or differently, selected from 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 in Formula 1, the ring A, the ring B and the ring C are, at each occurrence identically or differently, selected from an aromatic ring having 6 to 12 carbon atoms or a heteroaromatic ring having 3 to 12 carbon atoms.
According to an embodiment of the present disclosure, wherein in Formula 1, the ring A, the ring B and the ring C are, at each occurrence identically or differently, selected from a five-membered carbocyclic ring, a benzene ring, a five-membered heteroaromatic ring or a six-membered heteroaromatic ring.
According to an embodiment of the present disclosure, wherein in the first compound, H has a structure represented by Formula 1-a:
wherein A1 to A3 are, at each occurrence identically or differently, selected from N or CR, and F1 to F10 are, at each occurrence identically or differently, selected from CRf or N;
R and Rf are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
adjacent substituents R, Rf can be optionally joined to form a ring.
According to an embodiment of the present disclosure, wherein in the first compound, R and Rf are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group and combinations thereof;
adjacent substituents R, Rf can be optionally joined to form a ring.
According to an embodiment of the present disclosure, wherein in the first compound, at least one of R and Rf is selected from deuterium, substituted or unsubstituted aryl having 6 to 30 carbon atoms or substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms.
According to an embodiment of the present disclosure, wherein in the first compound, at least one of R and Rf is selected from deuterium, phenyl, biphenyl or pyridyl.
According to an embodiment of the present disclosure, wherein in the first compound, for adjacent substituents R in A1 to A3, adjacent substituents Rf in F1 to F3, adjacent substituents Rf in F4 to F6, and adjacent substituents Rf in F7 to F10, at least one group of these groups of adjacent substituents is joined to form a ring.
According to an embodiment of the present disclosure, wherein in the first compound, the H is selected from the group consisting of the following structures:
According to an embodiment of the present disclosure, wherein hydrogens in the structures of H-1 to H-57 can be partially or fully substituted with deuterium.
According to an embodiment of the present disclosure, wherein in the first compound, the E has a structure represented by any one of Formula 2-a to Formula 2-h:
wherein Z1 to Z5 are, at each occurrence identically or differently, selected from CRz;
wherein Rz is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof.
According to a preferred embodiment of the present disclosure, wherein the Rz is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, 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 a preferred embodiment of the present disclosure, wherein the Rz is, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, phenyl, naphthyl, biphenyl, terphenyl, fluorenyl, dibenzofuranyl, dibenzothienyl, pyridyl and combinations thereof.
According to an embodiment of the present disclosure, wherein in the first compound, the E is selected from substituted or unsubstituted triazinyl.
According to an embodiment of the present disclosure, wherein in the first compound, the E is selected from the group consisting of the following structures:
wherein in the above structures, “” represents the position where the structure is joined to the structure of L.
According to an embodiment of the present disclosure, wherein hydrogens in the structures of E-1 to E-69 can be partially or fully substituted with deuterium.
According to an embodiment of the present disclosure, wherein in the first compound, the L is selected from a single bond or substituted or unsubstituted arylene having 6 to 30 carbon atoms.
According to an embodiment of the present disclosure, wherein in the first compound, the L is selected from the group consisting of: a single bond, phenylene, naphthylene, biphenylene, terphenylene, triphenylenylene, phenanthrylene and fluorenylidene.
According to an embodiment of the present disclosure, wherein in the first compound, the L is selected from the group consisting of the following structures:
wherein in the above structures, “*” represents the position where the structure is joined to the structure of H, and “” represents the position where the structure is joined to the structure of E.
According to an embodiment of the present disclosure, wherein hydrogens in the structures of L-1 to L-28 can be partially or fully substituted with deuterium.
According to an embodiment of the present disclosure, wherein the first compound is selected from the group consisting of Compound 1 to Compound 520, wherein the specific structures of Compound 1 to Compound 520 are referred to claim 9.
According to an embodiment of the present disclosure, wherein in the second compound, the metal M is selected from Ir, Rh, Re, Os, Pt, Au or Cu.
According to an embodiment of the present disclosure, wherein in the second compound, the M is selected from Ir, Pt or Os.
According to an embodiment of the present disclosure, wherein in the second compound, the M is Ir.
According to an embodiment of the present disclosure, wherein in the second compound, the La has a structure represented by any one of Formula 3-1 to Formula 3-5:
wherein,
the ring E is selected from a five-membered unsaturated carbocyclic ring, a benzene ring, a five-membered heteroaromatic ring or a six-membered heteroaromatic ring;
Re represents, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
X11 to X14 are, at each occurrence identically or differently, selected from CRx1 or N; X21 to X24 are, at each occurrence identically or differently, selected from CRx2 or N; X31 to X34 are, at each occurrence identically or differently, selected from CRx3 or N; X41 to X44 are, at each occurrence identically or differently, selected from CRx4 or N; and X51 to X54 are, at each occurrence identically or differently, selected from CRx5 or N;
Y is, at each occurrence identically or differently, selected from O, S, Se, NRd1, CRd1Rd1 or SiRd1Rd1; wherein in the presence of two Rd1, the two Rd1 may be the same or different; for example, when Y is selected from CRd1Rd1, the two Rd1 may be the same or different; in another example, when Y is selected from SiRd1Rd1, the two Rd1 may be the same or different;
preferably, Y is, at each occurrence identically or differently, selected from O or S;
Y3 and Y4 are, at each occurrence identically or differently, selected from CRd or N;
Rx1, Rx2, Rx3, Rx4, Rx5, Rd1, Rd and Re are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
adjacent substituents Rx1, Rx2, Rx4, Rx5, Rd1, Rd and Re can be optionally joined to form a ring;
when Rx3 is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms or substituted or unsubstituted amino having 0 to 20 carbon atoms, adjacent substituents Rx3 can be optionally joined to form a ring.
In the present disclosure, the expression that adjacent substituents Rx1, Rx2, Rx4, Rx5, Rd1, Rd and Re can be optionally joined to form a ring is intended to mean that in the presence of substituents Rx1, Rx2, Rx4, Rx5, Re, Rd or Rd1, any one or more of groups of adjacent substituents, such as adjacent substituents Rx1, adjacent substituents Rx2, adjacent substituents Rx4, adjacent substituents Rx5, adjacent substituents Rd1, substituents Rx1 and Rd, substituents Rx1 and Re, substituents Rx2 and Rd, substituents Rx4 and Re, substituents Rx5 and Rd1, substituents Rd1 and Re, and substituents Rd and Re, can be joined to form a ring. Obviously, it is possible that none of these substituents are joined to form a ring.
In the present disclosure, the expression that when Rx3 is selected from the group of substituents, adjacent substituents Rx3 can be optionally joined to form a ring is intended to mean that only when substituent Rx3 is present and Rx3 is selected from the group consisting of alkyl, cycloalkyl, arylalkyl, alkenyl, aryl, heteroaryl, alkylsilyl, arylsilyl and amino, can adjacent substituents Rx3 be joined to form a ring; and when substituent Rx3 is selected from substituents that are not in the above group of substituents, adjacent substituents Rx3 cannot be joined to form a ring. Obviously, when substituent Rx3 is selected from the above group of substituents, it is possible that adjacent substituents Rx3 are not joined to form a ring.
According to an embodiment of the present disclosure, wherein in the second compound, the La has a structure represented by any one of Formula 3-6 to Formula 3-13:
wherein
X11 to X14 are, at each occurrence identically or differently, selected from CRx1 or N; X21 to X24 are, at each occurrence identically or differently, selected from CRx2 or N; X31 to X34 are, at each occurrence identically or differently, selected from CRx3 or N; X41 to X44 are, at each occurrence identically or differently, selected from CRx4 or N; and X51 to X54 are, at each occurrence identically or differently, selected from CRx5 or N;
Y3 and Y4 are, at each occurrence identically or differently, selected from CRd or N;
Y5, Y6, Y7 and Y8 are, at each occurrence identically or differently, selected from CRe or N;
Y is, at each occurrence identically or differently, selected from O, S, Se, NRd1, CRd1Rd1 or SiRd1Rd1; wherein in the presence of two Rd1, the two Rd1 may be the same or different; for example, when Y is selected from CRd1Rd1, the two Rd1 may be the same or different; in another example, when Y is selected from SiRd1Rd1, the two Rd1 may be the same or different;
Rx1, Rx2, Rx3, Rx4, Rx5, Rd1, Rd and Re are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
adjacent substituents Rx1, Rx2, Rx4, Rx5, Rd1, Rd and Re can be optionally joined to form a ring;
when Rx3 is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms or substituted or unsubstituted amino having 0 to 20 carbon atoms, adjacent substituents Rx3 can be optionally joined to form a ring.
According to an embodiment of the present disclosure, wherein the La has a structure represented by any one of Formula 3-6 to Formula 3-13, wherein the Y is, at each occurrence identically or differently, selected from O or S.
According to an embodiment of the present disclosure, wherein the La has a structure represented by Formula 3-6, Formula 3-7, Formula 3-9, Formula 3-10, Formula 3-11, Formula 3-12 or Formula 3-13.
According to an embodiment of the present disclosure, wherein the La has a structure represented by Formula 3-6 or Formula 3-9.
According to an embodiment of the present disclosure, wherein in Formula 3-6 to Formula 3-11, at least one of Y3 and Y4 is N.
According to an embodiment of the present disclosure, wherein in Formula 3-6,
Formula 3-7, Formula 3-9, Formula 3-10 and Formula 3-11, Y4 is N; and in Formula 3-8, Y3 is N.
According to an embodiment of the present disclosure, wherein in Formula 3-6 to Formula 3-13, Y3 and Y4 are, at each occurrence identically or differently, selected from CRd, and Y5, Y6, Y7 and Y8 are, at each occurrence identically or differently, selected from CRe.
According to an embodiment of the present disclosure, wherein in Formula 3-6 to Formula 3-13, Y3 and/or Y4 are/is selected from CRd, and the Rd is, at each occurrence identically or differently, selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof.
According to an embodiment of the present disclosure, wherein in Formula 3-6 to Formula 3-13, Y3 and/or Y4 are/is selected from CRd, and the Rd is, at each occurrence identically or differently, selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, wherein in Formula 3-6 to Formula 3-13, at least one or two of Y5 to Y8 are selected from CRe, and the Re is, at each occurrence identically or differently, selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof.
According to an embodiment of the present disclosure, wherein in Formula 3-6 to Formula 3-13, at least one or two of Y5 to Y8 are selected from CRe, and the Re is, at each occurrence identically or differently, selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, wherein in Formula 3-6 and Formula 3-9, Y6 is selected from CRe; in Formula 3-8, Y4 is selected from CRd and/or at least one of Y6 to Y8 is selected from CRe; in Formula 3-10 and Formula 3-11, at least one of Y5 and Y6 is CRe; and the Rd and Re are, at each occurrence identically or differently, selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof.
According to an embodiment of the present disclosure, wherein in Formula 3-6 and Formula 3-9, Y6 is selected from CRe; in Formula 3-8, Y4 is selected from CRd and/or at least one of Y6 to Y8 is selected from CRe; in Formula 3-10 and Formula 3-11, at least one of Y5 and Y6 is CRe; and the Rd and Re are, at each occurrence identically or differently, selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, wherein in Formula 3-10 and Formula 3-11, at least one of Y5 and Y6 is selected from CRe, and the Re is, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof.
According to an embodiment of the present disclosure, wherein in Formula 3-10 and Formula 3-11, Y5 and Y6 are each independently selected from CRe, and two Re are joined to form a five-membered aromatic ring, a benzene ring, a five-membered heteroaromatic ring or a six-membered heteroaromatic ring.
According to an embodiment of the present disclosure, wherein in Formula 3-6 to Formula 3-13, at least one or two of X11 to X14 are selected from CRx1, at least one or two of X21 to X24 are selected from CRx2, at least one or two of X31 to X34 are selected from CRx3, at least one or two of X41 to X44 are selected from CRx4, at least one or two of X51 to X54 are selected from CRx5, and the Rx1, Rx2, Rx3, Rx4 and Rx5 are, at each occurrence identically or differently, selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof.
According to an embodiment of the present disclosure, wherein in Formula 3-6 to Formula 3-13, at least one or two of X11 to X14 are selected from CRx1, at least one or two of X21 to X24 are selected from CRx2, at least one or two of X31 to X34 are selected from CRx3, at least one or two of X41 to X44 are selected from CRx4, at least one or two of X51 to X54 are selected from CRx5, and the Rx1, Rx2, Rx3, Rx4 and Rx5 are, at each occurrence identically or differently, selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, wherein in Formula 3-6 to Formula 3-13, X12 and/or X14 are/is selected from CRx1, X22 and/or X24 are/is selected from CRx2, X32 and/or X34 are/is selected from CRx3, X42 and/or X44 are/is selected from CRx4, X52 and/or X54 are/is selected from CRx5, and the Rx1, Rx2, Rx3, Rx4 and Rx5 are, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 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 3-6 to Formula 3-13, X12 and/or X14 are/is selected from CRx1, X22 and/or X24 are/is selected from CRx2, X32 and/or X34 are/is selected from CRx3, X42 and/or X44 are/is selected from CRx4, X52 and/or X54 are/is selected from CRx5, and the Rx1, Rx2, Rx3, Rx4 and Rx5 are, at each occurrence identically or differently, selected from the group consisting of: substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms and combinations thereof.
According to an embodiment of the present disclosure, wherein in Formula 3-6 to Formula 3-13, Xie and X14 are each independently selected from CRx1, X22 and X24 are each independently selected from CRx2, X32 and X34 are each independently selected from CRx3, X42 and X44 are each independently selected from CRx4, X52 and X54 are each independently selected from CRx5, and the Rx1, Rx2, Rx3, Rx4 and Rx5 are, at each occurrence identically or differently, selected from the group consisting of: deuterium, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl and combinations thereof.
According to an embodiment of the present disclosure, wherein in the second compound, the La is, at each occurrence identically or differently, selected from the group consisting of La-1 to La-387, wherein the specific structures of La-1 to La-387 are referred to claim 22.
According to an embodiment of the present disclosure, wherein in the second compound, the Lb has a structure represented by Formula 4:
R1 to R7 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof
According to an embodiment of the present disclosure, wherein in the second compound, the Lb has the structure represented by Formula 4, wherein at least one or two of R1 to R3 are, at each occurrence identically or differently, selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms or a combination thereof and/or at least one or two of R4 to R6 are selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms or a combination thereof.
According to an embodiment of the present disclosure, wherein in the second compound, the Lb has the structure represented by Formula 4, wherein at least two of R1 to R3 are, at each occurrence identically or differently, selected from substituted or unsubstituted alkyl having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 2 to 20 carbon atoms or a combination thereof; and/or at least two of R4 to R6 are, at each occurrence identically or differently, selected from substituted or unsubstituted alkyl having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 2 to 20 carbon atoms or a combination thereof.
According to an embodiment of the present disclosure, wherein in the second compound, the Lb is, at each occurrence identically or differently, selected from the group consisting of Lb1 to Lb322, wherein the specific structures of Lb1 to Lb322 are referred to claim 24.
According to an embodiment of the present disclosure, wherein the second compound has a structure of Ir(La)2(Lb), wherein La is, at each occurrence identically or differently, selected from any one or any two of the group consisting of La-1 to La-387, and Lb is selected from any one of the group consisting of Lb1 to Lb322.
According to an embodiment of the present disclosure, wherein the second compound is selected from the group consisting of Compound 2-1 to Compound 2-34, Compound 2-39 to Compound 2-70, Compound 2-75 to Compound 2-106, Compound 2-111 to Compound 2-142, Compound 2-147 to Compound 2-178, Compound 2-183 to Compound 2-214, Compound 2-217 to Compound 2-227, Compound 2-229 to Compound 2-241, Compound 2-243 to Compound 2-255, Compound 2-257 to Compound 2-269, Compound 2-271 to Compound 2-283, Compound 2-285 to Compound 2-297 and Compound 2-299 to Compound 2-300, wherein the specific structures of Compound 2-1 to Compound 2-34, Compound 2-39 to Compound 2-70, Compound 2-75 to Compound 2-106, Compound 2-111 to Compound 2-142, Compound 2-147 to Compound 2-178, Compound 2-183 to Compound 2-214, Compound 2-217 to Compound 2-227, Compound 2-229 to Compound 2-241, Compound 2-243 to Compound 2-255, Compound 2-257 to Compound 2-269, Compound 2-271 to Compound 2-283, Compound 2-285 to Compound 2-297 and Compound 2-299 to Compound 2-300 are referred to claim 25.
According to an embodiment of the present disclosure, wherein the organic layer is a light-emitting layer, the first compound is a host material, and the second compound is a light-emitting material.
According to an embodiment of the present disclosure, wherein the electroluminescent device emits red light.
According to an embodiment of the present disclosure, wherein the electroluminescent device emits white light.
According to another embodiment of the present disclosure, further disclosed is a display assembly comprising an electroluminescent device. The specific structure of the electroluminescent device is as shown in any one of the embodiments described above.
According to another embodiment of the present disclosure, further disclosed is a compound combination comprising a first compound and a second compound;
the first compound has a structure of H-L-E;
H has a structure represented by Formula 1:
in Formula 1, A1, A2 and A3 are, at each occurrence identically or differently, selected from N or CR, and the ring A, the ring B and the ring C are, at each occurrence identically or differently, selected from a carbocyclic ring having 5 to 18 carbon atoms or a heterocyclic ring having 3 to 18 carbon atoms;
Rf represents, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
E has a structure represented by Formula 2:
in Formula 2, at least one of Z1 to Z5 is N, and the rest of Z1 to Z5 are each independently selected from CRz;
L is selected from a single bond, substituted or unsubstituted arylene having 6 to 30 carbon atoms, substituted or unsubstituted heteroarylene having 3 to 30 carbon atoms or a combination thereof;
R, Rf and Rz are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
adjacent substituents R, Rf can be optionally joined to form a ring;
the second compound is a metal complex having a general formula of M(La)m(Lb)n(Lc)q;
wherein the M is selected from a metal with a relative atomic mass greater than 40;
La, Lb and Lc are a first ligand, a second ligand and a third ligand coordinated to the M, respectively; La, Lb and Lc can be optionally joined to form a multidentate ligand;
La, Lb and Lc may be the same or different; m is 1, 2 or 3, n is 0, 1 or 2, q is 0 or 1, and m+n+q equals to the oxidation state of the M; when m is greater than or equal to 2, the multiple La may be the same or different; when n is equal to 2, the two Lb may be the same or different;
La has a structure represented by Formula 3:
wherein,
the ring D is selected from a five-membered heteroaromatic ring or a six-membered heteroaromatic ring;
the ring E is selected from a five-membered unsaturated carbocyclic ring, a benzene ring, a five-membered heteroaromatic ring or a six-membered heteroaromatic ring;
the ring D and the ring E are fused via Ya and Yb;
Ya and Yb are, at each occurrence identically or differently, selected from C or N;
Rd and Re represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
X1 to X4 are, at each occurrence identically or differently, selected from CRx or N;
Rd, Re and Rx are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
adjacent substituents Rd, Re, Rx can be optionally joined to form a ring;
Lb and Lc are each independently selected from any one of the following structures:
Ra, Rb and Rc represent, at each occurrence identically or differently, mono-substitution, multiple substitutions or non-substitution;
Xb is selected from the group consisting of: O, S, Se, NRN1 and CRC1RC2;
Xc and Xd are each independently selected from the group consisting of: O, S, Se and NRN2;
Ra, Rb, Rc, RN1, RN2, RC1 and RC2 are, at each occurrence identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 20 ring atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a sulfanyl group, a sulfinyl group, a sulfonyl group, a phosphino group and combinations thereof;
in structures of Lb and Lc, adjacent substituents Ra, Rb, Rc, RN1, RN2, RC1 and RC2 can be optionally joined to form a ring;
and, the following case is not comprised: the first compound is
while the second compound is
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, compounds 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.
Material Synthesis
Methods selected in the present disclosure for preparing a first compound and a second compound are not limited herein. Typically, the following compounds are taken as examples without limitations, and synthesis routes and preparation methods thereof are described below.
Step 1: Synthesis of Intermediate 1
Under nitrogen protection, 2-bromo-3-chloronitrobenzene (100 g, 425.5 mmol), 2-aminophenylboronic acid pinacol ester (102 g, 468.1 mmol), tetrakis(triphenylphosphine)palladium (4.9 g, 4.25 mmol), potassium carbonate (115 g, 852 mmol), toluene (1000 mL), water (200 mL) and ethanol (200 mL) were added to a three-necked flask and reacted at 100° C. for 48 h. After the reaction was complete, the reaction solution was cooled to room temperature, concentrated to remove solvents, and added with distilled water. The mixture was extracted with ethyl acetate. The organic phases were washed with water, dried over anhydrous magnesium sulfate, concentrated to remove the solvent, and purified through column chromatography (PE/EA=4:1) to obtain Intermediate 1 as a yellow oil (90 g, yield: 85%).
Step 2: Synthesis of Intermediate 2
Intermediate 1 (90 g, 363 mmol) and acetonitrile (1000 mL) were put into a three-necked flask, respectively. p-Toluenesulfonic acid (193.2 g, 1088 mmol) was added portion-wise at 0° C. and stirred for 30 min. At this temperature, an aqueous solution of a mixture of sodium nitrite (69 g, 726 mmol) and potassium iodide (150.6 g, 907 mmol) was slowly added dropwise. After the dropwise addition was complete, the mixture was slowly warmed to room temperature and reacted for 12 h. After the reaction was complete, a saturated aqueous solution of sodium thiosulfate was added dropwise to quench the reaction. The reaction solution was concentrated and diluted with water. The mixed solution was extracted three times with ethyl acetate. The organic phases were dried over anhydrous sodium sulfate and concentrated to remove solvents. The mixture was isolated through column chromatography (PE/DCM=10/1) to obtain Intermediate 2 as a yellow solid (85 g, yield: 65%).
Step 3: Synthesis of Intermediate 4
Under nitrogen protection, Intermediate 2 (20 g, 55.7 mmol), Intermediate 3 (24.5 g, 83.6 mmol), tetrakis(triphenylphosphine)palladium (1.9 g, 1.67 mmol), potassium carbonate (15.4 g, 111.4 mmol), tetrahydrofuran (500 mL), water (100 mL) and ethanol (100 mL) were added to a three-necked flask and reacted at 70° C. for 48 h. After the reaction was complete, the reaction solution was cooled to room temperature, concentrated to remove solvents, and added with distilled water. The mixture was extracted with ethyl acetate. The organic phases were washed with water, dried over anhydrous magnesium sulfate, concentrated to remove the solvent, and purified through column chromatography (PE/EA=4:1) to obtain Intermediate 4 as a yellow solid (12 g, yield: 55%).
Step 4: Synthesis of Intermediate 5
Under nitrogen protection, Intermediate 4 (12 g, 30.15 mmol), palladium acetate (338 mg, 1.5 mmol), tri-tert-butylphosphine (606 mg, 3.0 mmol), cesium carbonate (20 g, 60.3 mmol) and xylene (230 mL) were added to a three-necked flask and reacted at 140° C. for 10 h. After the reaction was complete, the reaction solution was cooled to room temperature, concentrated to remove solvents, and added with distilled water. The mixture was extracted with ethyl acetate. The organic phases were washed with water, dried over anhydrous magnesium sulfate, concentrated to remove the solvent, and purified through column chromatography (PE/EA=6:1) to obtain Intermediate 5 as a yellow solid (9 g, yield: 80%).
Step 5: Synthesis of Intermediate 6
Under nitrogen protection, Intermediate 5 (9 g, 24.9 mmol), triphenylphosphine (19.6 g, 74.7 mmol) and o-dichlorobenzene (o-DCB) (100 mL) were added to a three-necked flask and reacted at 200° C. for 12 h. After the reaction was complete, the reaction solution was concentrated to remove the solvent, and the crude product was isolated through column chromatography to obtain Intermediate 6 as a yellow solid (7 g, yield: 85%). 1H NMR (400 MHz, DMSO-d6) δ 11.41 (s, 1H), 8.20 (d, J=7.7 Hz, 1H), 8.14 (d, J=8.4 Hz, 1H), 8.03 (d, J=7.5 Hz, 1H), 7.91 (d, J=7.8 Hz, 1H), 7.58-7.46 (m, 2H), 7.41 (d, J=7.9 Hz, 1H), 7.39-7.31 (m, 4H), 7.28 (t, J=7.7 Hz, 1H), 7.15 (d, J=7.7 Hz, 1H).
Step 6: Synthesis of Compound 1-1
Under nitrogen protection, Intermediate 6 (2 g, 6.06 mmol), Intermediate 8 (1.8 g, 6.6 mmol), cesium carbonate (3.9 g, 12.12 mmol) and DMF (60 mL) were added to a three-necked flask and reacted at 80° C. for 5 h. After the reaction was complete, the reaction solution was cooled to room temperature, added with distilled water and filtered to obtain a solid. The crude product was washed three times (with THF/Tol=1:1) to obtain Compound 1-1 as a yellow solid (2.4 g, yield: 72%). The structure of the compound was confirmed as the target product with a molecular weight of 561.2.
Step 1: Synthesis of Compound 1-2
Under nitrogen protection, Intermediate 6 (3 g, 9.1 mmol), Intermediate 7 (3.87 g, 10 mmol), palladium acetate (40 mg, 0.02 mmol), 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl (147 mg, 0.04 mmol), cesium carbonate (5.9 g, 18.2 mmol) and xylene (100 ml) were added to a three-necked flask and reacted at 140° C. for 10 h. After the reaction was complete, the reaction solution was cooled to room temperature, concentrated to remove solvents, and added with distilled water. The mixture was extracted with ethyl acetate. The organic phases were washed with water and concentrated to remove the solvent. The crude product was washed with toluene, tetrahydrofuran and acetone to obtain Compound 1-2 as a yellow solid (3 g, yield: 51%). The structure of the compound was confirmed as the target product with a molecular weight of 637.2.
Those skilled in the art will appreciate that the above preparation methods are merely exemplary. Those skilled in the art can obtain other structures of the first compound and the second compound selected by the present disclosure through the modifications of the preparation methods. Alternatively, the other structures of the first compound and the second compound can be obtained with reference to Chinese Patent Application Nos. CN2020102702502 and CN2020102850167, which is not repeated herein.
The method for preparing an electroluminescent device is not limited. The preparation method in the following example is merely an example and not to be construed as a limitation. Those skilled in the art can make reasonable improvements on the preparation method in the following example based on the related art. Exemplarily, the proportions of various materials in a light-emitting layer are not particularly limited. Those skilled in the art can reasonably select the proportions within a certain range based on the related art. For example, based on the total weight of the materials in the light-emitting layer, the first compound accounts for 80%-99% and the second compound accounts for 1%-20%; or, preferably, the second compound accounts for 1%-10%.
First, a glass substrate having an Indium Tin Oxide (ITO) anode with a thickness of 120 nm was cleaned and then treated with oxygen plasma and UV ozone. After the treatment, the substrate was dried in a nitrogen-filled glovebox to remove moisture and then 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 0.01 to 5 Å/s and 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 EB was used as an electron blocking layer (EBL) with a thickness of 50 Å. Then, Compound 1-1 as a host and Compound 2-2 as a dopant were co-deposited as an emissive layer (EML) with a thickness of 400 Å. Compound HB was used as a hole blocking layer (HBL) with a thickness of 50 Å. On the HBL, Compound ET and 8-hydroxyquinolinolato-lithium (Liq) were co-deposited as an electron transporting layer (ETL) with a thickness of 350 Å. Finally, 8-hydroxyquinolinolato-lithium (Liq) with a thickness of 10 Å was deposited as an electron injection layer (EIL), and Al with a thickness of 1200 Å was deposited as a cathode. The device was transferred back to the glovebox and encapsulated with a glass lid to complete the device.
The implementation mode in Device Example 2 was the same as that in Device Example 1, except that Compound 1-1 was replaced with Compound 1-2 as the host in the emissive layer (EML).
The implementation mode in Device Example 3 was the same as that in Device Example 1, except that Compound 2-2 was replaced with Compound 2-125 as the dopant in the emissive layer (EML).
The implementation mode in Device Example 4 was the same as that in Device Example 2, except that Compound 2-2 was replaced with Compound 2-125 as the dopant in the emissive layer (EML).
The implementation mode in Device Example 5 was the same as that in Device Example 2, except that Compound 2-2 was replaced with Compound 2-43 as the dopant in the emissive layer (EML).
The implementation mode in Device Example 6 was the same as that in Device Example 2, except that Compound 2-2 was replaced with Compound 2-1 as the dopant in the emissive layer (EML).
The implementation mode in Device Comparative Example 1 was the same as that in Device Example 1, except that Compound 2-2 was replaced with Compound RD-A as the dopant in the emissive layer (EML).
The implementation mode in Device Comparative Example 2 was the same as that in Device Example 2, except that Compound 2-2 was replaced with Compound RD-A as the dopant in the emissive layer (EML).
The implementation mode in Device Comparative Example 3 was the same as that in Device Example 1, except that Compound 1-1 was replaced with Compound CBP as the host in the emissive layer (EML).
The implementation mode in Device Comparative Example 4 was the same as that in Device Comparative Example 3, except that Compound 2-2 was replaced with Compound RD-A as the dopant in the emissive layer (EML).
The implementation mode in Device Comparative Example 5 was the same as that in Device Comparative Example 3, except that Compound 2-2 was replaced with Compound 2-43 as the dopant in the emissive layer (EML).
The implementation mode in Device Comparative Example 6 was the same as that in Device Comparative Example 3, except that Compound 2-2 was replaced with Compound 2-1 as the dopant in the emissive layer (EML).
The implementation mode in Device Comparative Example 8 was the same as that in Device Example 5, except that Compound 1-2 was replaced with Compound A as the host in the emissive layer (EML).
The structures and thicknesses of layers of the devices are shown in the following table. A layer using more than one material is obtained by doping different compounds at their weight ratios as recorded.
The structures of the materials used in the devices are shown as follows:
The voltage (V), power efficiency (PE) and lifetime (LT97) of Device Examples 1-6 and Device Comparative Examples 1-6 and 8, which were measured at 15 mA/cm2, are listed in Table 2.
Discussion
As shown in Table 2, the device comparative examples in the present disclosure were set with reference to device experiments disclosed in the related art (such as KR1020150077220A), using a host material (such as Compound CBP) commonly used in the related art (such as KR1020150077220A), and a current commercial host material, Compound A, and a phosphorescent light-emitting material (such as Compound RD-A) commonly used in the related art (such as KR1020150077220A) as comparative compounds.
It can be seen from the device data that Example 1 which uses a combination of the present disclosure (first compound 1-1 and second compound 2-2) as the emissive layer has the same voltage as Comparative Example 1 (which uses first compound 1-1 and RD-A as the emissive layer), but the power efficiency of Example 1 is 10 lm/W (2.5 times) higher than that of Comparative Example 1 and the lifetime of Example 1 is 165 hours (41.3 times) longer than that of Comparative Example 1, which are unexpectedly improved. Similarly, it can be seen that Example 2 which uses a combination of the present disclosure (first compound 1-2 and second compound 2-2) as the emissive layer has a driving voltage (3.4 V) that is 0.2 V lower than that (3.6 V) of Comparative Example 2 (which uses first compound 1-2 and RD-A as the emissive layer), and the power efficiency of Example 2 is 11 lm/W (2.0 times) higher than that of Comparative Example 2 and the lifetime of Example 2 is 1511 hours (116 times) longer than that of Comparative Example 2, which are surprisingly improved. In particular, the lifetime has been improved more than 100 times.
Example 3 which uses a combination of the present disclosure (first compound 1-1 and second compound 2-125) as the emissive layer has substantially the same voltage as Comparative Example 1 (which uses first compound 1-1 and RD-A as the emissive layer), but the power efficiency of Example 3 is 12 lm/W (3.0 times) higher than that of Comparative Example 1 and the lifetime of Example 3 is 495.4 hours (123.9 times) longer than that of Comparative Example 1, which are also surprisingly improved.
Example 4 which uses a combination of the present disclosure (first compound 1-2 and second compound 2-125) as the emissive layer has the same voltage as Comparative Example 2 (which uses first compound 1-2 and RD-A as the emissive layer), but the power efficiency of Example 4 is 12 lm/W (2.0 times) higher than that of Comparative Example 2 and the lifetime of Example 4 is 2056 hours (158.2 times) longer than that of Comparative Example 2, which are unexpectedly improved. In particular, the lifetime has been further improved and reaches 2069 hours.
These results show that the combination of the first compound and the second compound of the present disclosure can greatly improve device performance (driving voltage, power efficiency and lifetime), which far exceeds the device effects when the first compound selected by the present disclosure is used in combination with the phosphorescent light-emitting material that is used as the dopant in the related art. This indicates the superiority of the combination of the first compound and the second compound of the present disclosure. In particular, this also fully proves the unexpected effects due to the use of the first compound selected by the present disclosure as a red phosphorescent host material in combination with the second compound with a particular structure.
Example 1 which uses the combination of the present disclosure (first compound 1-1 and second compound 2-2) as the emissive layer has a driving voltage (3.5 V) that is 5.1 V lower than that (8.6 V) of Comparative Example 3 (which uses CBP and second compound 2-2 as the emissive layer), and the power efficiency of Example 1 is 10 lm/W (2.5 times) higher than that of Comparative Example 3 and the lifetime of Example 1 is 162 hours (23.1 times) longer than that of Comparative Example 3, which are significantly improved.
Example 2 which uses the combination of the present disclosure (first compound 1-2 and second compound 2-2) as the emissive layer has a driving voltage (3.4 V) that is 5.2 V lower than that (8.6 V) of Comparative Example 3 (which uses CBP and second compound 2-2 as the emissive layer), and the power efficiency of Example 2 is 13 lm/W (3.3 times) higher than that of Comparative Example 3 and the lifetime of Example 2 is 1517 hours (216.7 times) longer than that of Comparative Example 3, which are significantly improved.
Example 5 which uses a combination of the present disclosure (first compound 1-2 and second compound 2-43) as the emissive layer has a driving voltage (3.6 V) that is 4.6 V lower than that (8.2 V) of Comparative Example 5 (which uses CBP and second compound 2-43 as the emissive layer), and the power efficiency of Example 5 is 21 lm/W (2.6 times) higher than that of Comparative Example 5 and the lifetime of Example 5 is 867.6 hours (135.6 times) longer than that of Comparative Example 5.
Example 6 which uses a combination of the present disclosure (first compound 1-2 and second compound 2-1) as the emissive layer has a driving voltage (3.5 V) that is 5.6 V lower than that (9.1 V) of Comparative Example 6 (which uses CBP and second compound 2-1 as the emissive layer), and the power efficiency of Example 6 is 13 lm/W (2.6 times) higher than that of Comparative Example 6 and the lifetime of Example 6 is 1215.8 hours (190 times) longer than that of Comparative Example 6.
These results show that the combination of the first compound and the second compound of the present disclosure can greatly improve device performance, which far exceeds the device effects when the second compound selected by the present disclosure is used as the dopant in combination with the compound in the related art as the host. This indicates the superiority of the combination of the first compound and the second compound of the present disclosure. In particular, this also fully proves the unexpected effects due to the use of the first compound selected by the present disclosure as the red phosphorescent host material in combination with the second compound with a particular structure.
Example 5 which uses the combination of the present disclosure (first compound 1-2 and second compound 2-43) as the emissive layer has a driving voltage (3.6 V) that is 0.8 V lower than that (4.4 V) of Comparative Example 8 which uses the current commercial host material, Compound A (using Compound A and second compound 2-43 as the emissive layer), and the power efficiency of Example 5 is 2 lm/W (7.4%) higher than that of Comparative Example 8 and the lifetime of Example 5 is 20 hours (2.3%) longer than that of Comparative Example 8. These data show that the material combination disclosed by the present disclosure can further improve the device performance based on the level of the commercial material, which is very rare.
These results show that the combination of the first compound and the second compound of the present disclosure can greatly improve the device performance and further improve the device performance based on the level of the current commercial host material. This further indicates the superiority of the combination of the first compound and the second compound of the present disclosure. In particular, this also fully proves the unexpected effects due to the use of the first compound selected by the present disclosure as the red phosphorescent host material in combination with the second compound with a particular structure.
In summary, the combination of the first compound and the second compound disclosed by the present disclosure, due to good matching in energy, can enable the device to exhibit excellent comprehensive performance, such as a lower driving voltage, higher efficiency and an ultra-long lifetime.
It is to be understood that various embodiments described herein are merely exemplary 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 is to be understood that various theories as to why the present disclosure works are not intended to be limitative.
| Number | Date | Country | Kind |
|---|---|---|---|
| 202010505871.4 | Jun 2020 | CN | national |
| 202110464966.0 | Apr 2021 | CN | national |
