Patent Application
20250034189
The present disclosure generally relates to organometallic compounds and formulations and their various uses including as emitters in devices such as organic light emitting diodes and related electronic devices.
Opto-electronic devices that make use of organic materials are becoming increasingly desirable for various 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.
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.
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 emissive layer (EML) device or a stack structure. Color may be measured using CIE coordinates, which are well known to the art.
In one aspect, the present disclosure provides a compound comprising a first ligand LA of Formula I,
In Formula I: moiety A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; moiety B is a fused ring structure comprising at least three rings, each of which is independently heterocyclic or carbocyclic; K is a direct bond, O, or S; each of Z1 and Z2 is independently C or N; each of RA and RB independently represents mono to the maximum possible number of substitutions, or no substitution; each RA and RB is independently hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; any two RA or RB can be joined or fused to form a ring; at least one RB comprises a cyclic group or an electron-withdrawing group; LA is coordinated to a metal M; metal M has an atomic mass of at least 40 and can be coordinated to other ligands; and the ligand LA is optionally linked with other ligands to comprise a tridentate, tetradentate, pentadentate, or hexadentate ligand.
In another aspect, the present disclosure provides a formulation including a compound having a first ligand LA of Formula I as described herein.
In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a compound having a first ligand LA of Formula I as described herein.
In yet another aspect, the present disclosure provides a consumer product comprising an OLED with an organic layer comprising a compound having a first ligand LA of Formula I as described herein.
Unless otherwise specified, the below terms used herein are defined as follows:
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.
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 “selenyl” refers to a —SeRs 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.
The term “germyl” refers to a —Ge(Rs)3 radical, wherein each Rs can be same or different.
The term “boryl” refers to a —B(Rs)2 radical or its Lewis adduct —B(Rs)3 radical, wherein 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 may be 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 may be 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 may be 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 may be optionally substituted.
The term “alkynyl” refers to and includes both straight and branched chain alkyne radicals. Alkynyl groups are essentially alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be 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 may be 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 may be 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, oxatiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.
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, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, selenyl, 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, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.
In some instances, the More 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 Most 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 R 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 zero or 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 instances, 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.
In one aspect, the present disclosure provides a compound comprising a first ligand LA of Formula I,
In some embodiments, each RA and RB is independently hydrogen or a substituent selected from the group consisting of the Preferred General Substituents defined herein. In some embodiments, each RA and RB is independently hydrogen or a substituent selected from the group consisting of the More Preferred General Substituents defined herein. In some embodiments, each RA and RB is independently hydrogen or a substituent selected from the group consisting of the Most Preferred General Substituents defined herein.
In some embodiments, the at least one RB that comprises a cyclic group or an electron-withdrawing group is not joined or fused with another RA or RB to form a ring.
In some embodiments, moiety A is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, triazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, benzimidazole derived carbene, aza-benzimidazole derived carbene, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, phenanthridine, fluorene, and aza-fluorene. In some embodiments, the aza variant includes one N on a benzo ring. In some embodiments, the aza variant includes one N on a benzo ring and the N is bonded to the metal M. In some embodiments, moiety A is benzimidazole substituted by at least one substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. In some such embodiments, the at least one substituent is at the 7-position of the benzimidazole. In some embodiments, moiety A is benzimidazole substituted by at least two same or different substituents independently selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof. In some embodiments, moiety A is benzimidazole substituted by a CD3. In some embodiments, moiety A is benzimidazole fused by a 5- or 6-membered ring. In some such embodiments, the 5- or 6-membered ring can be aromatic, or non-aromatic. In some embodiments, moiety A is benzimidazole fused by a benzene or naphthalene. In some such embodiments, moiety A is naphtho[1,2-d]imidazole.
In some embodiments, K can be a direct bond. In some embodiments, K can be O. In some embodiments, K can be S. It should be understood that when K is O or S, Z2 is C.
In some embodiments, when K is a direct bond and moiety A is an imidazole ring, then two RA are not joined to form a 6-membered ring. In some embodiments, when K is a direct bond and moiety A is an imidazole ring, then two RA are not joined to form a phenyl ring. In some embodiments, when K is a direct bond and moiety A is an imidazole ring and one N atom of the imidazole ring is coordinated to a metal, then two RA are not joined to form a 6-membered ring. In some embodiments, when K is a direct bond and moiety A is an imidazole ring and one N atom of the imidazole ring is coordinated to a metal, then two RA are not joined to form a phenyl ring. In some embodiments, when K is a direct bond and moiety A is a benzimidazole group and one N atom of the benzimidazole group is coordinated to a metal, then moiety B is a polycyclic fused ring structure comprising at least 5 rings. In some embodiments, when moiety A is a benzimidazole group and one N atom of the benzimidazole group is coordinated to a metal, then the ring of moiety B coordinated to the metal is not a benzene ring. In some embodiments, when moiety A of LA is a benzimidazole group, then LA does not form a metal complex with another ligand containing a substituted pyridine ring. In some embodiments, when moiety A of LA is a benzimidazole group, then LA does not form a metal complex with another ligand containing a silyl or germyl substituted pyridine moiety. In some embodiments, when moiety A of LA is a benzimidazole group, then LA does not form a metal complex with another ligand containing a 3-silyl or 3-germyl substituted pyridine moiety.
In some embodiments, moiety B comprises at least one ring of Formula II,
where Y is selected from the group consisting of BR′, BR′R″, NR′, PR′, P(O)R′, 0, S, Se, C═0, C═S, C═Se, C═NR′, C═CR′R″, S═0, SO2, CR′, CR′R″, SiR′R″, GeR′R″, alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof. In some embodiments, each R′ or R″ is independently hydrogen or a substituent selected from the group consisting of the General Substituents defined herein.
In some embodiments including Formula II, moiety B comprises at least two rings of Formula II, wherein the at least two rings of Formula II may be the same or different.
In some embodiments, moiety B comprises exactly three fused rings, each of which is independently heterocyclic or carbocyclic. In some of such embodiments, two rings are 6-membered rings, and one ring is a 5-membered ring. In some of such embodiments, the middle ring is a 5-membered ring. In some of such embodiments, moiety B may not be dibenzofuran. In some of such embodiments, each of the rings is independently 5-membered or 6-membered aryl or heteroaryl. In some embodiments, each of the rings is independently selected from the group consisting of phenyl, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole.
In some embodiments, moiety B is a fused ring structure comprising at least five rings, each of which is independently heterocyclic or carbocyclic.
In some embodiments, moiety B comprises at least four fused rings, and each of the at least four rings of moiety B is independently selected from the group consisting of phenyl, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, and triazole.
In some embodiments, moiety B comprises at least three six-membered rings. In some embodiments, moiety B comprises at least three six-membered rings that are each independently phenyl or pyridine.
In some embodiments, moiety B comprises at least four six-membered rings. In some embodiments, moiety B comprises at least four six-membered rings that are each independently phenyl or pyridine.
In some embodiments, moiety B is a polycyclic fused ring structure. In some embodiments, moiety B is a polycyclic fused ring structure comprising at least three fused rings. In some embodiments, the polycyclic fused ring structure has two 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to metal M and the second 6-membered ring is fused to the 5-membered ring. In some embodiments, moiety B is selected from the group consisting of dibenzofuran, dibenzothiophene, dibenzoselenophene, and aza-variants thereof. In some such embodiments, moiety B can be further substituted at the position ortho- or meta- to the O, S, or Se atom by a substituent selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some such embodiments, the aza-variants contain exactly one N atom at the 6-position (ortho to the O, S, or Se) with a substituent at the 7-position (meta to the O, S, or Se).
In some embodiments, moiety B is a polycyclic fused ring structure comprising at least four fused rings. In some embodiments, the polycyclic fused ring structure comprises three 6-membered rings and one 5-membered ring. In some such embodiments, the 5-membered ring is fused to the ring coordinated to metal M, the second 6-membered ring is fused to the 5-membered ring, and the third 6-membered ring is fused to the second 6-membered ring. In some such embodiments, the third 6-membered ring is further substituted by a substituent selected from the group consisting of deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
In some embodiments, moiety B is a polycyclic fused ring structure comprising at least five fused rings. In some embodiments, the polycyclic fused ring structure comprises four 6-membered rings and one 5-membered ring or three 6-membered rings and two 5-membered rings. In some embodiments comprising two 5-membered rings, the 5-membered rings are fused together. In some embodiments comprising two 5-membered rings, the 5-membered rings are separated by at least one 6-membered ring. In some embodiments with one 5-membered ring, the 5-membered ring is fused to the ring coordinated to metal M, the second 6-membered ring is fused to the 5-membered ring, the third 6-membered ring is fused to the second 6-membered ring, and the fourth 6-membered ring is fused to the third 6-membered ring.
In some embodiments, moiety B is independently an aza version of the fused rings as described above. In some such embodiments, moiety B independently contains exactly one aza N atom. In some such embodiments, moiety B contains exactly two aza N atoms, which can be in one ring, or in two different rings. In some such embodiments, the ring having aza N atom is at least separated by another two rings from the Ir atom. In some such embodiments, the ring having aza N atom is at least separated by another three rings from the Ir atom. In some such embodiments, each of the ortho positions of the aza N atom is substituted.
In some embodiments, Z1 is N and Z2 is C. In some embodiments, Z1 is C and Z2 is N. In some embodiments, Z1 is C and Z2 is C. In some embodiments, Z1 is N and Z2 is N.
In some embodiments, at least one RA is other than hydrogen and deuterium.
In some embodiments, at least one RB is a cyclic group. In some embodiments, at least one RB comprises an aryl or heteroaryl group. In some embodiments, at least one RB comprises a cycloalkyl or heterocycloalkyl group, either of which may be substituted or unsubstituted.
In some embodiments, at least one RB comprises at least one monocyclic group. In some embodiments, at least one RB comprises a fused multicyclic group. In some of such embodiments, the fused multicyclic group may comprise all saturated carbocyclic or heterocyclic rings. In some of such embodiments, the fused multicyclic group may comprise all unsaturated carbocyclic or heterocyclic rings. In some of such embodiments, the fused multicyclic group may comprise both saturated and unsaturated carbocyclic or heterocyclic rings. In some of such embodiments, the fused multicyclic group may comprise aryl and/or heteroaryl rings. In some of such embodiments, the fused multicyclic group may be naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, phenanthridine, fluorene, and aza-fluorene. In some of such embodiments, the aza variant includes one N on a benzo ring. It should be understood that all the above fused multicyclic groups can be unsubstituted or further substituted.
In some embodiments, at least one RB is an electron-withdrawing group having Hammett constant larger than 0. In some embodiments, at least one RB is an electron-withdrawing group having Hammett constant equal or larger than the number selected from the group consisting of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, and 1.1. In these embodiments, the electron-withdrawing group commonly comprises one or more highly electronegative elements such as but not limited to fluorine, oxygen, sulfur, nitrogen, chlorine, and bromine.
In some embodiments, at least one RB comprises or is an electron-withdrawing group selected from the group consisting of the following LIST 1: F, CF3, CN, COCH3, CHO, COCF3, COOMe, COOCF3, NO2, SF3, SiF3, PF4, SFs, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC, *N(R)3, (R)2CCN, (R)2CCF3, CNC(CF3)2, BRR′, substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1,9-substituted carbazole, substituted or unsubstituted carbazole, substituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridazine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated alkyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate,
wherein Y′ is selected from the group consisting of BRe, NRe, PRe, O, S, Se, C═O, S═O, SO2, CReRf, SiReRf, and GeReRf′, and each R, Re, and Rf is independently a hydrogen or a substituent selected from the group consisting of the General Substituents defined herein. In some embodiments, R can be a mono up to the maximum number of allowable substitutions or no substitution.
In some embodiments of LA of Formula I, at least one RB is an electron-withdrawing group selected from the group consisting of:
In some embodiments of LA of Formula I, at least one RB is an electron-withdrawing group selected from the group consisting of:
In some embodiments, at least one RB is an electron-withdrawing group selected from the group consisting of:
In some embodiments, at least one RB is an electron-withdrawing group is selected from the group consisting of fluoride, perfluoroalkyl, perfluorocycloalkyl, perfluorovinyl, CN, SCN, SFs, and SCF3.
In some embodiments, at least one RB comprises a group selected from the group consisting of halogen, nitrile, fully fluorinated alkyl, and partially fluorinated alkyl. In some embodiments, at least one RB is selected from the group consisting of F; CN, CF3, cycloalkyl, and CH2CF3.
In some embodiments, the at least one RB that comprises a cyclic group or an electron-withdrawing group is bonded to a distal ring of the fused ring structure of moiety B. As used herein, “distal” refers to the ring (or rings) that is farthest from the metal M.
In some embodiments, at least one RA is other than hydrogen or deuterium. In some embodiments, at least one RA is partially or fully deuterated alkyl. In some embodiments, at least one RA is an electron withdrawing group selected from LIST 1 defined herein.
In some embodiments, at least two RA are other than hydrogen or deuterium. In some embodiments, at least two RA are each independently partially or fully deuterated alkyl.
In some embodiments, two adjacent RA or RB may be joined to form a ring. In some embodiments, two adjacent RA or RB may be joined to form a 5-membered or 6-membered carbocyclic or heterocyclic aromatic ring. In some embodiments, two adjacent RA or RB may be joined to form a 5-membered or 6-membered carbocyclic or heterocyclic non-aromatic ring. In some embodiments, two adjacent RA or RB may be joined to form a ring selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, and thiazole.
In some embodiments, the metal M is selected from the group consisting of Ir, Os, Rh, Re, Ru, Pt, Pd, Cu, Ag, and Au. In some embodiments, metal M is Ir. In some embodiments, metal M is Pt or Pd.
In some embodiments, the ligand LA is selected from the group consisting of the structures of the following LIST 2a:
wherein:
In some embodiments where ligand LA is selected from LIST 2a, at least one of RA or RB1 is independently a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof. In some embodiments, at least one RA is independently a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof. In some embodiments, at least two of RA or RB1 are independently a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof. In some embodiments, at least two RA are independently a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof.
In some embodiments, the ligand LA is selected from the group consisting of the structures of the following LIST 2:
wherein:
In some embodiments, one RB1 is an electron-withdrawing group selected from the group consisting of the structures of LIST 1 as defined herein.
In some embodiments, one RB1 is a 5-membered or 6-membered carbocyclic or heterocyclic aromatic ring. In some embodiments, one RB1 is a 5-membered or 6-membered carbocyclic or heterocyclic non-aromatic ring. In some embodiments, one RB1 is selected from the group consisting of benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, and thiazole.
In some embodiments, ligand LA is selected from the group consisting of the structures of the following LIST 3:
wherein:
In some embodiments where ligand LA is selected from LIST 3, at least one of RA, or RB1 is independently a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof. In some embodiments, at least one RA is independently a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof. In some embodiments, at least two of RA, or RB1 are independently a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof. In some embodiments, at least two RA are independently a substituent selected from the group consisting of halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, boryl, selenyl, and combinations thereof.
In some embodiments, ligand LA is selected from the group consisting of LAi-(Rn)(Rm)(Eo)(Wt), wherein i is an integer from 1 to 304, n and m are each independently an integer from 1 to 71, o is an integer from 1 to 125, and t is an integer from 1 to 18; wherein the structures of LA1-(R1)(R1)(E1)(W1) to LA304-(R71)(R71)(E125)(W18) are defined in the following LIST 4:
In some embodiments, ligand LA is selected from the group consisting of LAAg(Rn)(Rm)(Rl)(Eo)(Wt), wherein g is an integer from 1 to 298, n, m and l are each independently an integer from 1 to 71, o is an integer from 1 to 125, and t is an integer from 1 to 18; wherein structures of LAA1-(R)(R1)(R1)(E1)(W1) to LAA298-(R71)(R71)(R71)(E25)(W8) are defined in the following LIST 4a:
In some embodiments, the compound has a formula of M(LA)p(LB)q(LC)r wherein LB and LC are each a bidentate ligand; and wherein p is 1, 2, or 3; q is 0, 1, or 2; r is 0, 1, or 2; and p+q+r is the oxidation state of the metal M.
In some embodiments, the compound has a formula selected from the group consisting of Ir(LA)3, Ir(LA)(LB)2, Ir(LA)2(LB), Ir(LA)2(LC), and Ir(LA)(LB)(LC); and wherein LA, LB, and LC are different from each other.
In some embodiments, LB is a substituted or unsubstituted phenylpyridine, and LC is a substituted or unsubstituted acetylacetonate.
In some embodiments, the compound can have the formula Ir(LA)3, the formula Ir(LA)(LBk)2, the formula Ir(LAi-(Rn)(Rm)(Eo)(Wt))(LB)2, the formula Ir(LA)2(LBk), the formula Ir(LAi-(Rn)(Rm)(Eo)(Wt))2(LB), the formula Ir(LA)2(LCj-I), the formula Ir(LA)2(LCj-II), the formula Ir(LA)(LBk)(LCj-I), or the formula Ir(LA)(LBk)(LCj-II), wherein LA is a ligand with respect to Formula I as defined here; LBk is defined herein; and LCj-I and LCj-II are each defined herein. In some embodiments, the compound can have a formula Ir(LAi-(Rn)(Rm)(Eo)(Wt))3 consisting of the compounds of Ir(LA1-(R1)(R1)(E1)(W1))3 to Ir(LA304-(R71)(R71)(E125)(W18))3, Ir(LAAg-(Rn)(Rm)(Rl)(Eo)(Wt))3 consisting of the compounds of Ir(LAA1-(R1)(R1)(R1)(E1)(W1))3 to Ir(LAA298-(R71)(R71)(R71)(E125)(W18))3, Ir(LGw-(Rn)(Rm)(Wt))3 consisting of the compounds of Ir(LG1-(R1)(R1)(W1))3 to Ir(LG1 16-(R71)(R71)(W18))3, Ir(LGGd-(Rl)(Rn)(Rm)(Wt))3 consisting of the compounds of Ir(LGG1-(R1)(R1)(R1)(W1))3 to Ir(LGG50-(R71)(R71)(R71)(W18))3, Ir(LAi-(Rn)(Rm)(Eo)(Wt)(LBk)2 consisting of the compounds of Ir(LA1-(R1)(R1)(E1)(W1))(LB1)2 to Ir(LA304-(R71)(R71)(E125)(W18))(LB530)2, Ir(LAAg-(Rn)(Rm)(Rl)(Eo)(Wt))(LBk)2 consisting of the compounds of Ir(LAA1-(R1)(R1)(R1)(E1)(W1))(LB1)2 to Ir(LAA298-(R71)(R71)(R71)(E125)(W18))(LB530)2, Ir(LGw-(Rm)(Rn)(Wt))(LBk)2 consisting of the compounds of Ir(LG1-(R1)(R1)(W1))(LB1)2 to Ir(LG116-(R71)(R71)(W18))(LB530)2, Ir(LGGd-(Rn)(Rm)(Rn)(Wt))(LBk)2 consisting of the compounds of Ir(LGG1-(R1)(R1)(R1)(W1))(LB1)2 to Ir(LGG50-(R71)(R71)(R71)(W18))(LB530)2, Ir(LAi-(Rn)(Rm)(Eo)(Wt))2(LBk) consisting of the compounds of Ir(LA1-(R1)(R1)(E1)(W1))2(LB1) to Ir(LA289-(R71)(R71)(E125)(W18))2(LB530), Ir(LAAg-(Rn)(Rm)(Rl)(Eo)(Wt))2(LBk) consisting of the compounds of Ir(LAA1-(R1)(R1)(R1)(E1)(W1))2(LB1) to Ir(LAA298-(R71)(R71)(R71)(E125)(W18))2(LB530), Ir(LGw-(Rm)(Rn)(Wt))2(LBk) consisting of the compounds of Ir(LG1-(R1)(R1)(W1))2(LB1) to Ir(LG116-(R71)(R71)(W18))2(LB530), Ir(LGGd-(Rl)(Rn)(Rm)(Wt))2(LBk) consisting of the compounds of Ir(LGG1-(R1)(R1)(R1)(W1))2(LB1) to Ir(LGG50-(R71)(R71)(R71)(W18))2(LB530), Ir(LAi-(Rn)(Rm)(Eo)(Wt))2(LCj-I) consisting of the compounds of Ir(LA1-(R1)(R1)(E1)(W1))2(LCj-I) to Ir(LA304-(R71)(R71)(E125)(W18))2(LC1416-I), Ir(LAAg-(Rn)(Rm)(Rl)(Eo)(Wt))2(LCj-I) consisting of the compounds of Ir(LAA1-(R1)(R1)(R1)(E1)(W1))2(LCj-I) to Ir(LAA29-(R71)(R71)(R71)(E125)(W18))2(LC1416-I), Ir(LGw-(Rm)(Rn)(Wt))2(LCj-I) consisting of the compounds of Ir(LG1-(R1)(R1)(W1))2(LCj-I) to Ir(LG116-(R71)(R71)(W18))2(LC1416-I), Ir(LGGd-(Rn)(Rm)(Rn)(Wt))2(LCj-I) consisting of the compounds of Ir(LGG1-(R1)(R1)(R1)(W1))2(LCj-I) to Ir(LGG50-(R71)(R71)(R71)(W18))2(LC1416-1), Ir(LAi-(Rn)(Rm)(Eo)(Wt))2(LC1-I) consisting of the compounds of Ir(LA1-(R1)(R1)(E1)(W1))2(LCj-II) to Ir(LA304-(R71)(R71)(E125)(W18))2(LC1416-I), Ir(LAAg-(Rn)(Rm)(Rl)(Eo)(Wt))2(LC1-I) consisting of the compounds of Ir(LAA1-(R1)(R1)(R1)(E1)(W1))2(LCj-II) to Ir(LAA298-(R71)(R71)(R71)(E125)(W18))2(LC1416-II), Ir(LGw-(Rm)(Rn)(Wt))2(LCj-II) consisting of the compounds of Ir(LG1-(R1)(R1)(W1))2(LCj-II) to Ir(LG116-(R71)(R71)(W18))2(LC1416-II), Ir(LGGd-(Rn)(Rm)(Rn)(Wt))2(LCj-II) consisting of the compounds of Ir(LGG1-(R1)(R1)(R1)(W1))2(LCj-II) to Ir(LGG50-(R71)(R71)(R71)(W18))2(LC1416-II), Ir(LAi-(Rn)(Rm)(Eo)(Wt))(LBk)(LCj-I) consisting of the compounds of Ir(LA1-(R1)(R1)(E1)(W1))(LB1)(LC1-I) to Ir(LA304-(R71)(R71)(E125)(W18))(LB530)(LC1416-I), Ir(LAAg-(Rn)(Rm)(Rl)(Eo)(Wt))(LBk)(LCj-I) consisting of the compounds of Ir(LAA1-(R1)(R1)(R1)(E1)(W1))(LB)(LC1416-I) to Ir(LAA298-(R71)(R71)(R71)(E125)(W18))(LB530)(LC1416-I), Ir(LGw-(Rm)(Rn)(Wt))(LBk)(LCj-I) consisting of the compounds of Ir(LG1-(R1)(R1)(W1))(LB1)(LCj-I) to Ir(LG116-(R71)(R71)(W18) (LB530)(LC1416-I), Ir(LGGd-(Rn)(Rm)(Rn)(Wt))(LBk)(LCj-I) consisting of the compounds of Ir(LGG1-(R1)(R1)(R1)(W1))(LB1)(LC1416-I) to Ir(LGG50-(R71)(R71)(R71)(W18))(LB530)(LC1416-I), Ir(LAi-(Rn)(Rm)(Eo)(Wt))(LBk)(LCj-II) consisting of the compounds of Ir(LA1-(R1)(R1)(E1)(W1))(LB1)(LC1-II) to Ir(LA304-(R71)(R71)(E125)(W18))(LB530)(LC1416-II), Ir(LAAg-(Rn)(Rm)(Rl)(Eo)(Wt))(LBk)(LCj-I) consisting of the compounds of Ir(LAA1-(R1)(R1)(R1)(E1)(W1))(LB1)(LCj-II) to Ir(LAA298-(R71)(R71)(R71)(E125)(W18))(LB530)(LC1416-II), Ir(LGw-(Rm)(Rn)(Wt))(LBk)(LCj-II) consisting of the compounds of Ir(LG1-(R1)(R1)(W1))(LB1)(LC1-II) to Ir(LG116-(R71)(R71)(W18))(LB530)(LC1416-II), or Ir(LGGd-(Rl)(Rm)(Rn)(Wt))(LBk)(LCj-II) consisting of the compounds of Ir(LGG1-(R1)(R1)(R1)(W1))(LB1)(LC1-II) to Ir(LGG50-(R71)(R71)(R71)(W18))(LB530)(LC1416-II), wherein all the variables are the same as previously defined.
In some embodiments, the compound has a formula of Pt(LA)(LB); and wherein LA and LB can be same or different. In some such embodiments, LA and LB are connected to form a tetradentate ligand.
In some embodiments, LB and LC are each independently selected from the group consisting of the structures of the following LIST 8:
In some embodiments, LB and LC are each independently selected from the group consisting of the structures of the following LIST 9:
In some embodiments, LB comprises a structure of
wherein the variables are the same as previously defined. In some embodiments, each of Y1 to Y4 is independently carbon. In some embodiments, at least one of Y1 to Y4 is N. In some embodiments, exactly one of Y1 to Y4 is N. In some embodiments, Y1 is N. In some embodiments, Y2 is N. In some embodiments, Y3 is N. In some embodiments, Y4 is N. In some embodiments, at least one of Ra is a tertiary alkyl, silyl or germyl. In some embodiments, at least one of Ra is a tertiary alkyl. In some embodiments, Y3 is C and the Ra attached thereto is a tertiary alkyl, silyl or germyl. In some embodiments, Y1 to Y3 is C, Y4 is N, and the Ra attached to Y3 is a tertiary alkyl, silyl or germyl. In some embodiments, Y1 to Y3 is C, Y4 is N, and the Ra attached to Y2 is a tertiary alkyl, silyl or germyl. In some embodiments, at least one of Rb is a tertiary alkyl, silyl, or germyl. In some embodiments, the tertiary alkyl is tert-butyl. In some embodiments, at least one pair of Ra, one pair of Rb, or one pair of Ra and Rb are joined or fused into a ring.
In some embodiments, the compound has a formula selected from the group consisting of Formula Ir(LA)3, Formula Ir(LA)(LBk)2, Formula Ir(LA)2(LBk), Formula Ir(LA)2(LCj-I), and Formula Ir(LA)2(LCj-II),
In some embodiments, the compound is selected from the group consisting of only those compounds whose LBk corresponds to one of the following: LB1, LB30, LB31, LB109, LB110, LB112, LB113, LB114, LB125, LB127, LB138, LB140, LB149, LB150, LB170, LB171, LB172, LB174, LB208, LB241, LB312, LB315, LB356, LB367, LB371, LB382, LB439, LB440, LB455, LB456, LB457, LB458, LB461, LB462, LB463, LB469, and LB476.
In some embodiments, the compound is selected from the group consisting of only those compounds whose LBk corresponds to one of the following: LB1, LB30, LB31, LB125, LB138, LB171, LB172, LB356, LB367, LB371, LB382, LB455, and LB456.
In some embodiments, the compound is selected from the group consisting of only those compounds having LCj-I or LCj-II ligand whose corresponding R201 and R202 are defined to be one of the following structures: RD1, RD3, RD4, RD5, RD9, RD10, RD17, RD18, RD20, RD22, RD37, RD40, RD41, RD42, RD43, RD48, RD49, RD50, RD54, RD55, RD58, RD59, RD78, RD79, RD81, RD87, RD88, RD89, RD93, RD116, RD117, RD118, RD119, RD120, RD133, RD134, RD135, RD136, RD143, RD144, RD145, RD146, RD147, RD149, RD151, RD154, RD155, RD161, RD175, RD190, RD193, RD200, RD201, RD206, RD210, RD214, RD215, RD216, RD218, RD219, RD220, RD227, RD237, RD241, RD242, RD245, and RD246.
In some embodiments, the compound is selected from the group consisting of only those compounds having LCj-I or LCj-II ligand whose corresponding R201 and R202 are defined to be one of selected from the following structures: RD1, RD3, RD4, RD5, RD9, RD10, RD17, RD22, RD43, RD50, RD78, RD116, RD118, RD133, RD134, RD135, RD136, RD143, RD14, RD145, RD146, RD149, RD151, RD154, RD155, RD190, RD193, RD200, RD201, RD206, RD210, RD214, RD215, RD216, RD218, RD219, RD220, RD227, RD237, RD241, RD242, RD245, and RD246.
In some embodiments, the compound is selected from the group consisting of only those compounds having one of the following structures for the LCj-I ligand:
In some embodiments, the compound comprising a first ligand LA of Formula I is selected from the group consisting of the structures of the following LIST 12a:
wherein
In some embodiments, the compound is selected from the group consisting of the structures of the following LIST 13:
In some embodiments, the compound has the Formula III,
In some embodiments, moiety E and moiety F are both 6-membered aromatic rings.
In some embodiments, moiety F is a 5-membered or 6-membered heteroaromatic ring.
In some embodiments, L1 is O or CRR′.
In some embodiments, Z2 is N and Z1 is C.
In some embodiments, Z2 is C and Z1 is N.
In some embodiments, L2 is a direct bond. In some embodiments, L2 is NR.
In some embodiments, K1, K2, K3, and K4 are all direct bonds.
In some embodiments, one of K1, K2, K3, and K4 is O.
In some embodiments, the compound can be selected from the group consisting of compounds having the formula of Pt(LA′)(Ly):
wherein LA′ is selected from the group consisting of the structures shown in the following LIST 14:
In some embodiments, each RB is selected from the group consisting of the structures of LIST 5, LIST 6, or LIST 7 defined herein. In some embodiments, at least one RB comprises a cyclic group selected from the group consisting of W1 to W16 (LIST 6 defined herein) or an electron-withdrawing group selected from the group consisting of E1 to E125 (LIST 5 defined herein).
In some embodiments, the compound can be selected from the group consisting of the compounds having the formula of Pt(LA′)(Ly):
In some embodiments, the compound can be selected from the group consisting of the compounds of the following LIST 18:
In another aspect, the present disclosure provides a compound comprising a structure selected from the group consisting of the following LIST W1:
wherein:
In some embodiments, each YB and YC is independently selected from the group consisting of O, S, Se, and C(CH3)2. In some embodiments, each YB and YC is independently selected from the group consisting of O and C(CH3)2.
In yet another aspect, the present disclosure provides a compound comprising a structure selected from the group consisting of the following LIST W2:
wherein each YB and YC is independently as defined previously.
In some embodiments, each YB and YC is independently selected from the group consisting of O, S, Se, and C(CH3)2. In some embodiments, each YB and YC is independently selected from the group consisting of O, and C(CH3)2.
It should be understood that when a structure is selected from LIST W1 or LIST W2, further modifications may be necessary in order to meet one or more limitations of claim 1 or its dependent claims. Those modifications should be considered within the scope of the present disclosure.
In some embodiments, the compound having a first ligand LA of Formula I described herein can be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, percent deuteration has its ordinary meaning and includes the percent of possible hydrogen atoms (e.g., positions that are hydrogen, deuterium, or halogen) that are replaced by deuterium atoms.
In some embodiments of heteroleptic compound having the formula of M(LA)p(LB)q(LC), as defined herein, the ligand LA has a first substituent RI, where the first substituent R has a first atom a-I that is the farthest away from the metal M among all atoms in the ligand LA. Additionally, the ligand LB, if present, has a second substituent RII, where the second substituent RB has a first atom a-II that is the farthest away from the metal M among all atoms in the ligand LB. Furthermore, the ligand LC, if present, has a third substituent RIII, where the third substituent RIII has a first atom a-III that is the farthest away from the metal M among all atoms in the ligand LC.
In such heteroleptic compounds, vectors VD1, VD2, and VD3 can be defined as follows. VD1 represents the direction from the metal M to the first atom a-I and the vector VD1 has a value D1 that represents the straight line distance between the metal M and the first atom a-I in the first substituent RI. VD2 represents the direction from the metal M to the first atom a-II and the vector VD2 has a value D2 that represents the straight line distance between the metal M and the first atom a-II in the second substituent RII. VD3 represents the direction from the metal M to the first atom a-III and the vector VD3 has a value D3 that represents the straight line distance between the metal M and the first atom a-III in the third substituent RIII.
In such heteroleptic compounds, a sphere having a radius r is defined whose center is the metal M and the radius r is the smallest radius that will allow the sphere to enclose all atoms in the compound that are not part of the substituents RI, RII and RIII; and where at least one of D1, D2, and D3 is greater than the radius r by at least 1.5 Å. In some embodiments, at least one of D1, D2, and D3 is greater than the radius r by at least 2.9, 3.0, 4.3, 4.4, 5.2, 5.9, 7.3, 8.8, 10.3, 13.1, 17.6, or 19.1 Å.
In some embodiments of such heteroleptic compound, the compound has a transition dipole moment axis and angles are defined between the transition dipole moment axis and the vectors VD1, VD2, and VD3, where at least one of the angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 is less than 40°. In some embodiments, at least one of the angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 is less than 30°. In some embodiments, at least one of the angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 is less than 20°. In some embodiments, at least one of the angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 is less than 15°. In some embodiments, at least one of the angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 is less than 10°. In some embodiments, at least two of the angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 are less than 20°. In some embodiments, at least two of the angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 are less than 15°. In some embodiments, at least two of the angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 are less than 10°.
In some embodiments, all three angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 are less than 20°. In some embodiments, all three angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 are less than 15°. In some embodiments, all three angles between the transition dipole moment axis and the vectors VD1, VD2, and VD3 are less than 10°.
In some embodiments of such heteroleptic compounds, the compound has a vertical dipole ratio (VDR) of 0.33 or less. In some embodiments of such heteroleptic compounds, the compound has a VDR of 0.30 or less. In some embodiments of such heteroleptic compounds, the compound has a VDR of 0.25 or less. In some embodiments of such heteroleptic compounds, the compound has a VDR of 0.20 or less. In some embodiments of such heteroleptic compounds, the compound has a VDR of 0.15 or less.
One of ordinary skill in the art would readily understand the meaning of the terms transition dipole moment axis of a compound and vertical dipole ratio of a compound. Nevertheless, the meaning of these terms can be found in U.S. Pat. No. 10,672,997 whose disclosure is incorporated herein by reference in its entirety. In U.S. Pat. No. 10,672,997, horizontal dipole ratio (HDR) of a compound, rather than VDR, is discussed. However, one skilled in the art readily understands that VDR=1−HDR.
In another aspect, the present disclosure also provides an OLED device comprising a first organic layer that contains a compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode, where the organic layer comprises a compound having a first ligand LA of Formula I as described herein.
In some embodiments, the organic layer may be an emissive layer and the compound as described herein may be an emissive dopant or a non-emissive dopant.
In some embodiments, the emissive layer comprises one or more quantum dots.
In some embodiments, the organic layer may further comprise a host, wherein the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan, wherein any substituent in the host is 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≡CCnH2n+1, Ar1, Ar1—Ar2, CnH2n—Ar1, or no substitution, wherein n is an integer from 1 to 10; and wherein Ar1 and Ar2 are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.
In some embodiments, the organic layer is selected from the group consisting of HIL, HTL, EBL, EML, HBL, ETL, and EIL. In some embodiments, the organic layer may be an emissive layer and the compound as described herein may be an emissive dopant or a non-emissive dopant.
In some embodiments, the organic layer may further comprise a host, wherein host comprises at least one chemical group selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, azaborinine, oxaborinine, dihydroacridine, xanthene, dihydrobenzoazasiline, dibenzooxasiline, phenoxazine, phenoxathiine, phenothiazine, dihydrophenazine, fluorene, naphthalene, anthracene, phenanthrene, phenanthroline, benzoquinoline, quinoline, isoquinoline, quinazoline, pyrimidine, pyrazine, pyridine, triazine, boryl, silyl, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).
In some embodiments, the host can be selected from the group consisting of the structures of the following HOST Group 1:
In some embodiments at least one of J1 to J3 is N. In some embodiments at least two of J1 to J3 are N. In some embodiments, all three of J1 to J3 are N. In some embodiments, each YCC and YDD is independently O, S, or SiRR′, or more preferably O or S. In some embodiments, at least one unsubstituted aromatic carbon atom is replaced with N to form an aza-ring.
In some embodiments, the host is selected from the group consisting of EG1-MG1-EG1 to EG53-MG27-EG53 with a formula of EGa-MGb-EGc, or EG1-EG1 to EG53-EG53 with a formula of EGa-EGc when MGb is absent, wherein a is an integer from 1 to 53, b is an integer from 1 to 27, c is an integer from 1 to 53. The structure of EG1 to EG53 is shown below:
The structures of MG1 to MG27 are shown below:
In the MGb structures shown above, the two bonding positions in the asymmetric structures MG18, MG11, MG12, MG13, MG14, MG17, MG24, and MG25 are labeled with numbers for identification purposes.
In some embodiments, the host can be any of the aza-substituted variants thereof, fully or partially deuterated variants thereof, and combinations thereof. In some embodiments, the host has formula EGa-MGb-Egc and is selected from the group consisting of hi to h112 defined in the following HOST Group 2 list, where each of MGb, EGa, and EGc are defined as follows:
In the table above, the EGa and EGc structures that are bonded to one of the asymmetric structures MG10, MG11, MG12, MG13, MG14, MG17, MG24, and MG25, are noted with a numeric prefix identifying their bonding position in the MGb structure.
In some embodiments, the host may be selected from the HOST Group consisting of:
and combinations thereof.
In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.
In some embodiments, the emissive layer can comprise two hosts, a first host and a second host. In some embodiments, the first host is a hole transporting host, and the second host is an electron transporting host. In some embodiments, the first host and the second host can form an exciplex.
In some embodiments, the compound as described herein may be a sensitizer; wherein the device may further comprise an acceptor; and wherein the acceptor may be selected from the group consisting of fluorescent emitter, delayed fluorescence emitter, and combination thereof.
In yet another aspect, the OLED of the present disclosure may also comprise an emissive region containing a compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the emissive region can comprise a compound having a first ligand LA of Formula I as described herein.
In some embodiments, at least one of the anode, the cathode, or a new layer disposed over the organic emissive layer functions as an enhancement layer. The enhancement layer comprises a plasmonic material exhibiting surface plasmon resonance that non-radiatively couples to the emitter material and transfers excited state energy from the emitter material to non-radiative mode of surface plasmon polariton. The enhancement layer is provided no more than a threshold distance away from the organic emissive layer, wherein the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer and the threshold distance is where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed over the enhancement layer on the opposite side of the organic emissive layer. In some embodiments, the outcoupling layer is disposed on opposite side of the emissive layer from the enhancement layer but still outcouples energy from the surface plasmon mode of the enhancement layer. The outcoupling layer scatters the energy from the surface plasmon polaritons. In some embodiments this energy is scattered as photons to free space. In other embodiments, the energy is scattered from the surface plasmon mode into other modes of the device such as but not limited to the organic waveguide mode, the substrate mode, or another waveguiding mode. If energy is scattered to the non-free space mode of the OLED other outcoupling schemes could be incorporated to extract that energy to free space. In some embodiments, one or more intervening layer can be disposed between the enhancement layer and the outcoupling layer. The examples for intervening layer(s) can be dielectric materials, including organic, inorganic, perovskites, oxides, and may include stacks and/or mixtures of these materials.
The enhancement layer modifies the effective properties of the medium in which the emitter material resides resulting in any or all of the following: a decreased rate of emission, a modification of emission line-shape, a change in emission intensity with angle, a change in the stability of the emitter material, a change in the efficiency of the OLED, and reduced efficiency roll-off of the OLED device. Placement of the enhancement layer on the cathode side, anode side, or on both sides results in OLED devices which take advantage of any of the above-mentioned effects. In addition to the specific functional layers mentioned herein and illustrated in the various OLED examples shown in the figures, the OLEDs according to the present disclosure may include any of the other functional layers often found in OLEDs.
The enhancement layer can be comprised of plasmonic materials, optically active metamaterials, or hyperbolic metamaterials. As used herein, a plasmonic material is a material in which the real part of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material includes at least one metal. In such embodiments the metal may include at least one of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca alloys or mixtures of these materials, and stacks of these materials. In general, a metamaterial is a medium composed of different materials where the medium as a whole acts differently than the sum of its material parts. In particular, we define optically active metamaterials as materials which have both negative permittivity and negative permeability. Hyperbolic metamaterials, on the other hand, are anisotropic media in which the permittivity or permeability are of different sign for different spatial directions. Optically active metamaterials and hyperbolic metamaterials are strictly distinguished from many other photonic structures such as Distributed Bragg Reflectors (“DBRs”) in that the medium should appear uniform in the direction of propagation on the length scale of the wavelength of light. Using terminology that one skilled in the art can understand: the dielectric constant of the metamaterials in the direction of propagation can be described with the effective medium approximation. Plasmonic materials and metamaterials provide methods for controlling the propagation of light that can enhance OLED performance in a number of ways.
In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the wavelength-sized features and the sub-wavelength-sized features have sharp edges.
In some embodiments, the outcoupling layer has wavelength-sized features that are arranged periodically, quasi-periodically, or randomly, or sub-wavelength-sized features that are arranged periodically, quasi-periodically, or randomly. In some embodiments, the outcoupling layer may be composed of a plurality of nanoparticles and in other embodiments the outcoupling layer is composed of a plurality of nanoparticles disposed over a material. In these embodiments the outcoupling may be tunable by at least one of varying a size of the plurality of nanoparticles, varying a shape of the plurality of nanoparticles, changing a material of the plurality of nanoparticles, adjusting a thickness of the material, changing the refractive index of the material or an additional layer disposed on the plurality of nanoparticles, varying a thickness of the enhancement layer, and/or varying the material of the enhancement layer. The plurality of nanoparticles of the device may be formed from at least one of metal, dielectric material, semiconductor materials, an alloy of metal, a mixture of dielectric materials, a stack or layering of one or more materials, and/or a core of one type of material and that is coated with a shell of a different type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles wherein the metal is selected from the group consisting of Ag, Al, Au, Ir, Pt, Ni, Cu, W, Ta, Fe, Cr, Mg, Ga, Rh, Ti, Ru, Pd, In, Bi, Ca, alloys or mixtures of these materials, and stacks of these materials. The plurality of nanoparticles may have additional layer disposed over them. In some embodiments, the polarization of the emission can be tuned using the outcoupling layer. Varying the dimensionality and periodicity of the outcoupling layer can select a type of polarization that is preferentially outcoupled to air. In some embodiments the outcoupling layer also acts as an electrode of the device.
In yet another aspect, the present disclosure also provides a consumer product comprising an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound having a first ligand LA of Formula I as described herein.
In some embodiments, the consumer product can be one of a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign.
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.
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.
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, also referred to as organic vapor jet deposition (OVJD)), 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 are 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 disclosure 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 present disclosure 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 present disclosure can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. 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 disclosure, 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° C.), but could be used outside this temperature range, for example, from −40 degree c. to +80° C.
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.
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.
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.
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, or a monovalent or polyvalent variant thereof. In other words, the inventive compound, or a monovalent or polyvalent variant thereof, 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 or bonds to the rest of the chemical structure. In the instance of a supramolecule, the inventive compound can also be incorporated into the supramolecule complex without covalent bonds.
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.
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.
A hole injecting/transporting material to be used in the present disclosure 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.
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.
The light emitting layer of the organic EL device of the present disclosure 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:
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,
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, WO06121811, WO07018067, WO07108362, WO07115970, WO07115981, 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.
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:
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,
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. The minimum amount of hydrogen of the compound being deuterated is selected from the group consisting of 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. 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.
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.
1-Bromo-4-chloro-2-iodobenzene (1) (50 g, 158 mmol), copper(I) iodide (0.750 g, 3.94 mmol) and bis(triphenylphosphine)palladium (II) chloride (2.76 g, 3.94 mmol) were combined and suspended in THF (315 ml) and triethylamine (132 ml, 945 mmol). The flask was vacuum/backfilled with N2 10 times (until boiling). Ethynyltrimethylsilane (17.02 g, 173 mmol) was then added over the course of 75 minutes via syringe pump and the reaction stirred at RT for 18 h. Reaction mixture turned from yellow to black over the course of 2 hours. The reaction was filtered through celite (10 g cartridge), and the filter washed with THF (200 mL). The organics were diluted with ether (1 L) and washed with brine (3×250 ml) before drying over MgSO4. Filtering and subsequent concentration in vacuo provided a dark orange oil (47 g). The oil was suspended in iso-hexane (200 mL), filtered through a plug of silica (approx. 20 g) and the plug washed with additional iso-hexane (300 mL). Concentration in vacuo provided an orange oil which was dissolved in iso-hexane (200 ml) and activated charcoal added (1 spatula). The suspension was filtered through a silica plug (20 g) and washed with iso-hexane (200 ml) before removing solvents in vacuo to provide ((2-bromo-5-chlorophenyl) ethynyl) trimethylsilane (2) (45.6 g, 155 mmol, 99% yield) as a yellow oil.
Dibenzo[b,d]furan-4-ylboronic acid (3) (34.5 g, 163 mmol), tetrakistriphenylphosphinepalladium (0) (8.96 g, 7.75 mmol), sodium carbonate (49.3 g, 465 mmol), ((2-bromo-5-chlorophenyl)ethynyl)trimethylsilane (2) (44.6 g, 155 mmol) and toluene (500 ml) were added to a 3-neck 2 L flask fitted with a condenser. The vessel was vacuum/backfilled with nitrogen 3 times whereupon ethanol (125 ml) and water (125 mL) were then added. The reaction vessel was vacuum/backfilled with nitrogen 3 times (until the solvent was boiling) and the reaction sparged with nitrogen for 30 minutes. The reaction mixture was heated to 80° C. for 22 h. The reaction was then allowed cooled down to RT and diluted with ethyl acetate (500 mL). Then washed with brine (3×250 mL). The organics were dried over MgSO4 and concentrated in vacuo to give a brown oil which was suspended in iso-hexane. The resulting brown solid was filtered away and discarded. The remaining dark orange oil was purified using a silica plug, eluting with neat iso-hexane. Fractions were combined and concentrated in vacuo to give ((5-chloro-2-(dibenzo [b, d] furan-4-yl) phenyl) ethynyl) trimethylsilane (4) (52.75 g, 139 mmol, 90% yield) as an orange oil which slowly crystallised to a solid.
((5-Chloro-2-(dibenzo [b, d] furan-4-yl) phenyl) ethynyl) trimethylsilane (4) (46.92 g, 125 mmol) was dissolved in MeOH (600 ml) and DCM (150 ml) and potassium carbonate (17.29 g, 125 mmol) was added in one portion. The reaction was stirred at 25° C. for 17 h over which time a thick white precipitate formed. The solid was collected by filtration and washed with MeOH (200 mL). The solid was then dissolved in DCM (1 L) and washed with water (250 ml) and saturated brine (aq., 250 ml) before passing through a phase separator cartridge and concentrating in vacuo to provide 4-(4-chloro-2-ethynylphenyl)dibenzo[b,d]furan (5) (33.2 g, 107 mmol, 86% yield) as a light orange solid.
4-(4-chloro-2-ethynylphenyl) dibenzo [b, d] furan (5) (34.9 g, 115 mmol) was dissolved in toluene (1200 mL) and the solution sparged with nitrogen for 20 min before adding gold (III) chloride (7.00 g, 23.06 mmol) in one portion. The suspension was sparged with nitrogen for an additional 5 min then heated to 100° C. and stirred at this temperature for 24 hrs. The brown reaction was hot filtered through celite and then left to stand at RT overnight. The light brown crystals which formed were collected by filtration and washed with iso-hexane (approx. 200 mL). Concentration of the filtrate in vacuo gave a dark brown solid. The crystals were dissolved in hot DCM (2 L) and then stirred over silica (4 large spatulas) and charcoal (1 large spatula) for 30 mins at 40° C. The suspension was filtered through celite, and silica (4× spatulas) and charcoal (1× spatula) added to the resultant yellow filtrate and stirred at 40° C. for an additional 30 min. Filtration through celite gave a pale-yellow solution which was concentrated in vacuo to afford a yellow solid, 13 g. The filtrate was dissolved in hot toluene (550 mL) and left to crystallise at RT overnight. The resultant light brown crystals were collected by filtration and washed with iso-hexane, Concentration of the filtrate in vacuo gave a dark brown solid. The crystals were dissolved in warm DCM (1.5 L, 40° C.) and stirred over silica (3× spatulas) and charcoal (1× spatula) for 30 mins. Filtration through celite gave a yellow solution to which was added silica (3× spatulas) and charcoal (1× spatula) and stirred at 40° C. for 30 mins. Filtration through celite gave a pale-yellow solution which was combined with the previous isolated 13 g and concentrated in vacuo to afford a yellow solid, 22.8 g. The second filtrate was dissolved in hot toluene (250 mL) and left to crystallise at RT overnight. The resultant light brown crystals were collected by filtration and washed with iso-hexane. The crystals were dissolved in warm DCM (500 mL, 40° C.) and stirred over silica (3× spatulas) and charcoal (1× spatula) for 30 mins. Filtration through celite gave a yellow solution to which was added silica (3× spatulas) and charcoal (1× spatula) and stirred at 40° C. for 30 min. Filtration through celite gave a pale-yellow solution which was combined with the previous 22 g batch and concentrated in vacuo to provide a yellow solid, 24.8 g. This solid was dissolved in hot toluene (450 mL) and left to stand at RT for 64 h. The resultant crystals were collected by filtration and washed with iso-hexane (250 mL) before drying at 50° C. under vacuum for 90 min. Afforded light yellow fine crystals, 21.16 g that were subsequently was dissolved in warm DCM (1.5 L, 40° C.) and stirred over silica (3× spatulas) and charcoal (1× spatula) for 30 min. Filtration through celite gave a pale yellow solution to which was added silica (3× spatulas) and charcoal (1× spatula) and stirred at 40° C. for 30 min. Filtration through celite gave a pale yellow solution which was concentrated in vacuo to provide a light yellow fluffy solid, 19.01 g (62.8 mmol, 54.5%).
3-Chlorophenanthro[4,3-b] benzofuran (6) (3.0 g, 9.91 mmol) and phenylboronic acid (2.4 g, 2 eq.) were suspended in 75 mL of toluene and 20 mL of water. Palladium G2 XPhos catalyst (2 mol. %) and XPhos ligand (5 mol. %) were added as one portion. The reaction mixture was degassed and heated to 100° C. for 5 h, then it was cooled down to room temperature and evaporated. The residue was subjected to column chromatography on silica gel, eluting with heptane/DCM 1/1 (v/v), providing 3-phenylphenanthro[4,3-b] benzofuran (3.24 g, 90% yield) as white solid.
3-Phenylphenanthro[4,3-b] benzofuran (7) (7.2 g, 20.91 mmol) was dissolved in 150 mL of dry THF under nitrogen atmosphere and cooled in acetone/dry ice bath. Sec-Bu lithium solution in hexanes (30 ml, 41.8 mmol) was added via syringe, the reaction mixture was stirred for 45 min, then 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.78 g, 41.8 mmol) was added via syringe dropwise. The reaction mixture was allowed to warm up to room temperature and stirred for 12 h. It was quenched with ammonium chloride 10% aqueous solution, extracted with ethyl acetate, filtered and evaporated. The residue was subjected to column chromatography on silica gel column, eluted with heptanes/ethyl acetate gradient mixture, providing 4,4,5,5-tetramethyl-2-(3-phenylphenanthro[4,3-b] benzofuran-12-yl)-1,3,2-dioxaborolane as white solid (4.9 g, 50% yield).
The 4,4,5,5-tetramethyl-2-(3-phenylphenanthro[4,3-b]benzofuran-12-yl)-1,3,2-dioxaborolane (8) (3.2 g, 6.80 mmol) and 2-chloro-4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)pyridine were suspended in DME (150 mL)/water (30 mL), added Pd catalyst (160 mg, 2 mol. %) and potassium carbonate (1.88 g, 2 eq.). The reaction mixture was degassed and heated to 80° C. for 16 h. The reaction mixture was cooled down, diluted with ethyl acetate, washed with water, filtered, and evaporated. The residue was subjected to column chromatography on silica gel, eluted with gradient mixture heptane/ethyl acetate, providing 4-(2,2-dimethylpropyl-1,1-d2)-5-(methyl-d3)-2-(3-phenylphenanthro[4,3-b] benzofuran-12-yl) pyridine (9) as white solid (3.12 g, 90% yield).
Iridium triflate complex (1.8 g) and ligand (1.8 g, 1.75 eq.) were suspended in 40 mL of DMF/2-ethoxyethanol 1/1 mixture. The reaction mixture was degassed and heated to 100° C. for 120 h. The material was dissolved in ethyl acetate, washed with brine, and evaporated. The residue was subjected to column chromatography on silica gel column, eluted with toluene/heptane/DCM 3/1/1 mixture. Pure fractions were combined, evaporated, and crystallized from toluene/ethanol, providing 920 mg of pure product as yellow needles.
The synthesis of the comparative example can be found in US20190280219, which is incorporated in its entirety herein by reference.
A representative procedure: A 1 L round-bottom flask containing 1,4-dioxane (450 mL) was degassed with nitrogen for 15 minutes. 1 (62.5 g, 295 mmol), bis(pinacolato)diborane (82.3 g, 324 mmol), potassium acetate (145 g, 1.47 mol) and PdCl2(dppf)-CH2Cl2 adduct (12.0 g, 14.7 mmol) were then added, the headspace was repurged, and the mixture was heated in an 80° C. oil bath overnight. The reaction was cooled and diluted with EtOAc (600 mL) and water (600 mL). The mixture was stirred and filtered through a Celite bed, and the bed was washed with EtOAc (100 mL). The layers were separated, and the organic layer was washed with water (5×300 mL), dried (MgSO4), filtered and stripped to give the crude product. The crude was dissolved in a minimum of DCM and filtered through a silica gel bed (2.5 L) in a sintered glass funnel, eluting with 35% EtOAc in heptanes to give 3 as a yellow solid (42 g, 61% yield). 1H NMR contains impurities. Used as is.
A representative procedure: A 1 L round-bottom flask containing 1,4-dioxane (200 mL) and water (65 mL) was degassed with nitrogen for 15 minutes. 2 (84.4 g, 311 mmol), 3 (61.9 g, 239 mmol), sodium carbonate (55.7 g, 526 mmol) and PdCl2(dppf)-CH2Cl2 adduct (9.76 g, 11.9 mmol) were then added, the headspace was repurged, and the mixture was heated in an 80° C. oil bath overnight. The reaction was cooled and diluted with EtOAc (500 mL) and water (500 mL). The mixture was filtered through a Celite bed, and the bed was washed with EtOAc (300 mL). The layers were separated, and the organic layer was washed with water (3×200 mL), dried (MgSO4), filtered and stripped to give the crude product. The crude was absorbed onto silica (using DCM) and applied to a bed of 3.5 L of silica gel in a sintered glass funnel, eluting with 15% EtOAc in heptanes to give 4 as a yellow solid (26.5 g, 34% yield). There was more DP in impure fractions, which were set aside. 1H NMR spectra suggest restricted rotation.
A representative procedure: A 2 L round-bottom flask containing 1,4-dioxane (540 mL) and water (270 mL) was degassed with nitrogen for 15 minutes. 5 (29.9 g, 160 mmol), 4 (40.0 g, 123 mmol), sodium carbonate (39.2 g, 370 mmol) and PdCl2(dppf)-CH2Cl2 adduct (5.04 g, 6.17 mmol) were then added, the headspace was purged, and the mixture was heated in an 80° C. oil bath overnight with mechanical stirring. (6 is very insoluble. In some runs, 6 precipitates from the reaction mixture and it gets very thick, and in other runs it does not and remains essentially a liquid. Mechanical stirring should be used in case precipitation occurs). The reaction was cooled, and DCM (2 L) and water (500 mL) were added. The layers were separated, and the organic layer was washed with water (4×300 mL). The organic layer was dried (MgSO4), filtered and concentrated to give the crude product. The crude was absorbed onto silica and applied to a bed of 3.5 L of silica gel in a sintered glass funnel, eluting with 40 to 80% DCM in heptanes to give a solid. This material was recrystallized from a minimum of boiling ethyl acetate (˜10 mL/gram) and heptanes (an equal amount), allowing it to cool overnight. The solid was filtered and dried to give 6 as a white solid (40.5 g, 85% yield), NMR pure.
A representative procedure: To a cooled (ice bath) mixture of 3″-chloro-2′,5′-difluoro-2,2″-dimethoxy-[1,1′: 4′,1″-terphenyl]-4-carbonitrile 6 (48.0 g, 124 mmol) and DCM (280 mL) in a 1 L flask was slowly added BBr3 (118 mL, 1.24 mol) to give a clear yellow solution, which was stirred in the ice bath for 1 hour, then allowed to warm to rt overnight. The reaction was quenched by adding dropwise to a bucket containing ice, adding more ice as needed. The mixture was then brought to pH˜3 using concentrated NaOH, then to pH˜7 using saturated NaHCO3. EtOAc (3 L) was then added, and the layers were separated. The aqueous layer was extracted with ethyl acetate (500 mL). The combined organic layers were washed with water (3×500 mL), dried (MgSO4), filtered and evaporated to give the crude product. The crude was purified by preabsorbing onto silica gel (using MeOH) and eluted through a silica gel bed (2 L) using 0 to 15% EA in DCM as eluent to give 7 as a light-yellow solid (35.5 g, 78% yield), NMR pure, contained EtOAc.
A representative procedure: To a 1 L round-bottom flask containing 7 (35.5 g, 99.23 mmol) was added NMP (525 mL) and potassium carbonate (41.1 g, 298 mmol) and the mixture was heated in a 170° C. oil bath overnight. The reaction was cooled and EtOAc (500 mL) was added. A precipitate formed, and the mixture was stirred for 1 hour. The solids were filtered and washed with EtOAc (100 mL), then with water (2×500 mL). The solids were transferred to a round-bottomed flask and stirred with water (500 mL) overnight. The solids were filtered and washed again with water until the washes are neutral (˜750 mL). The solids were washed with EtOH (500 mL) and heptanes (300 mL) and dried to give desired product as a grey solid, (22.0 g, 69%). This material was used as is. (A sample was washed with 10 mL/gram DMSO at 90 degrees overnight, then cooled and filtered. This gave purer material, but this was not done with the bulk of the material used in the next step). The 1H NMR was taken in CDCl3, in which it has limited solubility.
A representative procedure: A 250 mL round-bottom flask containing 1,4-dioxane (52 mL) was degassed for 20 minutes. To the flask was added starting material (3.00 g, 9.44 mmol), bis(pinacolato)diborane (2.88 g, 11.3 mmol), potassium acetate (2.78 g, 28.3 mmol), tris(dibenzylideneacetone)dipalladium (432 mg, 472 μmol) and XPhos (900. mg, 1.89 mmol), and the headspace was purged with nitrogen and the reaction was heated in a 100° C. oil bath overnight. The reaction was filtered hot through a Celite bed, and the bed was washed with hot 1,2-dichloroethane (100 mL) and DCM (100 mL). The filtrate was washed with water (2×50 mL), and the organic layer was dried (MgSO4), filtered and evaporated to give an orange oil. The oil was taken up in ethyl acetate (10 mL) and heptanes (10 mL) was added. A precipitate formed, which was filtered and washed with heptanes to give 8 as a light orange solid, (3.48 g, 90%). This material was used as is in the next step. (It is important to precipitate 8 as a solid as shown above.
A representative procedure: A 500 mL round-bottom flask containing water (18.1 mL) and 1,4-dioxane (100 mL) was degassed for 20 minutes. The degassed solvent was added to a 500 mL round-bottom flask containing 8 (3.48 g, 8.50 mmol), and then 2-chloro-5-(2,2-dimethylpropyl-1,1-d2)-4-(methyl-d3)pyridine 9 (1.38 g, 6.80 mmol) (only 0.8 equivalents was used intentionally −8 was impure and wanted to conserve the amount of valuable deuterated 0587-9 that was used), potassium phosphate (5.42 g, 25.5 mmol) and tetrakis(triphenylphosphine)palladium(0) (491 mg, 425 μmol) were added. The headspace was purged and heated in a 100° C. oil bath overnight. The mixture was cooled and diluted with EtOAc (450 mL) and water (150 mL), and the resulting mixture was stirred for 2 hours, during which time all solids dissolved. The layers were separated, and the organic layer was washed with water (2×100 mL). The organic layer was dried (MgSO4), filtered and evaporated to give crude product. The crude was chromatographed by preabsorbing onto silica gel (using DCM) and eluting with 0 to 5% THF in DCM to give ligand as a light-yellow solid. This material was recrystallized by dissolving in 35 mL/gram of boiling dichloroethane, then adding 35 mL/gram EtOAc and allowing to cool to rt overnight. The precipitate was filtered and dried to give ligand as a white solid (1.53 g, 40% yield, 99.98% purity by HPLC).
One 250 ml RBF was charged with Iridium complexes (2.601 g, 1.0 Eq, 2.915 mmol), Ligand (1.150 g, 1 Eq, 2.915 mmol), 2,6-dimethylpyridine (624.8 mg, 2 Eq, 5.831 mmol), 2-ethoxyethanol (50.00 mL). The reaction was heated to 100c for 4 days. Reaction mixture was evaporated to dryness and subject to column (sio2, 330 g×7, 75% toluene 25% heptane to 100% toluene) to yield desired compound (1.32 g, 42%).
A representative procedure: In a 1000 mL round bottom flask, 1,4-dioxane (400.0 mL) was bubbled vigorously with nitrogen for 10 minutes. 2-Bromo-5-cyanoanisole (40.00 g, 98% Wt., 1 Eq, 184.9 mmol, Ambeed), Bis(pinacolato)diborane (52.59 g, 99% Wt., 1.109 Eq, 205.0 mmol, Oakwood Chemical), PdCl2(dppf) (6.860 g, 95% Wt., 0.04818 Eq, 8.907 mmol, Combi-Blocks) and potassium acetate (92.26 g, 99.7% Wt, 5.070 Eq, 937.3 mmol, Sigma-Aldrich) were added to the degassed dioxane and again degassed with nitrogen for 10 minutes. The reaction mixture was heated at 80° C. in a preheated oil bath for 16 hours. The dioxane was removed completely under reduced pressure and the residue was diluted with ethylacetate (EtOAc) (100 mL) and water (100 mL). The phases were separated, and the aqueous layer was additionally extracted twice with EtOAc (50 mL). The combined organic extract was washed with saturated brine (20-30 mL), then dried with sodium sulphate. The drying agent was filtered off, and the filtrates were concentrated under vacuum at 45° C. to yield a brown colored solid. The crude product was dissolved in dichloromethane (DCM), loaded onto a silica gel column and eluted with 100% heptanes to 23% EtOAc/heptanes. The product was obtained as an off-white solid with a pinch of orange color, 47.88 g (68%) and 1H NMR confirmed it was pure.
A representative procedure: In a 500 mL round bottom flask, a mixture of 1,4-dioxane (145.0 mL) and water (36.20 mL) was bubbled vigorously with nitrogen for 10 minutes. Then, 3-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzonitrile (47.88 g, 1 Eq, 125.7 mmol), 1,4-dibromo-2,3-difluorobenzene (45.39 g, 98% Wt, 1.302 Eq, 163.6 mmol, Ambeed), sodium carbonate (29.50 g, 99.5% Wt, 2.204 Eq, 276.9 mmol, Sigma-Aldrich), and 1,1′-bis(diphenylphosphino)ferrocene-palladium(II) dichloride (3.381 g, 95% Wt, 0.03493 Eq, 4.389 mmol, Combi-Blocks) were added to the 1,4 dioxane in one portion. The headspace of the flask was purged with nitrogen for a few minutes, and the reaction mixture stirred vigorously at 80° C. is a preheated oil bath overnight. The dioxane was removed under reduced pressure. The residue was diluted with water (100 mL) and dichloromethane (100 mL). The phases were separated, and the aqueous layer was extracted twice with dichloromethane (50 mL). The combined organic layer was then dried with sodium sulphate. The drying agent was filtered off, and the filtrates were concentrated under vacuum at 45° C. to yield brown colored solid.
The crude product was dissolved in dichloromethane, loaded onto a silica gel column and eluted with 10% to 15% EtOAc/heptanes to remove less polar impurities. Then, elution was continued at 21% EtOAc/heptanes to elute the product. The product was obtained as a white fluffy solid, 23 g (54%). 96% purity by liquid chromatography mass spectroscopy (LCMS).
A representative procedure: In a 500 mL round bottom flask, a mixture of 1,4-dioxane (77.00 mL) and water (39.00 mL) was bubbled vigorously with nitrogen for 10 minutes. Then, (3-chloro-2-methoxyphenyl)boronic acid (19.44 g, 98% Wt, 1.5 Eq, 102.2 mmol, Combi-Blocks), 4′-bromo-2′,3′-difluoro-2-methoxy-[1,1′-biphenyl]-4-carbonitrile (23.00 g, 96% Wt, 1 Eq, 68.12 mmol), sodium carbonate (22.06 g, 99.5% Wt, 3.04 Eq, 207.1 mmol, Sigma-Aldrich), and 1,1′-bis(diphenylphosphino)ferrocene-palladium(II) dichloride (2.623 g, 95% Wt, 0.05 Eq, 3.406 mmol, Combi-Blocks) were added to the dioxane in one portion. The headspace of the flask was purged with nitrogen for a few minutes, and the reaction mixture stirred vigorously at 80° C. using a preheated oil bath overnight. The dioxane was removed under reduced pressure. The residue was diluted with water (100 mL) and dichloromethane (100 mL). The phases were separated, and the aqueous layer was extracted twice with dichloromethane (50 mL), and the combined organic layer was dried with sodium sulphate. The drying agent was filtered off, and the filtrates were concentrated under vacuum at 45° C. to give a brown colored solid.
The crude material after adsorption on silica was loaded onto a silica gel column preequilibrated with heptanes. Eluted with 15% to 20% EtOAc/heptanes to remove less polar impurities. Then, elution continued at 25% EtOAc/heptanes to elute the product as an off-white solid, 24 g (89%). 97% purity by LCMS.
A representative procedure: In a 2 L three-neck round bottom flask equipped with a septum, a solution of 3″-chloro-2′,3′-difluoro-2,2″-dimethoxy-[1,1′: 4′,1″-terphenyl]-4-carbonitrile (10.00 g, 97% Wt, 1.0 Eq, 25.14 mmol) in anhydrous dichloromethane (50 mL) was prepared under nitrogen and cooled to −75° C. (external temperature) in a dry ice-acetone bath. Neat boron tribromide (66.20 g, 25.5 mL, 99.9% Wt, 10.5 Eq, 264.0 mmol) was added dropwise to yield a clear yellow colored solution. A nitrogen balloon was attached, and the mixture was stirred allowing it to warm up slowly to room temperature (−22° C.) for 24 hours.
An aliquot (partitioned between EtOAc/aq. NaHCO3) was analyzed by thin-layer chromatography (TLC) (30% EtOAc in heptanes) and LCMS confirmed 92% conversion. The mixture was cooled in a dry ice/acetone bath and then carefully quenched with methanol (MeOH) (36 mL). Then, the cooling bath was removed, and saturated aq. NaHCO3 (˜1000 mL) was added carefully (to minimize effervescence), initially dropwise, cooling in a water bath towards the end of the addition. After a brief stirring, EtOAc (300 mL) was added, and two clear phases were separated. The aq. layer (pH˜7) was additionally extracted twice with EtOAc (100 mL), and the combined organic extract was dried with Na2SO4. The drying agent was filtered off, and the filtrates were concentrated under vacuum at 45° C. to give a crude dark brown solid, ˜9.67 g. The crude solid product was purified by column chromatography to yield 19.37 g (˜100%). 96% purity by LCMS.
A representative procedure: In a 500 mL round bottom flask 3″-chloro-2′,3′-difluoro-2,2″-dihydroxy-[1,1′: 4′,1″-terphenyl]-4-carbonitrile (13.65 g, 96% Wt, 1 Eq, 36.63 mmol) and potassium carbonate (15.87 g, 99.5% Wt, 3.12 Eq, 114.3 mmol) were added to N-methyl-2-pyrrolidone (NMP) (55 mL) to give a yellow-colored solution. The resulting mixture was stirred for 6 hours at 130° C. in a preheated oil bath temperature. The reaction mixture was diluted with 20 mL of ethyl acetate and the resulting precipitate was filtered. The precipitate was washed each with 20 mL of water, ethanol and heptanes to produce the product as an off-white solid, 11 g (94%). 99% purity by LCMS.
A mixture of 18-chloro-3,20-dioxapentacyclo[11.7.0.02,10.04,9.014,19]icosa-1,4(9),5,7,10,12,14,16,18-nonaene-6-carbonitrile (2.00 g, 6.29 mmol), Bis(pinacolato)diboron (2.40 g, 9.44 mmol), Potassium acetate (1.24 g, 12.6 mmol), 2-(Dicyclohexylphosphino)-2′,4′,6′-tri-isopropyl-1,1′-biphenyl (XPhos) (0.60 g, 1.26 mmol) and 1,4-dioxane (60 mL) was sparged with nitrogen for 10 minutes. (2-Dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II) methanesulfonate (XPhos Pd G3) (0.53 g, 0.629 mmol) was added and the mixture sparged with nitrogen for an additional five minutes. The reaction mixture was then heated at 100° C. for 2 hours. The reaction mixture was diluted with EtOAc (200 mL), then passed through a phase separator. The organics were washed with water (100 ml) and brine (100 mL), dried with MgSO4, filtered, then evaporated to dryness. The solid obtained was washed with a mixture of pentane/Et2O (10:1, 30 ml), then dried under vacuum at 40° C. to give 18-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,20-dioxapentacyclo[11.7.0.02,10.04,9.014,19]icosa-1,4,6,8,10,12,14,16,18-nonaene-6-carbonitrile (2.10 g, 4.11 mmol, 65.22%) (purity=80% by LCMS) as a grey solid.
A mixture of 18-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3,20-dioxapentacyclo[11.7.0.02,10.04,9.014,19]icosa-1,4,6,8,10,12,14,16,18-nonaene-6-carbonitrile (2.10 g, 5.13 mmol), 6-chloro-2-(1,1-dideuterio-2,2-dimethyl-propyl)-3-(trideuteriomethyl)pyridine (1.04 g, 5.13 mmol), cesium carbonate (4.18 g, 12.8 mmol), 1,4-dioxane (50 mL) and water (10 mL) was sparged with nitrogen for 10 minutes. XPhos Pd G3 (0.22 g, 0.257 mmol) was added and the mixture was sparged for an additional 5 minutes before heating at 90° C. for 2 hours. The cooled reaction mixture was filtered and the collected grey solid re-dissolved in dichloromethane (DCM) (100 mL), washed with water/brine (100 mL), passed through a phase separator, and evaporated to give an off-white solid. The off-white solid was purified by column chromatography (SFAR-KP-Amino, 10-35% DCM in iso-hexane) then recrystallized from isopropyl alcohol (IPA) to yield 18-[4-(1,1-dideuterio-2,2-dimethyl-propyl)-5-(trideuteriomethyl)-2-pyridyl]-3,20-dioxapentacyclo[11.7.0.02,10.04,9.014,19]icosa-1,4,6,8,10,12,14,16,18-nonaene-6-carbonitrile (1.39 g, 3.09 mmol, 60.23%) as a white solid (Inertsil-HPLC, 99.68%).
One 100 ml round-bottom flask (RBF) was charged with. iridium complexes (3.817 g, 1 Eq, 4.449 mmol), ligand (2.000 g, 1 Eq, 4.449 mmol), 2,6-dimethylpyridine (953.5 mg, 2 Eq, 8.898 mmol) and 2-ethoxyethanol (50.00 mL) and heated to 100° C. for 200 hours. The crude product was purified by column to yield 2.18 g of Inventive Compound 3 (47.1%).
All example devices were fabricated by high vacuum (<10−7 Torr) thermal evaporation. The anode electrode was 800 Å of indium tin oxide (ITO). The cathode consisted of 10 Å of Liq (8-hydroxyquinoline lithium) followed by 1,000 Å of Al. All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H2O and O2) immediately after fabrication with a moisture getter incorporated inside the package. The organic stack of the device examples consisted of sequentially, from the ITO Surface: 100 Å of LG101 (purchased from LG Chem) as the hole injection layer (HIL); 400 Å of HTM as a hole transporting layer (HTL); emissive layer (EML) with thickness 400 Å; 50 Å of EBM as an electron blocking layer (EBL); Emissive layer containing H-host (H1): E-host (H2) in 6:4 ratio and 5 weight % of green emitter; 350 Å of Liq (8-hydroxyquinoline lithium) doped with 35% of ETM as the ETL. The device structure is shown in Table 1. The chemical structures of the device materials are shown below.
Upon fabrication, the device was tested to measure EL and JVL. For this purpose, the samples were energized by the 2 channel Keysight B2902 Å SMU at a current density of 10 mA/cm2 and measured by the Photo Research PR735 Spectroradiometer. Radiance (W/str/cm2) from 380 nm to 1080 nm, and total integrated photon count were collected. The devices were then placed under a large area silicon photodiode for the JVL sweep. The integrated photon counts of the device at 10 mA/cm2 is used to convert the photodiode current to photon count. The voltage is swept from 0 to a voltage equating to 200 mA/cm2. The EQE of the device is calculated using the total integrated photon count. All results are summarized in Table 2. Voltage, LE, EQE and PE of inventive example are reported as relative numbers normalized to the results of the comparative example.
Table 2 provides a summary of performance of electroluminescence device of the materials. Inventive examples 1 show higher efficiency and longer LT than their comparative example 1. Inventive example 2 show higher M/T and longer LT than their comparative example 2. Inventive example 3 shows higher M/T and twice of LT than comparative example 3. The effect of narrowness for inventive compound 1 is demonstrated in the EL spectrum overlay as shown in
This application is a continuation-in-part of co-pending U.S. patent application Ser. No. 18/297,676, filed Apr. 10, 2023, U.S. patent application Ser. No. 18/058,461, filed Nov. 23, 2022, and U.S. patent application Ser. No. 18/177,178, filed on Mar. 2, 2023. In addition, U.S. patent application Ser. No. 18/297,676, filed Apr. 10, 2023, claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Applications No. 63/481,143, filed on Jan. 23, 2023, No. 63/476,204, filed Dec. 20, 2022, No. 63/385,994, filed Dec. 5, 2022, No. 63/385,730, filed Dec. 1, 2022, No. 63/382,134, filed Nov. 3, 2022, No. 63/417,746, filed Oct. 20, 2022, No. 63/408,686, filed Sep. 21, 2022, No. 63/408,357, filed Sep. 20, 2022, No. 63/407,981, filed Sep. 19, 2022, No. 63/406,019, filed Sep. 13, 2022, No. 63/392,731, filed Jul. 27, 2022, No. 63/356,191, filed Jun. 28, 2022, No. 63/353,920, filed Jun. 21, 2022, No. 63/351,049, filed Jun. 10, 2022, No. 63/350,150, filed Jun. 8, 2022, No. 63/332,165, filed Apr. 18, 2022; and U.S. patent application Ser. No. 18/058,461, filed Nov. 23, 2022, claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Applications No. 63/354,721, filed Jun. 23, 2022, the entire contents of all the above referenced applications are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 63481143 | Jan 2023 | US | |
| 63476204 | Dec 2022 | US | |
| 63385994 | Dec 2022 | US | |
| 63385730 | Dec 2022 | US | |
| 63382134 | Nov 2022 | US | |
| 63417746 | Oct 2022 | US | |
| 63408686 | Sep 2022 | US | |
| 63408357 | Sep 2022 | US | |
| 63407981 | Sep 2022 | US | |
| 63406019 | Sep 2022 | US | |
| 63392731 | Jul 2022 | US | |
| 63356191 | Jun 2022 | US | |
| 63353920 | Jun 2022 | US | |
| 63351049 | Jun 2022 | US | |
| 63350150 | Jun 2022 | US | |
| 63332165 | Apr 2022 | US | |
| 63354721 | Jun 2022 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 18297676 | Apr 2023 | US |
| Child | 18814299 | US | |
| Parent | 18058461 | Nov 2022 | US |
| Child | 18814299 | US | |
| Parent | 18177178 | Mar 2023 | US |
| Child | 18814299 | US |
