Organic electroluminescent material containing spiroalkene structure and device
1. A compound having a structure represented by formula 1:
in the formula 1, the reaction mixture is,
said L1Represents a single bond, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
ar is1Has a structure represented by formula 2:
wherein A is1To A6Each independently selected from C, CR15Or N, and A1To A6At least two of which are N;
substituent R1And R2R is2And R3R is3And R4R is6And R7R is7And R8R is8And R9R is9And R10R is10And R11R is11And R12R is12And R13R is13And R14Two adjacent substituents can optionally be linked to form a ring;
R15each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl 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 unsubstitutedSubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, thio groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
two adjacent substituents R15Can optionally be linked to form a ring;
R1to R14Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid group, ester group, cyano, isocyano, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.
2. The compound of claim 1, wherein R is for the substituent in formula 11To R14None of these substituents is linked to form a ring.
3. The compound of claim 1, wherein said L1Each independently selected from the group consisting of a single bond, phenylene, biphenylene, naphthylene, terphenylene, and pyridylene.
4. The compound of claim 1 or 3, wherein Ar is1Has a structure represented by formula 2-1:
in the formula 2-1, A1To A4Each independently selected from C, N or CR15And A is1To A4At least 2 of (A) are N, A5To A8Each independently selected from CR15；
R15Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, cyano groups, and combinations thereof;
adjacent substituents R15Can optionally be linked to form a ring.
5. The compound of claim 1 or 3, wherein Ar is1Has a structure represented by one of formulas 3-1 to 3-12:
wherein R is15Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, cyano groups, and combinations thereof;
wherein the adjacent substituents R15Can optionally be linked to form a ring.
6. The compound of claim 5, wherein R15Each occurrence, identically or differently, is selected from hydrogen, deuterium, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms;
adjacent substituents R15Can optionally be linked to form a ring.
7. The compound of claim 6, wherein R15Each occurrence, identically or differently, is selected from hydrogen, deuterium, phenyl, biphenyl or naphthyl.
8. The compound of claim 1, wherein said Ar is1A structure selected from the group consisting of structures represented by one of formulas 4-1 to 4-40:
9. the compound of claim 1, wherein R1To R14Each independently selected from hydrogen or deuterium.
10. The compound of claim 1, wherein the compound is selected from the group consisting of compound 1 through compound 162:
optionally, wherein the hydrogen in the above compounds can be partially or fully deuterated.
11. An electroluminescent device, comprising:
an anode, a cathode, a anode and a cathode,
a cathode electrode, which is provided with a cathode,
and an organic layer disposed between the anode and the cathode, the organic layer comprising a compound having the structure of formula 1:
in the formula 1, the reaction mixture is,
said L1Represents a single bond, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
ar is1Has a structure represented by formula 2:
wherein A is1To A6Each independently selected from C, CR15Or N, and A1To A6At least two of which are N;
substituent R1And R2R is2And R3R is3And R4R is6And R7R is7And R8R is8And R9R is9And R10R is10And R11R is11And R12R is12And R13R is13And R14Two adjacent substituents can optionally be linked to form a ring;
R15each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl silicon group having 6 to 20 carbon atoms.An alkyl group, a substituted or unsubstituted amine group having 0-20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a thio group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
two adjacent substituents R15Can optionally be linked to form a ring;
R1to R14Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid group, ester group, cyano, isocyano, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.
12. The device of claim 11, wherein the organic layer is an emissive layer, the compound is a host material, and the emissive layer further comprises a phosphorescent emissive material.
13. The electroluminescent device of claim 12, wherein the phosphorescent light-emitting material is a metal complex comprising at least one ligand comprising the structure of any one of:
wherein the content of the first and second substances,
Ra，Rband RcRepresents mono-, poly-, or unsubstituted, and Ra，RbAnd RcEach at each occurrence is the same or different;
Xbselected from the group consisting of: o, S, Se, NRN1And CRC1RC2；
XcAnd XdEach independently selected from the group consisting of: o, S, Se and NRN2；
Ra，Rb，Rc，RN1，RN2，RC1And RC2The same or different at each occurrence is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0-20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, thio groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
in the ligand structure, adjacent substituents can optionally be linked to form a ring.
14. An electroluminescent device as claimed in claim 13 in which the phosphorescent light-emitting material is an Ir, Pt or Os complex.
15. An electroluminescent device as claimed in claim 13 wherein the phosphorescent light-emitting material is an Ir complex and has Ir (L)a)(Lb)(Lc) The structure of (1);
wherein L isa，LbAnd LcEach independently selected from any one of said ligands.
16. An electroluminescent device as claimed in claim 15 wherein the phosphorescent light-emitting material is selected from any one of:
wherein, XfSelected, identically or differently on each occurrence, from O, S, Se, NRN3Or CRC3RC4；
Wherein, XeSelected from CR, identically or differently at each occurrencedOr N;
Raand RbRepresents mono-, poly-or unsubstituted, and is each, at each occurrence, the same or different;
Ra、Rb、Rc、Rd、RN3、RC3and RC4Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl 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 aryl having 3 to 20 carbon atoms, or a combination thereofSubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, thio groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof.
17. A compound formulation comprising the compound of claim 1.
Background
Organic electronic devices include, but are not limited to, the following classes: organic Light Emitting Diodes (OLEDs), organic field effect transistors (O-FETs), Organic Light Emitting Transistors (OLETs), Organic Photovoltaics (OPVs), dye-sensitized solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field effect devices (OFQDs), light emitting electrochemical cells (LECs), organic laser diodes, and organic plasma light emitting devices.
In 1987, Tang and Van Slyke of Islamic Kodak reported a two-layer organic electroluminescent device comprising an arylamine hole transport layer and a tris-8-hydroxyquinoline-aluminum layer as an electron transport layer and a light-emitting layer (Applied Physics Letters, 1987,51(12): 913-915). Upon biasing the device, green light is emitted from the device. The invention lays a foundation for the development of modern Organic Light Emitting Diodes (OLEDs). The most advanced OLEDs may comprise multiple layers, such as charge injection and transport layers, charge and exciton blocking layers, and one or more light emitting layers between the cathode and anode. Since OLEDs are a self-emissive solid state device, it offers great potential for display and lighting applications. Furthermore, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications, such as in the fabrication of flexible substrates.
OLEDs can be classified into three different types according to their light emitting mechanisms. The OLEDs invented by Tang and van Slyke are fluorescent OLEDs. It uses only singlet luminescence. The triplet states generated in the device are wasted through the non-radiative decay channel. Therefore, the Internal Quantum Efficiency (IQE) of fluorescent OLEDs is only 25%. This limitation hinders the commercialization of OLEDs. In 1997, Forrest and Thompson reported phosphorescent OLEDs, which use triplet emission from complex-containing heavy metals as emitters. Thus, singlet and triplet states can be harvested, achieving 100% IQE. Due to its high efficiency, the discovery and development of phosphorescent OLEDs directly contributes to the commercialization of active matrix OLEDs (amoleds). Recently, Adachi has achieved high efficiency through Thermally Activated Delayed Fluorescence (TADF) of organic compounds. These emitters have a small singlet-triplet gap, making it possible for excitons to return from the triplet state to the singlet state. In TADF devices, triplet excitons are able to generate singlet excitons through reverse intersystem crossing, resulting in high IQE.
OLEDs can also be classified into small molecule and polymer OLEDs depending on the form of the material used. Small molecule refers to any organic or organometallic material that is not a polymer. The molecular weight of small molecules can be large, as long as they have a precise structure. Dendrimers with well-defined structures are considered small molecules. The polymeric OLED comprises a conjugated polymer and a non-conjugated polymer having a pendant light-emitting group. Small molecule OLEDs can become polymer OLEDs if post-polymerization occurs during the fabrication process.
Various OLED manufacturing methods exist. Small molecule OLEDs are typically fabricated by vacuum thermal evaporation. Polymer OLEDs are fabricated by solution processes such as spin coating, ink jet printing and nozzle printing. Small molecule OLEDs can also be made by solution processes if the material can be dissolved or dispersed in a solvent.
The light emitting color of the OLED can be realized by the structural design of the light emitting material. An OLED may comprise one light emitting layer or a plurality of light emitting layers to achieve a desired spectrum. Green, yellow and red OLEDs, phosphorescent materials have been successfully commercialized. Blue phosphorescent devices still have the problems of blue unsaturation, short device lifetime, high operating voltage, and the like. Commercial full-color OLED displays typically employ a hybrid strategy, using either blue fluorescence and phosphorescent yellow, or red and green. At present, the rapid decrease in efficiency of phosphorescent OLEDs at high luminance is still a problem. In addition, it is desirable to have a more saturated emission spectrum, higher efficiency and longer device lifetime.
CN103524398A discloses a naphthalene-based compound with a high condensed ring-aza [6] helicene structure and a preparation method thereof:
wherein R is1-R13Each independently is H, alkyl, halogen, or an aromatic or heteroaromatic ring containing C, N, O, S atoms. Specific examples are:the application seems to focus on the synthesis of such compounds, only mentioning broadly a possible range of uses of the compounds, and does not focus on such naphthalene-based highly fused ring-aza [6]]The properties of the spiroalkene structure further do not disclose or teach any property changes and applications that may be brought about by the introduction of polyaza-heteroaryl groups in such compound systems.
A compound comprising a benzophenanthrene fused structure is disclosed in US20150255726a 1:wherein, is selected from R1To R12At least one group of adjacent 2 of the above-mentioned members are bonded to each other to formThe disclosed compounds haveThe skeleton structure of (1). It is clear that this unique property brought about by the indolo fused ring structure is noted, but it does not disclose or teach the use of introducing indolo rings elsewhere on the benzophenanthrene ring.
Patent KR20180031385A discloses a compound having a naphthocarbazole structure:however, it does not disclose or teach the use of spiroalkene compounds having a phenanthrocarbazole structure.
However, there is still room for improvement in the currently reported host materials, and in order to meet the increasing demand in the industry, a more excellent novel host material still needs to be synthesized and developed. Compared with the prior art, the organic electroluminescent device containing the compound can obtain higher efficiency and provide better device performance.
Disclosure of Invention
The present invention aims to solve at least part of the above problems by providing novel compounds containing a spiroalkene structure, which can be used as host materials in electroluminescent devices and provide higher current efficiency and external quantum efficiency, and better device performance.
According to one embodiment of the present invention, a compound is disclosed having a structure represented by formula 1:
in the formula 1, the reaction mixture is,
said L1Represents a single bond, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
ar is1Has a structure represented by formula 2:
wherein A is1To A6Each independently selected from C, CR15Or N, and A1To A6At least two of which are N;
R1to R14Wherein two adjacent substituents can optionally be linked to form a ring;
two adjacent substituents R15Can optionally be linked to form a ring;
R1to R15Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted with 1 to 20 carbon atomsSubstituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl 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 amine having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid group, ester group, cyano, isocyano, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.
According to another embodiment of the present invention, there is also disclosed an electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprising a compound having the structure of formula 1:
in the formula 1, the reaction mixture is,
said L1Represents a single bond, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
ar is1Has a structure represented by formula 2:
wherein A is1To A6Each independently selected from C, CR15Or N, and A1To A6At least two of which are N;
R1to R14Wherein two adjacent substituents can optionally be linked to form a ring;
two adjacent substituents R15Can optionally be linked to form a ring;
R1to R15Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0-20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, thio groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof.
According to another embodiment of the present invention, a compound formulation comprising the compound having the structure of formula 1 is also disclosed.
The novel compound with the spiroalkene structure can be used as a main body material in an electroluminescent device. These novel compounds provide higher current and external quantum efficiencies, providing better device performance.
Drawings
FIG. 1 is a schematic representation of an organic light emitting device that can contain the compounds and compound formulations disclosed herein.
Fig. 2 is a schematic view of another organic light emitting device that can contain compounds and compound formulations disclosed herein.
Detailed Description
OLEDs can be fabricated on a variety of substrates, such as glass, plastic, and metal. Fig. 1 schematically, but without limitation, illustrates an organic light emitting device 100. The figures are not necessarily to scale, and some of the layer structures in the figures may be omitted as desired. The device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, an emissive layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180, and a cathode 190. The device 100 may be fabricated by sequentially depositing the described layers. The nature and function of the layers, as well as exemplary materials, are described in more detail in U.S. patent US7,279,704B2, columns 6-10, which is incorporated herein by reference in its entirety.
There are more instances of each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is doped with F at a molar ratio of 50:14TCNQ m-MTDATA as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of host materials are disclosed in U.S. patent No. 6,303,238 to Thompson et al, which is incorporated by reference 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 in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, disclose examples of cathodes including composite cathodes having a thin layer of a metal such as Mg: Ag and an overlying layer of transparent, conductive, sputter-deposited ITO. The principles and use of barrier layers are described in more detail in U.S. patent No. 6,097,147 and U.S. patent application publication No. 2003/0230980, which are incorporated by reference in their entirety. Examples of injection layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of the protective layer may be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.
The above-described hierarchical structure is provided via non-limiting embodiments. The function of the OLED may be achieved by combining the various layers described above, or some layers may be omitted entirely. It may also include other layers not explicitly described. Within each layer, a single material or a mixture of materials may be used to achieve optimal performance. Any functional layer may comprise several sub-layers. For example, the light emitting layer may have two layers of different light emitting materials to achieve a desired light emission spectrum.
In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. The organic layer may include one or more layers.
The OLED also requires an encapsulation layer, as shown in fig. 2, which is an exemplary, non-limiting illustration of an organic light emitting device 200, which differs from fig. 1 in that an encapsulation layer 102 may also be included over the cathode 190 to protect against harmful substances from the environment, such as moisture and oxygen. Any material capable of providing an encapsulation function may be used as the encapsulation layer, such as glass or a hybrid organic-inorganic layer. The encapsulation layer should be placed directly or indirectly outside the OLED device. Multilayer film encapsulation is described in U.S. patent US7,968,146B2, the entire contents of which are incorporated herein by reference.
Devices manufactured according to embodiments of the present invention may be incorporated into various consumer products having one or more electronic component modules (or units) of the device. Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and/or signaling, head-up displays, fully or partially transparent displays, flexible displays, smart phones, tablet computers, tablet handsets, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicle displays, and tail lights.
The materials and structures described herein may also be used in other organic electronic devices as previously listed.
As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. Where a first layer is described as being "disposed on" a second layer, the first layer is disposed farther from the substrate. Other layers may be present 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 can be described as being "disposed on" an anode even though various organic layers are present between the cathode and the anode.
As used herein, "solution processable" means capable of being dissolved, dispersed or transported in and/or deposited from a liquid medium in the form of a solution or suspension.
A ligand may be referred to as "photoactive" when it is believed that the ligand directly contributes to the photoactive properties of the 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 the emissive material, but the ancillary ligand may alter the properties of the photoactive ligand.
It is believed that the Internal Quantum Efficiency (IQE) of fluorescent OLEDs can be limited by delaying fluorescence beyond 25% spin statistics. Delayed fluorescence can generally be divided into two types, i.e., P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence results from triplet-triplet annihilation (TTA).
On the other hand, E-type delayed fluorescence does not depend on collision of two triplet states, but on conversion between triplet and singlet excited states. Compounds capable of producing E-type delayed fluorescence need to have a very small mono-triplet gap in order to switch 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 significant feature of TADF is that the retardation component increases with increasing temperature. If the reverse intersystem crossing (RISC) rate is fast enough to minimize non-radiative decay from the triplet state, then the fraction of backfill singlet excited states may reach 75%. The total singlet fraction may be 100%, far exceeding 25% of the spin statistics of the electrogenerated excitons.
The delayed fluorescence characteristic of type E can be found in excited complex systems or in single compounds. Without being bound by theory, it is believed that E-type delayed fluorescence requires the light emitting material to have a small mono-triplet energy gap (Δ Ε)S-T). Organic non-metal containing donor-acceptor emissive materials may be able to achieve this. The emission of these materials is generally characterized as donor-acceptor Charge Transfer (CT) type emission. Spatial separation of HOMO from LUMO in these donor-acceptor type compounds generally results in small Δ ES-T. These states may include CT states. Generally, donor-acceptor light emitting materials are constructed by linking an electron donor moiety (e.g., an amino or carbazole derivative) to an electron acceptor moiety (e.g., a six-membered, N-containing, aromatic ring).
Definitions for substituent terms
Halogen or halide-as used herein, includes fluorine, chlorine, bromine and iodine.
Alkyl-comprises both straight and branched chain alkyl groups. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl. In addition, the alkyl group may be optionally substituted. The carbons in the alkyl chain may be substituted with other heteroatoms. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl and neopentyl are preferable.
Cycloalkyl-as used herein, comprises a cyclic alkyl group. Preferred cycloalkyl groups are those containing 4 to 10 ring carbon atoms and include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4, 4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like. In addition, the cycloalkyl group may be optionally substituted. The carbon in the ring may be substituted with other heteroatoms.
Alkenyl-as used herein, encompasses both straight and branched chain olefinic groups. Preferred alkenyl groups are those containing 2 to 15 carbon atoms. Examples of the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a1, 3-butadienyl group, a 1-methylvinyl group, a styryl group, a 2, 2-diphenylvinyl group, a 1-methylallyl group, a1, 1-dimethylallyl group, a 2-methylallyl group, a 1-phenylallyl group, a 3, 3-diphenylallyl group, a1, 2-dimethylallyl group, a 1-phenyl-1-butenyl group and a 3-phenyl-1-butenyl group. In addition, alkenyl groups may be optionally substituted.
Alkynyl-as used herein, straight and branched alkynyl groups are contemplated. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. In addition, alkynyl groups may be optionally substituted.
Aryl or aromatic-as used herein, non-fused and fused systems are contemplated. Preferred aryl groups are those containing from 6 to 60 carbon atoms, more preferably from 6 to 20 carbon atoms, and even more preferably from 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, the aryl group may be optionally substituted. Examples of non-fused 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 '-methyldiphenyl, 4' -tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2, 3-xylyl, 3, 4-xylyl, 2, 5-xylyl, mesityl and m-quaterphenyl.
Heterocyclyl or heterocyclic-as used herein, aromatic and non-aromatic cyclic groups are contemplated. Heteroaryl also refers to heteroaryl. Preferred non-aromatic heterocyclic groups are those containing 3 to 7 ring atoms, which include at least one heteroatom such as nitrogen, oxygen and sulfur. The heterocyclic group may also be an aromatic heterocyclic group having at least one hetero atom selected from a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom.
Heteroaryl-as used herein, non-fused and fused heteroaromatic groups are contemplated which may contain 1 to 5 heteroatoms. Preferred heteroaryl groups are those containing from 3 to 30 carbon atoms, more preferably from 3 to 20 carbon atoms, more preferably from 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridine indole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indoline, benzimidazole, indazole, indenozine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuropyridine, furobipyridine, benzothienopyridine, thienobipyridine, cinnolino, benzoselenophenopyridine, selenobenzene, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1, 2-azaborine, 1, 3-azaborine, 1, 4-azaborine, borazole, and aza analogues thereof. In addition, the heteroaryl group may be optionally substituted.
Alkoxy-is represented by-O-alkyl. Examples and preferred examples of the alkyl group are the same as those described above. Examples of the alkoxy group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy and hexyloxy. The alkoxy group having 3 or more carbon atoms may be linear, cyclic or branched.
Aryloxy-is represented by-O-aryl or-O-heteroaryl. Examples and preferred examples of aryl and heteroaryl groups are the same as described above. Examples of the aryloxy group having 6 to 40 carbon atoms include a phenoxy group and a biphenyloxy group.
Aralkyl-as used herein, an alkyl group having an aryl substituent. In addition, the aralkyl group may be optionally substituted. Examples of the aralkyl group include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α -naphthylmethyl, 1- α -naphthylethyl, 2- α -naphthylethyl, 1- α -naphthylisopropyl, 2- α -naphthylisopropyl, β -naphthylmethyl, 1- β -naphthylethyl, 2- β -naphthylethyl, 1- β -naphthylisopropyl, 2- β -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. Among the above, benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl are preferable.
The term "aza" in aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more C-H groups in the corresponding aromatic moiety are replaced by a nitrogen atom. For example, azatriphenylenes include dibenzo [ f, h ] quinoxalines, dibenzo [ f, h ] quinolines, and other analogs having two or more nitrogens in the ring system. Other nitrogen analogs of the above-described aza derivatives may be readily envisioned by one of ordinary skill in the art, and all such analogs are intended to be encompassed within the terms described herein.
In this disclosure, unless otherwise defined, when any one of the terms in the group consisting of: substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted amine, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, substituted sulfonyl, substituted phosphino, meaning alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, alkenyl, alkynyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amine, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphino, any of which may be substituted by one or more ring carbons selected from deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbons, unsubstituted heteroalkyl having 1 to 20 carbon atoms, unsubstituted aralkyl having 7 to 30 carbon atoms, unsubstituted alkoxy having 1 to 20 carbon atoms, unsubstituted aryloxy having 6 to 30 carbon atoms, unsubstituted alkenyl having 2 to 20 carbon atoms, unsubstituted alkynyl having 2 to 20 carbon atoms, unsubstituted aryl having 6 to 30 carbon atoms, unsubstituted heteroaryl having 3 to 30 carbon atoms, unsubstituted alkylsilyl having 3 to 20 carbon atoms, unsubstituted arylsilyl having 6 to 20 carbon atoms, unsubstituted amine having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid group, ester group, cyano, isocyano, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.
It will be understood that when a molecular fragment is described as a substituent or otherwise attached to another moiety, its name may be written depending on whether it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or depending on whether it is an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying substituents or linking fragments are considered to be equivalent.
In the compounds mentioned in the present disclosure, a hydrogen atom may be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen may also be replaced by their other stable isotopes. Substitution of other stable isotopes in the compounds may be preferred because it enhances the efficiency and stability of the device.
In the compounds mentioned in the present disclosure, polysubstitution is meant to encompass disubstituted substitutions up to the maximum range of available substitutions. When a substituent in a compound mentioned in the present disclosure represents multiple substitution (including di-substitution, tri-substitution, tetra-substitution, etc.), that is, it means that the substituent may exist at a plurality of available substitution positions on its connecting structure, and the substituent existing at each of the plurality of available substitution positions may be the same structure or different structures.
In the compounds mentioned in the present disclosure, adjacent substituents in the compounds cannot be linked to form a ring unless specifically defined, for example, adjacent substituents can be optionally linked to form a ring. In the compounds mentioned in the present disclosure, adjacent substituents can be optionally linked to form a ring, including both the case where adjacent substituents may be linked to form a ring and the case where adjacent substituents are not linked to form a ring. When adjacent substituents can optionally be joined to form a ring, the ring formed can be monocyclic or polycyclic, as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic rings. In this expression, adjacent substituents may refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to carbon atoms further away. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom as well as substituents bonded to carbon atoms directly bonded to each other.
The expression that adjacent substituents can optionally be linked to form a ring is also intended to mean that two substituents bonded to the same carbon atom are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:
the expression that adjacent substituents can optionally be linked to form a ring is also intended to mean that two substituents bonded to carbon atoms directly bonded to each other are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:
further, the expression that adjacent substituents can be optionally connected to form a ring is also intended to be taken to mean that, in the case where one of two substituents bonded to carbon atoms directly bonded to each other represents hydrogen, the second substituent is bonded at a position to which the hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following equation:
according to one embodiment of the present invention, a compound is disclosed having a structure represented by formula 1:
in the formula 1, the reaction mixture is,
said L1Represents a single bond, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
ar is1Has a structure represented by formula 2:
wherein A is1To A6Each independently selected from C, CR15Or N, and A1To A6At least two of which are N;
R1to R14Wherein two adjacent substituents can optionally be linked to form a ring;
two adjacent substituents R15Can optionally be linked to form a ring;
R1to R15Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0-20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, thio groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof.
In this embodiment, R1To R14Wherein two adjacent substituents can optionally be linked to form a ring, is intended to indicate that in formula 1, the substituent R1And R2R is2And R3R is3And R4R is5And R6R is6And R7R is7And R8R is8And R9R is9And R10R is10And R11R is11And R12R is12And R13R is13And R14Optionally linked to form a ring. It is obvious to those skilled in the art that these substituents may not be connected to each other to form a ring.
In this embodiment, in formula 2, the position indicated by "+" is Ar1In formula 1 with L1The location of the connection.
According to an embodiment of the present invention, wherein said L1Each independently selected from the group consisting of a single bond, phenylene, biphenylene, naphthylene, terphenylene, and pyridylene.
According to an embodiment of the present invention, wherein said Ar1Has a structure represented by formula 2-1:
wherein A is1To A4Each independently selected from C, N or CR15And A is1To A4At least 2 of (A) are selected from N, A5To A8Each independently selected from CR15；R15Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted aralkyl having 7 to 30 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, or a salt thereofSubstituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, cyano, and combinations thereof;
adjacent substituents R15Can optionally be linked to form a ring.
In this embodiment, in formula 2-1, the position indicated by "+" is Ar1In formula 1 with L1The location of the connection.
According to an embodiment of the present invention, wherein said Ar1Has a structure represented by formula 3-1 to formula 3-12:
wherein R is15Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, cyano groups, and combinations thereof;
wherein the adjacent substituents R15Can optionally be linked to form a ring.
In this embodiment, the position marked by "+" is Ar in formula 11And L1The location of the connection.
According to one embodiment of the invention, wherein R is15Each occurrence, identically or differently, is selected from the group consisting of hydrogen, deuterium, and a substituted or unsubstituted aryl group having 6 to 30 carbon atoms;
adjacent substituents R15Can optionally be linked to form a ring.
In this example, the adjacent substituents R15Can optionally be linked to form a ring, intended to denote adjacent substituents R15The rings may or may not be linked to each other.
According to one embodiment of the invention, wherein R is15Selected, identically or differently on each occurrence, from hydrogen, deuteriumPhenyl, biphenyl or naphthyl.
According to an embodiment of the present invention, wherein said Ar1Selected from the group consisting of structures represented by the following formulae 4-1 to 4-40:
in this embodiment, the position marked by "+" is Ar in formula 11And L1The location of the connection.
According to an embodiment of the present invention, wherein in said formula 1, R1To R14Each independently selected from hydrogen or deuterium.
According to one embodiment of the present invention, wherein the compound is selected from the group consisting of compound 1 to compound 162:
according to an embodiment of the present invention, wherein the hydrogen energy in said compounds 1 to 162 is partially or completely substituted by deuterium.
According to an embodiment of the present invention, there is also disclosed an electroluminescent device, including:
an anode, a cathode, a anode and a cathode,
a cathode electrode, which is provided with a cathode,
and an organic layer disposed between the anode and the cathode, the organic layer comprising a compound having the structure of formula 1:
in the formula 1, the reaction mixture is,
said L1Represents a single bond, or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
ar is1Has a structure represented by formula 2:
wherein A is1To A6Each independently selected from C, CR15Or N, and A1To A6At least two of which are N;
R1to R14Wherein two adjacent substituents can optionally be linked to form a ring;
two adjacent substituents R15Can optionally be linked to form a ring;
R1to R15Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0-20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, thio groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof.
According to one embodiment of the invention, in the device, the organic layer is a light emitting layer.
According to one embodiment of the present invention, in the device, the organic layer is a light emitting layer, and the compound is a host material.
According to one embodiment of the invention, in the device, the organic layer is a light emitting layer, which further comprises a phosphorescent light emitting material.
According to one embodiment of the invention, in the device, the phosphorescent light emitting material is a metal complex comprising at least one ligand comprising the structure of any one of:
wherein the content of the first and second substances,
Ra，Rband RcMay represent mono-, poly-, or unsubstituted, and Ra，RbAnd RcEach may be the same or different at each occurrence;
Xbselected from the group consisting of: o, S, Se, NRN1Or CRC1RC2；
XcAnd XdEach independently selected from the group consisting of: o, S, Se or NRN2；
Ra，Rb，Rc，RN1，RN2，RC1And RC2The same or different at each occurrence is selected from the group consisting of: hydrogen, deuterium, halogen, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0-20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, thio groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
in the ligand structure, adjacent substituents can optionally be linked to form a ring.
According to one embodiment of the present invention, in the device, the phosphorescent light emitting material is an Ir, Pt or Os complex.
According to one embodiment of the present invention, in the device, the phosphorescent light emitting material is an Ir complex and has Ir (L)a)(Lb)(Lc) The structure of (1);
wherein L isa，LbAnd LcEach independently selected from any of the above ligands.
According to one embodiment of the invention, in the device, the phosphorescent light emitting material is:
wherein, XfSelected, identically or differently on each occurrence, from O, S, Se, NRN3Or CRC3RC4；
Wherein, XeSelected from CR, identically or differently at each occurrencedOr N;
Raand RbRepresents mono-, poly-or unsubstituted, and each may be the same or different at each occurrence;
Ra、Rb、Rc、Rd、RN3、RC3and RC4Each occurrence, the same or different, is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted amine groups having 0-20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, thio groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof.
According to another embodiment of the present invention, a compound formulation comprising a compound represented by formula 1 is also disclosed. The specific structure of the compound is shown in any one of the embodiments.
In combination with other materials
The materials described herein for use in particular layers in an organic light emitting device may be used in combination with various other materials present in the device. Combinations of these materials are described in detail in U.S. patent application Ser. No. 0132-0161 of U.S. 2016/0359122A1, the entire contents of which are incorporated herein by reference. The materials described or referenced therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.
Materials described herein as being useful for particular layers in an organic light emitting device can be used in combination with a variety of other materials present in the device. For example, the compounds disclosed herein may be used in conjunction with a variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. Combinations of these materials are described in detail in U.S. patent application Ser. No. US2015/0349273A1, paragraph 0080-0101, the entire contents of which are incorporated herein by reference. The materials described or referenced therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.
In the examples of material synthesis, all reactions were carried out under nitrogen unless otherwise stated. All reaction solvents were anhydrous and used as received from commercial sources. The synthesis product is subjected to structural validation and characterization using one or more equipment conventional in the art (including, but not limited to, Bruker's nuclear magnetic resonance apparatus, Shimadzu's liquid chromatograph-mass spectrometer, gas chromatograph-mass spectrometer, differential scanning calorimeter, Shanghai prism-based fluorescence spectrophotometer, Wuhan Corset's electrochemical workstation, Anhui Beidek's sublimator, etc.) in a manner well known to those skilled in the art. In an embodiment of the device, the device characteristics are also tested using equipment conventional in the art (including, but not limited to, an evaporator manufactured by Angstrom Engineering, an optical test system manufactured by Fushida, Suzhou, an ellipsometer manufactured by Beijing Mass., etc.) in a manner well known to those skilled in the art. Since the relevant contents of the above-mentioned device usage, testing method, etc. are known to those skilled in the art, the inherent data of the sample can be obtained with certainty and without being affected, and therefore, the relevant contents are not described in detail in this patent.
Materials synthesis example:
the preparation method of the compound of the present invention is not limited, and the following compounds are typically but not limited to, and the synthetic route and the preparation method thereof are as follows:
synthesis example 1: synthesis of Compound 1
Step 1: synthesis of intermediate A
4-Bromocarbazole (20g, 81.3mmol), pinacol diborate (24.8g, 97.6mmol) and potassium acetate (12g, 122mmol) were charged in a 1L two-necked flask, stirred in dioxane (400mL), purged with nitrogen for 10min and then Pd (dppf) Cl was added2(3g, 4.1mmol), warm to 100 ℃ under nitrogen and react overnight. After completion of the reaction, it was cooled, Ethyl Acetate (EA) was added, washed with water, the organic phase was spin-dried, and the residue was purified by column chromatography (PE/DCM: 3/1) to give intermediate a (21.5g, yield: 90%) as a white solid.
Step 2: synthesis of intermediate B
Intermediate A (11.5g, 39.2mmol), 1-bromo-2-naphthaldehyde (9.2g, 39.2mmol), tripotassium phosphate (16.6g, 78.4mmol), toluene/ethanol/water (160/40/40mL) were added to a 500mL two-neck flask and stirred, after 10min of nitrogen sparging, palladium tetratriphenylphosphine (2.3g, 2mmol) was added, and the mixture was warmed to 100 ℃ under nitrogen and refluxed overnight. After completion of the reaction, it was cooled, washed with water, and the organic phase was dried by spinning and the residue was purified by column chromatography (PE/EA: 10/1) to obtain intermediate B (5.3g, yield: 43%) as a white solid.
And step 3: synthesis of intermediate C
A250 mL flask was charged with methoxymethyltriphenylphosphonium chloride (10.3g, 30.9mmol), THF (30mL) was added, the mixture was stirred under a dry ice ethanol bath for 10min, potassium tert-butoxide (3.17g, 28.3mmol) was added, the mixture was stirred for 1-2h, after which a solution of intermediate B (5.3g, 16.6mmol) in THF (30mL) was added, dropped over 15min, and allowed to slowly warm to room temperature for overnight reaction. After the reaction was completed, the reaction mixture was quenched by adding ammonium chloride solution, EA and water were added to separate the solution, the organic phase was spin-dried, and the residue was purified by silica gel column chromatography, PE/DCM ═ 2/1 was eluted to give the product as a white yellowish solid (5.3g, yield: 91.3%).
And 4, step 4: synthesis of intermediate D
A250 mL flask was charged with intermediate C (5.3g, 15.2mmol), and 75mL of 1, 2-dichloroethane was added and dissolved with stirring, and bismuth trifluoromethanesulfonate (cas:88189-03-1) (500mg, 0.76mmol) was added at room temperature and stirred at room temperature overnight. After the reaction was completed, the dichloroethane was removed by rotary evaporation, and the residue was dissolved in DCM and purified by silica gel column chromatography, eluting with PE/DCM-3/1 to 1/1 to give crude product, which was washed with ethanol to give intermediate D (3.7g, yield: 77%) as a white solid.
And 5: synthesis of Compound 1
A 250mL flask was charged with intermediate D (1.88g, 5.9mmol), 2-chloro-4-phenylquinazoline (1.71g, 7.1mmol), cesium carbonate (3.86g, 11.8mmol), 50mL DMF, and heated to 130 ℃ under nitrogen for 4h reaction, after completion of the reaction, cooled, added water, filtered to give a solid product, which was dissolved in DCM and purified by silica gel column chromatography, PE/DCM ═ 2/1 to 3/2 to give compound 1(2.9g, yield: 93.9%) as a pale yellow solid. The product was identified as the target product, molecular weight 521.2.
Synthesis example 2: synthesis of Compound 3
Step 1: synthesis of Compound 3
A250 mL flask is added with the intermediate D (1.9g, 6.0mmol), 2-chloro-3-phenylquinoxaline (1.73g, 7.2mmol), DMAP (730mg, 6.0mmol), cesium carbonate (3.9g, 12.0mmol) and 80mL of DMSO, the temperature is raised to 100 ℃ under the protection of nitrogen for reaction overnight, after the reaction is finished, the mixture is cooled, 100mL of water is added, a solid crude product is obtained by suction filtration, and after drying, the solid crude product is washed by an EA/EtOH mixed solvent to obtain a light yellow solid compound 3(2.9g, the yield: 92.9%). The product was identified as the target product, molecular weight 521.2.
It will be appreciated by those skilled in the art that the above preparation method is only an illustrative example, and that those skilled in the art can modify it to obtain other structures of the compounds of the present invention.
Device embodiments
First, a glass substrate, having an Indium Tin Oxide (ITO) anode 120nm thick, was cleaned and then treated with UV ozone and oxygen plasma. After the treatment, the substrate was dried in a glove box filled with nitrogen gas to remove moisture, and then the substrate was mounted on a substrate holder and loaded into a vacuum chamber. The organic layer specified below was in a vacuum of about 10 degrees-8In the case of Torr Rate ofThe evaporation was carried out in sequence on the ITO anode by thermal vacuum. Compound HI was used as a Hole Injection Layer (HIL) with a thickness ofThe compound HT is used as Hole Transport Layer (HTL) with a thickness ofCompound H1 was used as an Electron Blocking Layer (EBL) with a thickness ofThen, the compound 1 of the present invention as a host and a compound RD (weight ratio 97:3) as a dopant were co-evaporated to be used as an emission layer (EML) with a thickness ofCompound H2 was used as a Hole Blocking Layer (HBL) with a thickness ofOn the hole blocking layer, compound ET and 8-hydroxyquinoline-lithium (Liq) were co-evaporated as an Electron Transport Layer (ETL). Finally, evaporationLiq of thickness as Electron Injection Layer (EIL) and evaporatedAs a cathode. The device was then transferred back to the glove box and encapsulated with a glass lid to complete the device.
Device example 2
Device example 2 was carried out in the same manner as in device example 1 except that the present compound 3 was used as a host in place of the present compound 1 in the light-emitting layer (EML).
Device comparative example 1
Device comparative example 1 was the same as device example 1 except that compound H3 was used as a host in place of compound 1 of the present invention in the light emitting layer (EML).
The detailed device layer structure and thickness are shown in the table below. Wherein more than one layer of the materials used is obtained by doping different compounds in the stated weight ratios.
TABLE 1 device structures of device examples and comparative examples
The material structure used in the device is as follows:
at 15mA/cm2The luminous efficiency (cd/a) and external quantum efficiency (%) of the device were measured, and the CIE color coordinates of the device were measured at a constant luminance of 1000 nits. These data are recorded and presented in table 2.
TABLE 2 device data
Device ID
CE(cd/A)
EQE(％)
CIE(x,y)
Example 1
17.3
21.3
(0.686,0.313)
Example 2
18.0
22.2
(0.686,0.313)
Comparative example 1
17.1
20.3
(0.685,0.314)
Discussion:
as shown in table 2, the CIE coordinates of example 1 and example 2 substantially agreed with those of comparative example 1 at a constant luminance of 1000 nits. The current efficiencies of example 1 and example 2 were 17.3cd/A and 18.0cd/A, respectively, and were 1% and 5% improvements, respectively, as compared to 17.1cd/A for comparative example 1. The external quantum efficiencies of example 1 and example 2 were 21.3% and 22.2%, respectively, which were 4.9% and 9.3% respectively higher than 20.3% of comparative example 1.
These results indicate that the novel compounds having a spiroalkene structure disclosed in the present invention can provide higher luminous efficiency and external quantum efficiency and can provide better performance when used as a host material of a light emitting layer in an organic electroluminescent device.
It should be understood that the various embodiments described herein are illustrative only and are not intended to limit the scope of the invention. Thus, the invention as claimed may include variations from the specific embodiments and preferred embodiments described herein, as will be apparent to those skilled in the art. Many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the present invention. It should be understood that various theories as to why the invention works are not intended to be limiting.
