Patent Grant
12171137
The present invention relates to compounds for use as emitters, and devices, such as organic light emitting diodes, including the same.
Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.
OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Alternatively the OLED can be designed to emit white light. In conventional liquid crystal displays emission from a white backlight is filtered using absorption filters to produce red, green and blue emission. The same technique can also be used with OLEDs. The white OLED can be either a single EML device or a stack structure. Color may be measured using CIE coordinates, which are well known to the art.
One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)3, which has the following structure:
In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.
As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.
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 substrate. There may be other layers between the first and second layer, 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 processable” 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.
As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.
As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.
More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.
A compound comprising a ligand LA of Formula I coordinated to a metal M as represented by the dotted lines
wherein
ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring;
ring B is a multicyclic ring system comprising four to eight fused 5-membered or 6-membered, carbocyclic or heterocyclic rings; wherein the ring B includes a structure of Formula II
wherein ring C is a 5-membered or 6-membered carbocyclic or heterocyclic ring, and the dotted lines of Formula II represent fusion of the structure of Formula II as part of the multicyclic ring system of ring B;
T1, T2, and T3 are independently selected from N or C;
RA, RB, and RC represent mono to the maximum allowable substitution, or no substitution, and each RA, RB, and RC is independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; or optionally, any two adjacent RA, RB, and RC can join to form a ring;
L is a linker L2-L1 with L2 and L1 independently selected from the group consisting of O, S, NRN, CR1R2, CR3R4, SiR1R2, and SiR3R4; wherein at least one of L1 or L2 is CR1CR2 or SiR1R2;
R1, R2, R3, and R4 are independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, silyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof; or optionally, R1 and R2, or R3 and R4 of CR1R2, CR3R4, SiR1R2, or SiR3R4 can join to form a ring; or optionally, any two adjacent R1, R2, R3, R4, and RN can join to form a ring;
RN is selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof;
wherein the metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Au, and Cu; and
the ligand LA is optionally joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand that is complexed to the metal M.
An OLED that includes an organic layer, and the organic layer comprises a compound that includes a ligand LA of Formula I above.
A consumer product with an OLED that includes an organic layer. The organic layer comprising a compound that includes a ligand LA of Formula I above.
Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
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 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 in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. 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 entireties, disclose examples of cathodes including compound 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 is 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 in their entireties. 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 protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
The simple layered structure illustrated in
Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in
Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and organic vapor jet printing (OVJP). Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. A consumer product comprising an OLED that includes the compound of the present disclosure in the organic layer in the OLED is disclosed. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays (displays that are less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, a light therapy device, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.), but could be used outside this temperature range, for example, from −40 degree C. to +80 degree C.
The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
The terms “halo,” “halogen,” and “halide” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.
The term “acyl” refers to a substituted carbonyl radical (C(O)—Rs).
The term “ester” refers to a substituted oxycarbonyl (—O—C(O)—Rs or —C(O)—O—Rs) radical.
The term “ether” refers to an —ORs radical.
The terms “sulfanyl” or “thio-ether” are used interchangeably and refer to a —SRs radical.
The term “sulfinyl” refers to a —S(O)—Rs radical.
The term “sulfonyl” refers to a —SO2—Rs radical.
The term “phosphino” refers to a —P(Rs)3 radical, wherein each Rs can be same or different.
The term “silyl” refers to a —Si(Rs)3 radical, wherein each Rs can be same or different.
In each of the above, Rs can be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combination thereof. Preferred Rs is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combination thereof.
The term “alkyl” refers to and includes both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group is optionally substituted.
The term “cycloalkyl” refers to and includes monocyclic, polycyclic, and spiro alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Additionally, the cycloalkyl group is optionally substituted.
The terms “heteroalkyl” or “heterocycloalkyl” refer to an alkyl or a cycloalkyl radical, respectively, having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si and Se, preferably, O, S or N. Additionally, the heteroalkyl or heterocycloalkyl group is optionally substituted.
The term “alkenyl” refers to and includes both straight and branched chain alkene radicals. Alkenyl groups are essentially alkyl groups that include at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl groups are essentially cycloalkyl groups that include at least one carbon-carbon double bond in the cycloalkyl ring. The term “heteroalkenyl” as used herein refers to an alkenyl radical having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group is optionally substituted.
The term “alkynyl” refers to and includes both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group is optionally substituted.
The terms “aralkyl” or “arylalkyl” are used interchangeably and refer to an alkyl group that is substituted with an aryl group. Additionally, the aralkyl group is optionally substituted.
The term “heterocyclic group” refers to and includes aromatic and non-aromatic cyclic radicals containing at least one heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Hetero-aromatic cyclic radicals may be used interchangeably with heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino, and the like, and cyclic ethers/thio-ethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. Additionally, the heterocyclic group may be optionally substituted.
The term “aryl” refers to and includes both single-ring aromatic hydrocarbyl groups and polycyclic aromatic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is an aromatic hydrocarbyl group, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group is optionally substituted.
The term “heteroaryl” refers to and includes both single-ring aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. The heteroatoms include, but are not limited to O, S, N, P, B, Si, and Se. In many instances, O, S, or N are the preferred heteroatoms. Hetero-single ring aromatic systems are preferably single rings with 5 or 6 ring atoms, and the ring can have from one to six heteroatoms. The hetero-polycyclic ring systems can have two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. The hetero-polycyclic aromatic ring systems can have from one to six heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group is optionally substituted.
Of the aryl and heteroaryl groups listed above, the groups of triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and the respective aza-analogs of each thereof are of particular interest.
The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl, as used herein, are independently unsubstituted, or independently substituted, with one or more general substituents.
In many instances, the general substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.
In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, sulfanyl, and combinations thereof.
In yet other instances, the more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
The terms “substituted” and “substitution” refer to a substituent other than H that is bonded to the relevant position, e.g., a carbon or nitrogen. For example, when R1 represents mono-substitution, then one R1 must be other than H (i.e., a substitution). Similarly, when R1 represents di-substitution, then two of R1 must be other than H. Similarly, when R1 represents no substitution, R1, for example, can be a hydrogen for available valencies of ring atoms, as in carbon atoms for benzene and the nitrogen atom in pyrrole, or simply represents nothing for ring atoms with fully filled valencies, e.g., the nitrogen atom in pyridine. The maximum number of substitutions possible in a ring structure will depend on the total number of available valencies in the ring atoms.
As used herein, “combinations thereof” indicates that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can envision from the applicable list. For example, an alkyl and deuterium can be combined to form a partial or fully deuterated alkyl group; a halogen and alkyl can be combined to form a halogenated alkyl substituent; and a halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one instance, the term substitution includes a combination of two to four of the listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituent groups are those that contain up to fifty atoms that are not hydrogen or deuterium, or those which include up to forty atoms that are not hydrogen or deuterium, or those that include up to thirty atoms that are not hydrogen or deuterium. In many instances, a preferred combination of substituent groups will include up to twenty atoms that are not hydrogen or deuterium.
The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H groups in the respective aromatic ring can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. 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.
As used herein, “deuterium” refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400, Patent Pub. No. WO 2006/095951, and U.S. Pat. Application Pub. No. US 2011/0037057, which are hereby incorporated by reference in their entireties, describe the making of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan, et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65, which are incorporated by reference in their entireties, describe the deuteration of the methylene hydrogens in benzyl amines and efficient pathways to replace aromatic ring hydrogens with deuterium, respectively.
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 some instance, a pair of adjacent substituents can be optionally joined or fused into a ring. The preferred ring is a five, six, or seven-membered carbocyclic or heterocyclic ring, includes both instances where the portion of the ring formed by the pair of substituents is saturated and where the portion of the ring formed by the pair of substituents is unsaturated. As used herein, “adjacent” means that the two substituents involved can be on the same ring next to each other, or on two neighboring rings having the two closest available substitutable positions, such as 2, 2′ positions in a biphenyl, or 1, 8 position in a naphthalene, as long as they can form a stable fused ring system.
A compound comprising a ligand LA of Formula I coordinated to a metal M as represented by the dotted lines
wherein
ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring;
ring B is a multicyclic ring system comprising four to eight fused 5-membered or 6-membered, carbocyclic or heterocyclic rings; wherein the ring B includes a structure of Formula II
wherein ring C is a 5-membered or 6-membered carbocyclic or heterocyclic ring, and the dotted lines of Formula II represent fusion of the structure of Formula II as part of the multicyclic ring system of ring B;
T1, T2, and T3 are independently selected from N or C;
RA, RB, and RC represent mono to the maximum allowable substitution, or no substitution, and each RA, RB, and RC is independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; or optionally, any two adjacent RA, RB, and RC can join to form a ring;
L is a linker L2-L1 with L2 and L1 independently selected from the group consisting of O, S, NRN, CR1R2, CR3R4, SiR1R2, and SiR3R4; wherein at least one of L1 or L2 is CR1CR2 or SiR1R2;
R1, R2, R3, and R4 are independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, silyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof; or optionally, R1 and R2, or R3 and R4 of CR1R2, CR3R4, SiR1R2, or SiR3R4 can join to form a ring; or optionally, any two adjacent R1, R2, R3, R4, and RN can join to form a ring;
RN is selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof;
wherein the metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Au, and Cu; and
the ligand LA is optionally joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand that is complexed to the metal M.
Additional embodiments include compounds that include a ligand LA of Formula I with each RA, RB, and RC, being independently selected from any one group list of preferred general substituents, or any one group list of more preferred substituents, defined above. For example, in one embodiment, each RA, RB, and RC is independently selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.
Compounds of particular interest include a ligand LA of Formula I selected from the group consisting of;
wherein the ligand LA complexes to M to form a 5-membered chelate ring, and as defined above, Ring A is a 5-membered, or a 6-membered heteroaromatic ring, T3 is C or N, and the linker L2-L1 with L2 and L1 independently selected from the group consisting of O, S, NRN, CR1R2, CR3R4, SiR1R2, and SiR3R4; wherein at least one of L1 or L2 is CR1CR2 or SiR1R2. Z1, Z2, Z3, Z4, Z5, Z6, Z7, and Z8 are independently selected from CRD or N, wherein no more than two of Z1, Z2, Z3, Z4, Z5, Z6, Z7, and Z8 are N. RD is independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; or optionally, any two adjacent RD can join to form a ring; and X is selected from NRN, O, S, Se, or CRC═CRC, preferably, X is O or CRC═CRC.
In one embodiment, the compounds will have a ligand LA of Formula I in which one of L1 or L2 is selected from O, S, or Se. Likewise, other embodiments include the compounds of particular interest above with one of L1 or L2 selected from O, S, or Se. In each of these class embodiments, preferably one of L1 or L2 is O, and the other as stated above, is CR1CR2 or SiR1R2.
In any one compound with a ligand LA of Formula I, or any one of the compounds of Formulae I1 to I32, it can be advantageous in terms of device stability or emission characteristics where R1 and R2 is selected from hydrogen, deuterium, or methyl, the latter of which is optionally fully or partially deuterated.
In one embodiment, the compounds will have a ligand LA of Formula I in which Ring A is an optionally substituted pyridyl, or optionally two adjacent RA join to form an optionally substituted quinoline ring. Likewise, other embodiments include the compounds of Formulae I1 to I32 with a Ring A being an optionally substituted pyridyl, or optionally two adjacent RA join to form an optionally substituted quinoline ring.
In another embodiment, the compounds will have a ligand LA of Formula I with one or two of RA being methyl or phenyl, each of which is optionally fully or partially deuterated. Likewise, other embodiments include the compounds of Formulae I1 to I32 with one or two of RA being methyl or phenyl, each of which is optionally fully or partially deuterated.
In another embodiment, any one compound will have a ligand LA of Formula I, or any one compound of Formulae I1 to I32, with a linker L2-L1 selected from the group consisting of; —O—CR1R2—, —O—SiR1R2—, —S—CR1R2—, —S—SiR1R2—, —NRN—CR2R3—, —NRN—SiR2R3—, and —SiR1R2—SiR3R4—.
Select compounds will include one or more ligands LA independently selected from Formula A to Formula X represented below:
wherein the ligand LA complexes to M to form a 5-membered chelate ring, As shown, Ring A is an optionally substituted pyridyl, or optionally, two RA join to form an optionally substituted quinoline ring. Z1, Z2, Z3, and Z4 are independently selected from CRD or N, wherein no more than two of Z1, Z2, Z3, and Z4 are N. RA, RB, RD, X, and the linker L2-L1, are as defined above.
A class of compounds of select interest will have a ligand LA selected from the group consisting of; Formula A, Formula B, Formula C, Formula D, Formula E, Formula F, Formula G, Formula H, Formula I, Formula J, Formula K, Formula L, Formula M, Formula N, Formula O, Formula P, Formula Q, Formula R, Formula S, Formula T, Formula U, Formula V, Formula W, and Formula X in which one of L1 or L2 is selected from O, S, or Se. In each of these embodiments, preferably one of L1 or L2 is O. Additional embodiments of interest are the compounds that include a ligand LA of Formula A to Formula X in which the linker L2-L1 is selected from the group consisting of; —O—CR1R2—, —O—SiR1R2—, —S—CR1R2—, —S—SiR1R2—, —NRN—CR2R3—, —NRN—SiR2R3—, and —SiR1R2—SiR3R4—. Moreover, as already noted in any one of these embodiments of ligand LA of Formula A to Formula X, it can be advantageous in terms of device stability or emission characteristics where R1 and R2 is selected from hydrogen, deuterium, or methyl, the latter of which is optionally fully or partially deuterated.
We also describe a select class of compounds of the formula M(LA)x(LB)y(LC); wherein LA is the ligand LA of Formula I and generic ligands LB and LC are each a bidentate ligand; and x is 1, 2, or 3; y is 1 or 2; z is 0, 1, or 2; and x+y+z is the oxidation state of the metal M, wherein the bidentate ligands LB and LC are independently selected from the group consisting of;
wherein Ra, Rb, and Rc represent mono to the maximum allowable substitution, or no substitution, and each Ra, Rb, and Rc is independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; or optionally, any two adjacent Ra, Rb, and Rc can join to form a ring.
Compounds of select interest will include a ligand LA defined in Table I. The select compounds include one or more of a ligand LA of Formula A to Formula X above.
wherein the groups E1 to E7, G1, and G2 are as follows
We also describe a select class of compounds of Formula I with a formula of M(LA)x(LB)y(LC); wherein x is 1, 2, or 3; y is 1 or 2; z is 0, 1, or 2; and x+y+z is the oxidation state of the metal M. For example, the compound can include a ligand LA of Formula I, a ligand LA of Formulae I1 to I32, or a ligand LA of one of Formula A to Formula X. In another example, the compounds can include one to three ligands LA selected from the group consisting of LA1 to LA413. In each instance, the ligands LA can be the same or different. In still other embodiments, the compounds will have one or two of the ligands LA1 to LA413, the same or different, and one or two of the generic bidentate ligands LB and LC (see, above).
In some embodiments, LB is selected from the group consisting of:
In a first subset of embodiments, the ligand LB is selected from the group consisting of:
In a second subset of embodiments, the ligand LB is selected from the group consisting of:
We also describe select compounds that includes one ligand LA listed in Table I as LA1 to LA413, and two of the same ligands LB selected from LB1 to LB237 as described above. The compounds can be defined as a compound By of the formula LAiIr(LBj)2; wherein y=237i+j−237, and i is an integer from 1 to 413, and represents one of the ligands LA1 to LA413, and j is an integer from 1 to 237, and represents one of the ligands LB1 to LB237. As noted above, some select compounds includes one ligand LA listed in Table I as LA1 to LA413, and two of the same ligands LB selected from the first subset of the ligands LB above. Moreover, some select compounds includes one ligand LA listed in Table I as LA1 to LA413, and two of the same ligands LB selected from the second subset of the ligands LB above.
In some embodiments, the ligand LC is of Formula X and is selected from the group consisting of;
wherein RD1 to RD21 have the following structures:
We also describe Compounds Cz having the formula Ir(LAi)2(LCk); wherein z=1260i+k−1260; wherein i is an integer from 1 to 413, and k is an integer from 1 to 1260. The collective set of compounds will include compounds with two of the same ligands LA listed in Table I, and a ligand LC selected from LC1 to LC1260 as described above.
We also describe a chemical structure selected from the group consisting of a monomer, a polymer, a macromolecule, and a supramolecule, wherein the chemical structure comprises a compound of Formula I, or any one of the above described embodiments of Formula I, or a monovalent or polyvalent variant thereof.
We also describe an organic light emitting device (OLED) that includes an anode, a cathode, and an organic layer disposed between the anode and the cathode, the organic layer including a compound comprising a ligand LA of Formula I coordinated to a metal M as represented by the dotted lines
wherein
ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring;
ring B is a multicyclic ring system comprising four to eight fused 5-membered or 6-membered, carbocyclic or heterocyclic rings; wherein the ring B includes a structure of Formula II
wherein ring C is a 5-membered or 6-membered carbocyclic or heterocyclic ring, and the dotted lines of Formula II represent fusion of the structure of Formula II as part of the multicyclic ring system of ring B;
T1, T2, and T3 are independently selected from N or C;
RA, RB, and RC represent mono to the maximum allowable substitution, or no substitution, and each RA, RB, and RC is independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; or optionally, any two adjacent RA, RB, and RC can join to form a ring;
L is a linker L2-L1 with L2 and L1 independently selected from the group consisting of O, S, NRN, CR1R2, CR3R4, SiR1R2, and SiR3R4; wherein at least one of L1 or L2 is CR1CR2 or SiR1R2;
R1, R2, R3, and R4 are independently selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, silyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof; or optionally, R1 and R2, or R3 and R4 of CR1R2, CR3R4, SiR1R2, or SiR3R4 can join to form a ring; or optionally, any two adjacent R1, R2, R3, R4, and RN can join to form a ring;
RN is selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof;
wherein the metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Au, and Cu; and
the ligand LA is optionally joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand that is complexed to the metal M.
In one embodiment of an OLED, the compound present in the organic layer comprises a ligand LA of Formula I as described. In another embodiment of an OLED, the compound present in the organic layer will include a ligand LA selected from the group consisting of Formula I1 to Formula I32 as defined above. In another embodiment of an OLED, the compound present in the organic layer will include a ligand LA as defined in Table I above. In yet another OLED embodiment, the compound present in the organic layer is a Compound By having the formula Ir(LAi)(LBj)2, or a Compound Cz having the formula Ir(LAi)2(LCk); wherein y=490i+j−490, and z=1260i+k−1260; wherein i is an integer from 1 to 413, j is an integer from 1 to 490, and k is an integer from 1 to 1260.
An OLED with an organic layer that includes any one compound with a ligand LA as described above will have a light emission in a range from about 520 nm to about 630 nm, that is from green to a yellow green or yellow/orange to red depending upon the number of fused rings on the ligand LA. For example, one can provide an organic layer of an OLED with from about 540 nm to about 590 nm. One performance advantage of the compounds can be a narrow linewidth compared to a fused three ring system.
A consumer product comprising an organic light-emitting device (OLED) that includes an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer includes a metal compound that comprises a ligand LA of Formula I, wherein the dashed lines represent coordination to a metal M. Of course, any one of the described OLED embodiments above can be present in such a consumer product.
In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, being rollable, being foldable, being stretchable, and being curved. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.
In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises a RGB pixel arrangement or white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel having less than 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a display panel having at least 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a lighting panel.
In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence; see, e.g., U.S. application Ser. No. 15/700,352, which is hereby incorporated by reference in its entirety), triplet-triplet annihilation, or combinations of these processes. In some embodiments, the emissive dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from others). When there are more than one ligand coordinated to a metal, the ligands can all be the same in some embodiments. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, every ligand can be different from each other. This is also true in embodiments where a ligand being coordinated to a metal can be linked with other ligands being coordinated to that metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, where the coordinating ligands are being linked together, all of the ligands can be the same in some embodiments, and at least one of the ligands being linked can be different from the other ligand(s) in some other embodiments.
In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED where one or multiple layers in the OLED contains an acceptor in the form of one or more fluorescent and/or delayed fluorescence emitters. In some embodiments, the compound can be used as one component of an exciplex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor and the acceptor will emit the energy or further transfer energy to a final emitter. The acceptor concentrations can range from 0.001% to 100%. The acceptor could be in either the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission can arise from any or all of the sensitizer, acceptor, and final emitter.
According to another aspect, a formulation comprising the compound described herein is also disclosed.
The OLED disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.
The organic layer can also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the hosts used maybe a) bipolar, b) electron transporting, c) hole transporting or d) wide band gap materials that play little role in charge transport. In some embodiments, the host can include a metal complex. The host can be a triphenylene containing benzo-fused thiophene or benzo-fused furan. Any substituent in the host can be an unfused substituent independently selected from the group consisting of CnH2n+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═CH—CnH2n+1, C≡C—CnH2n+1, Ar1, Ar1—Ar2, and CnH2n—Ar1, or the host has no substitutions. In the preceding substituents n can range from 1 to 10; and Ar1 and Ar2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. The host can be an inorganic compound. For example a Zn containing inorganic material e.g. ZnS.
The host can be a compound comprising at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. The host can include a metal complex. The host can be, but is not limited to, a specific compound selected from the group consisting of:
and combinations thereof.
Additional information on possible hosts is provided below.
In yet another aspect of the present disclosure, a formulation that comprises the novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, electron blocking material, hole blocking material, and an electron transport material, disclosed herein.
The present disclosure encompasses any chemical structure comprising the novel compound of the present disclosure. In other words, a monovalent or polyvalent variant of the inventive compound can be a part of a larger chemical structure. Such chemical structure can be selected from the group consisting of a monomer, a polymer, a macromolecule, and a supramolecule (also known as supermolecule). As used herein, a “monovalent variant of a compound” refers to a moiety that is identical to the compound except that one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a “polyvalent variant of a compound” refers to a moiety that is identical to the compound except that more than one hydrogen has been removed and replaced with a bond to the rest of the chemical structure.
Combination with Other Materials
The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below 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.
Conductivity Dopants:
A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.
Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.
HIL/HTL:
A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:
Each of Ar1 to Ar9 is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each Ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, Ar1 to Ar9 is independently selected from the group consisting of:
wherein k is an integer from 1 to 20; X101 to X108 is C (including CH) or N; Z101 is NAr1, O, or S; Ar1 has the same group defined above.
Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:
wherein Met is a metal, which can have an atomic weight greater than 40; (Y101—Y102) is a bidentate ligand, Y101 and Y102 are independently selected from C, N, O, P, and S; L101 is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
In one aspect, (Y101—Y102) is a 2-phenylpyridine derivative. In another aspect, (Y101—Y102) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc+/Fc couple less than about 0.6 V.
Non-limiting examples of the HIL and HTL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, U.S. Ser. No. 06/517,957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, U.S. Pat. Nos. 5,061,569, 5,639,914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018.
EBL:
An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and/or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.
Host:
The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied.
Examples of metal complexes used as host are preferred to have the following general formula:
wherein Met is a metal; (Y103—Y104) is a bidentate ligand, Y103 and Y104 are independently selected from C, N, O, P, and S; L101 is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
In one aspect, the metal complexes are:
wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.
In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y103—Y104) is a carbene ligand.
In one aspect, the host compound contains at least one of the following groups selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each option within each group may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, the host compound contains at least one of the following groups in the molecule:
wherein R101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. k is an integer from 0 to 20 or 1 to 20. X101 to X108 are independently selected from C (including CH) or N. Z101 and Z102 are independently selected from NR101, O, or S.
Non-limiting examples of the host materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, U.S. Pat. No. 7,154,114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, U.S. Pat. No. 9,466,803,
Additional Emitters:
One or more additional emitter dopants may be used in conjunction with the compound of the present disclosure. Examples of the additional emitter dopants are not particularly limited, and any compounds may be used as long as the compounds are typically used as emitter materials. Examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
Non-limiting examples of the emitter materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, U.S. Ser. No. 06/699,599, U.S. Ser. No. 06/916,554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930, US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US20100244004, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US2014103305, U.S. Pat. Nos. 6,303,238, 6,413,656, 6,653,654, 6,670,645, 6,687,266, 6,835,469, 6,921,915, 7,279,704, 7,332,232, 7,378,162, 7,534,505, 7,675,228, 7,728,137, 7,740,957, 7,759,489, 7,951,947, 8,067,099, 8,592,586, 8,871,361, WO06081973, WO006121811, WO07018067, WO07108362, WO07115970, WO007115981, WO08035571, WO2002015645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842, WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO2011044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO2013174471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450.
HBL:
A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.
In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
In another aspect, compound used in HBL contains at least one of the following groups in the molecule:
wherein k is an integer from 1 to 20; L101 is an another ligand, k′ is an integer from 1 to 3.
ETL:
Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
In one aspect, compound used in ETL contains at least one of the following groups in the molecule:
wherein R101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar1 to Ar3 has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X101 to X108 is selected from C (including CH) or N.
In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:
wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.
Non-limiting examples of the ETL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, U.S. Pat. Nos. 6,656,612, 8,415,031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,
Charge Generation Layer (CGL)
In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.
In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. may be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof.
Synthesis of the LA809 and the ligand of the comparative example.
A suspension of 1-bromo-2-naphthaldehyde (25.6 g, 109 mmol), (3-chloro-2-methoxyphenyl)boronic acid (20.3 g, 109 mmol), potassium carbonate (60.2 g, 436 mmol) was taken into degassed dioxane (512 ml)/water (128 ml) solution. The reaction mixture was sparged with nitrogen for 15 min. and then added Pd(Ph3p)4 (12.59 g, 10.89 mmol). The mixture was heated at 110° C. overnight (12 hours). All the solvents were evaporated to dryness at 40° C. The residue was extracted with dichloromethane, After the solvents were evaporated to dryness, the residue was dissolved in 200 ml of DCM and adsorbed in silica gel. It was chromatographed over silica gel. The product containing fractions were evaporated to dryness. Yield: 30.5 g, 94%.
A ice cold solution of 1-(3-chloro-2-methoxyphenyl)-2-naphthaldehyde (30.45 g, 103 mmol) in methanol (250 ml) and tetrahydrofuran (500 ml) mixture at ice cold water bath. The reaction mixture was stirred for 10 minutes, and then was added sodium borohydride (4.66 g, 123 mmol) portion wise, to keep inner temperature of the reaction mixture below 10° C. and stirred for 90 minutes. All the solvents were evaporated under reduced pressure. The aqueous layer was extracted with dichloromethane (2×500 ml), combined dichloromethane layers, washed again by water (2×300 ml), dried over Na2SO4, pass through the silica gel, washed with dichloromethane, all the solvents were evaporated to dryness. Yield: 30.0 g, 98%.
To a solution of (3-(3-chloro-2-methoxyphenyl)naphthalen-2-yl)methanol (30 g, 100 mmol) in dichloromethane (537 ml), was added triphenylphosphane (39.5 g, 151 mmol) and cooled to 0° C., stirred for 10 minutes. Then, the mixture was added portion wise perbromomethane (49.9 g, 151 mmol) for 10 min. The reaction mixture was allowed to reach room temperature and stirred for an hour. After all the solvents were evaporated to dryness, it was dissolved in dichloromethane (200 ml) and silica gel was added. The product was adsorbed in silica gel, was chromatographed over silica gel, eluting with 30% dichloromethane in heptanes. Yield: 35.6 g, 98%
Into a 500 ml flask, tribromoborane (123 ml, 123 mmol, 1M in dichloromethane) was charged, the mixture was cool down to 0° C. and was added 2-(bromomethyl)-3-(3-chloro-2-methoxyphenyl)naphthalene (35.5 g, 98 mmol) in 550 ml of DCM. The reaction mixture was stirred overnight (12 hrs). After the reaction mixture was cool down to −25° C. and quenched with methanol. It was stirred for 5 min. and at 0° C. neutralized with sat. NaHCO3 solution to pH 7. It was extracted with methylene chloride (3×500 ml). The organics were combined, washed with brine (300 ml), dried (Na2SO4, 50 g), filtered and concentrated to a liquid. Yield: 33.9 g, 99%
Into a 250 ml RB flask, 2-(3-(bromomethyl)naphthalen-2-yl)-6-chlorophenol (33.8 g, 97 mmol) in DMF (389 ml) was charged and treated with Cs2CO3 (31.7 g, 97 mmol). The mixture was stirred at room temperature under nitrogen atmosphere for two hours. All the solvents were evaporated under reduced pressure. It was treated with 1N HCl (500 ml) and extracted with ethyl acetate (3×300 ml), the organic layer was washed with sat. sodium chloride (300 ml), dried over sodium sulfate (50 g) All the solvents were evaporated and it was triturated with 500 ml of heptanes and solid was filtered and dried. Yield: 25.3 g, 98%.
In 500 ml round bottom flask, 4-chloro-6H-naphtho[2,3-c]chromene (9.07 g, 34. mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (Bpin)2 (13.38 g, 52.7 mmol), dicyclohexyl(2′,4′,6′-triisopropyl-[1,1′-biphenyl]-2-yl)phosphane (3.24 g, 6.80 mmol), potassium acetate (10.01 g, 102 mmol) and Pd2(dba)3 (4.67 g, 5.10 mmol) in 1,4-dioxane (182 ml) were charged and sparged with nitrogen for 10 min. at room temperature. The reaction mixture was heated at 85-90° C. After 2 h, a small amount of sample from the reaction mixture was taken and checked the NMR and LC-MS, after confirming the product formation. It was directly taken to next step, without purifying.
In 3 liter flask, dicyclohexyl(2′,4′,6′-triisopropyl-[1,1′-biphenyl]-2-yl)phosphane (2.70 g, 5.66 mmol), Pd2(dba)3 (3.89 g, 4.25 mmol), K3PO4 (42.5 ml, 85 mmol, 2 M aqueous solution) and 2-chloro-4,5-dimethylpyridine (4.01 g, 28.3 mmol) were charged in 1,4-dioxane (1133 ml) and sparged with nitrogen for 10 min. The reaction mixture from the previous reaction was added and sparged with nitrogen for 15 min. The reaction mixture was refluxed for 15 h, cooled to room temperature. The aqueous layer was extracted with 3×500 ml of ethyl acetate. The combined organic layer was combined and evaporated to dryness. The crude reaction mixture was purified on silica gel to yield product 6.2 g, 65%.
A suspension of (3-chloro-2-methoxyphenyl)boronic acid (20.0 g, 107 mmol), 2-bromobenzaldehyde (20.84 g, 113 mmol), potassium carbonate (59.3, 429 mmol) in a mixture of degassed 1,4-dioxane (400 ml)/water (100 ml) was sparged with nitrogen for 15 min. and then added Pd(PPh3)4 (12.40 g, 10.73 mmol). After further sparging for 5 mi. the mixture was heated to 100° C. and stirred for 7 h. The mixture was cooled to room temperature and the layers were separated. The aqueous layer was extracted with EtOAc. The organics were combined, dried (anhydrous Na2SO4), filtered and concentrated to get yellow residue. The material was purified by column chromatography over silica gel (880 g) with an eluent of 0-10% EtOAc in heptanes to get a white solid (23.7 g, 90% yield).
A solution of (3′-chloro-2′-[1,1′-biphenyl]-2-carbaldehyde (23.7 g, 96 mmol) in methanol (475 ml) was cooled to 0° C. and added sodium borohydride (5.45 g, 144 mmol) portion-wise in 15 min. The mixture was stirred for 30 min. at that temperature and gradually warmed to room temperature. After 1 h, the solution was concentrated, treated with aqueous ammonium chloride solution (250 ml) and extracted with dichloromethane (3×200 ml). The organics were combined, washed with 1N HCl (100 ml), brine (100 ml), dried (anhydrous Na2SO4), filtered and concentrated to get a white solid (23.65 g, 99% yield).
To a solution of (3′-chloro-2′-methoxy-[1,1′-biphenyl]-2-yl)methanol (23.25 g, 93 mmol) in dichloromethane (500 ml) was added triphenylphosphane (36.8 g, 140 mmol) and cooled to 0° C. Then, perbromomethane (46.5 g, 140 mmol) portion-wise was added. After 1 h, the material was purified by column chromatography over silica gel to get a white solid (30.46 g, 89.4% combined yield).
Into an oven dried 1 L 3NRB Flask, tribromoborane (122 ml, 122 mmol, 1.0 M in CH2Cl2) was charged and cooled to 0° C. Then, treated with a solution of 2′-(bromomethyl)-3-chloro-2-methoxy-1,1′-biphenyl (30.4 g, 98 mmol) in methylene chloride (300 ml) dropwise in 1 h. The mixture was warmed to room temperature and stirred overnight. The mixture were separated and the aqueous layer was extracted with methylene chloride. The organics were combined, washed with brine (100 ml), dried (Na2SO4), filtered and concentrated to get a liquid (28.4 g, 98% yield).
Into a solution of 2′-(bromomethyl)-3-chloro-[1,1′-biphenyl]-2-ol (28.4 g, 95 mmol) in DMF (250 ml) was added cesium carbonate (46.6 g, 143 mmol) portion-wise in 10 min. The mixture was stirred at RT under nitrogen for 1 h and proton NMR indicated the reaction was completed. Treated with 1N HCl (140 ml) dropwise using addition funnel until neutral pH and extracted with EtOAc (3×200 ml). The organics were combined, washed with brine and dried over anhydrous Na2SO4, filtered and concentrated to get off-white solid (20.5 g, 99% yield).
Into a 2 L RB flask, 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (15.44 g, 60.8 mmol), dicyclohexyl(2′,4′,6′-triisopropyl-[1,1′-biphenyl]-2-yl)phosphane (3.74 g, 7.85 mmol), potassium acetate (11.55 g, 118 mmol) and Pd2(dba)3 (5.39 g, 5.88 mmol) in 1,4-Dioxane (700 ml) were charged and sparged with nitrogen for 15 min. Then a solution of 4-chloro-6H-benzo[c]chromene (8.5 g, 39.2 mmol) in 1,4-Dioxane (150 ml) was prepared, sparged with nitrogen for 10 min. and was added to the mixture as one portion. The reaction mixture was heated to reflux and after 2 h, and then, dicyclohexyl(2′,4′,6′-triisopropyl-[1,1′-biphenyl]-2-yl)phosphane (3.12 g, 6.54 mmol), Pd2(dba)3 (4.49 g, 4.90 mmol), aqueous potassium phosphate solution (196 ml, 98 mmol, 0.5 M) and 2-chloro-4,5-dimethylpyridine (4.63 g, 32.7 mmol) were charged and sparged with nitrogen for 10 min. The mixture as heated to reflux and refluxed overnight. After the reaction was cooled to room temperature and the layers were separated. The aqueous layer extracted with EtOAc (2×100 ml). The organics were combined, washed with brine (100 ml), dried (anhydrous Na2SO4), filtered and concentrated to get crude material. The material was purified by column chromatography over silica gel to get off-white solid (7.1 g, 76% yield).
The preparation of the iridium compounds for both the inventive compound and the comparative example compound are prepared as follows. The ligand LA (or the comparative ligand above) is reacted with the Ir precursor, Ir(LB)2(MeOH)2OTf in ethanol at reflux overnight. The Ir precursor is made by reacting IrCl3 with LB in a mixture of 2-ethoxyethanol and water, and then treated with AgOTf in a mixture of dichloromethane and MeOH.
The structures of an inventive compound Ir(LB169)2LA809 and the comparative example were optimized by DFT calculations. DFT calculations were performed using the program Gaussian16. Geometries were optimized using B3LYP functional and CEP-31G basis set. Excited state energies were computed by TDDFT at the optimized ground state geometries. The energy of the lowest singlet (S1) and triplet (T1) excited states are indicated below.
As calculated, the two compounds have the same S1 energy, however, T1 energy of the inventive example is significantly lower in energy. The triplet energy difference can be explained by a more localized T1 excited state in the inventive compound. Accordingly, the inventive compound is expected to show improved performance when used as an emitter in and OLED such as a more narrow emission profile or improved device stability and lifetime.
Singlet energy S1, and triplet energy T1 were calculated within the Gaussian16 software package using the B3LYP hybrid functional set and cep-31G basis set. S1 and T1 were obtained using TDDFT at the optimized ground state geometry. A continuum solvent model was applied to simulate tetrahydrofuran solvent.
The calculations obtained with the above-identified DFT functional set and basis set are theoretical. Computational composite protocols, such as the Gaussian09 with B3LYP and CEP-31G protocol used herein, rely on the assumption that electronic effects are additive and, therefore, larger basis sets can be used to extrapolate to the complete basis set (CBS) limit. However, when the goal of a study is to understand variations in HOMO, LUMO, S1, T1, bond dissociation energies, etc. over a series of structurally-related compounds, the additive effects are expected to be similar. Accordingly, while absolute errors from using the B3LYP may be significant compared to other computational methods, the relative differences between the HOMO, LUMO, S1, T1, and bond dissociation energy values calculated with B3LYP protocol are expected to reproduce experiment quite well. See, e.g., Hong et al., Chem. Mater. 2016, 28, 5791-98, 5792-93 and Supplemental Information (discussing the reliability of DFT calculations in the context of OLED materials). Moreover, with respect to iridium or platinum complexes that are useful in the OLED art, the data obtained from DFT calculations correlates very well to actual experimental data. See Tavasli et al., J. Mater. Chem. 2012, 22, 6419-29, 6422 (Table 3) (showing DFT calculations closely correlating with actual data for a variety of emissive complexes); Morello, G. R., J. Mol. Model. 2017, 23:174 (studying of a variety of DFT functional sets and basis sets and concluding the combination of B3LYP and CEP-31G is particularly accurate for emissive complexes).
It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.
This application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 62/729,132, filed Sep. 10, 2018, the entire contents of which are incorporated herein by reference.
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| Number | Date | Country | |
|---|---|---|---|
| 20200083459 A1 | Mar 2020 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62729132 | Sep 2018 | US |
