Patent Application
20250228122
The present disclosure generally relates to organic or metal coordination compounds and formulations and their various uses including as emitters, sensitizers, charge transporters, or exciton transporters in devices such as organic light emitting diodes and related electronic devices and consumer products.
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, organic scintillators, 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 displays, illumination, and backlighting.
One application for 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 having a first ligand LA comprising a structure of Formula I,
In another aspect, the present disclosure provides a formulation comprising a compound having a first ligand LA comprising a structure 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 comprising a structure 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 comprising a structure of Formula I as described herein.
Unless otherwise specified, the below terms used herein are defined as follows:
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.
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.
Layers, materials, regions, and devices may be described herein in reference to the color of light they emit. In general, as used herein, an emissive region that is described as producing a specific color of light may include one or more emissive layers disposed over each other in a stack.
As used herein, a “NIR”, “red”, “green”, “blue”, “yellow” layer, material, region, or device refers to a layer, a material, a region, or a device that emits light in the wavelength range of about 700-1500 nm, 580-700 nm, 500-600 nm, 400-500 nm, 540-600 nm, respectively, or a layer, a material, a region, or a device that has a highest peak in its emission spectrum in the respective wavelength region. In some arrangements, separate regions, layers, materials, or devices may provide separate “deep blue” and “light blue” emissions. As used herein, the “deep blue” emission component refers to an emission having a peak emission wavelength that is at least about 4 nm less than the peak emission wavelength of the “light blue” emission component. Typically, a “light blue” emission component has a peak emission wavelength in the range of about 465-500 nm, and a “deep blue” emission component has a peak emission wavelength in the range of about 400-470 nm, though these ranges may vary for some configurations.
In some arrangements, a color altering layer that converts, modifies, or shifts the color of the light emitted by another layer to an emission having a different wavelength is provided. Such a color altering layer can be formulated to shift wavelength of the light emitted by the other layer by a defined amount, as measured by the difference in the wavelength of the emitted light and the wavelength of the resulting light. In general, there are two classes of color altering layers: color filters that modify a spectrum by removing light of unwanted wavelengths, and color changing layers that convert photons of higher energy to lower energy. For example, a “red” color filter can be present in order to filter an input light to remove light having a wavelength outside the range of about 580-700 nm. A component “of a color” refers to a component that, when activated or used, produces or otherwise emits light having a particular color as previously described. For example, a “first emissive region of a first color” and a “second emissive region of a second color different than the first color” describes two emissive regions that, when activated within a device, emit two different colors as previously described.
As used herein, emissive materials, layers, and regions may be distinguished from one another and from other structures based upon light initially generated by the material, layer or region, as opposed to light eventually emitted by the same or a different structure. The initial light generation typically is the result of an energy level change resulting in emission of a photon. For example, an organic emissive material may initially generate blue light, which may be converted by a color filter, quantum dot or other structure to red or green light, such that a complete emissive stack or sub-pixel emits the red or green light. In this case the initial emissive material, region, or layer may be referred to as a “blue” component, even though the sub-pixel is a “red” or “green” component.
In some cases, it may be preferable to describe the color of a component such as an emissive region, sub-pixel, color altering layer, or the like, in terms of 1931 CIE coordinates. For example, a yellow emissive material may have multiple peak emission wavelengths, one in or near an edge of the “green” region, and one within or near an edge of the “red” region as previously described. Accordingly, as used herein, each color term also corresponds to a shape in the 1931 CIE coordinate color space. The shape in 1931 CIE color space is constructed by following the locus between two color points and any additional interior points. For example, interior shape parameters for red, green, blue, and yellow may be defined as shown below:
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 group (—C(O)—Rs).
The term “ester” refers to a substituted oxycarbonyl (—O—C(O)—Rs or —C(O)—O—Rs) group.
The term “ether” refers to an —ORs group.
The terms “sulfanyl” or “thio-ether” are used interchangeably and refer to a —SRs group.
The term “selenyl” refers to a —SeRs group.
The term “sulfinyl” refers to a —S(O)—Rs group.
The term “sulfonyl” refers to a —SO2—Rs group.
The term “phosphino” refers to a group containing at least one phosphorus atom bonded to the relevant structure. Common examples of phosphino groups include, but are not limited to, groups such as a —P(Rs)2 group or a —PO(Rs)2 group, wherein each Rs can be same or different.
The term “silyl” refers to a group containing at least one silicon atom bonded to the relevant structure. Common examples of silyl groups include, but are not limited to, groups such as a —Si(Rs)3 group, wherein each Rs can be same or different.
The term “germyl” refers to a group containing at least one germanium atom bonded to the relevant structure. Common examples of germyl groups include, but are not limited to, groups such as a —Ge(R3)3 group, wherein each Rs can be same or different.
The term “boryl” refers to a group containing at least one boron atom bonded to the relevant structure. Common examples of boryl groups include, but are not limited to, groups such as a —B(Rs)2 group or its Lewis adduct —B(Rs)3 group, 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 the general substituents as defined in this application. Preferred Rs is 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. More preferably 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 groups having an alkyl carbon atom bonded to the relevant structure. Preferred alkyl groups are those containing from one to fifteen carbon atoms, preferably one to nine 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 can be further substituted.
The term “cycloalkyl” refers to and includes monocyclic, polycyclic, and spiro alkyl groups having a ring alkyl carbon atom bonded to the relevant structure. 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 can be further substituted.
The terms “heteroalkyl” or “heterocycloalkyl” refer to an alkyl or a cycloalkyl group, 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, Ge and Se, preferably, O, S or N. Additionally, the heteroalkyl or heterocycloalkyl group can be further substituted.
The term “alkenyl” refers to and includes both straight and branched chain alkene groups. Alkenyl groups are essentially alkyl groups that include at least one carbon-carbon double bond in the alkyl chain with one carbon atom from the carbon-carbon double bond that is bonded to the relevant structure. 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 group 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, Ge, 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 can be further substituted.
The term “alkynyl” refers to and includes both straight and branched chain alkyne groups. Alkynyl groups are essentially alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain with one carbon atom from the carbon-carbon triple bond that is bonded to the relevant structure. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group can be further substituted.
The terms “aralkyl” or “arylalkyl” are used interchangeably and refer to an aryl-substituted alkyl group having an alkyl carbon atom bonded to the relevant structure. Additionally, the aralkyl group can be further substituted.
The term “heterocyclic group” refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally the at least one heteroatom is selected from O, S, Se, N, P, B, Si, Ge, and Se, preferably, O, S, N, or B. Hetero-aromatic cyclic groups may be used interchangeably with heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 10 ring atoms, preferably 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 can be further substituted or fused.
The term “aryl” refers to and includes both single-ring and polycyclic aromatic hydrocarbyl groups. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”). Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty-four carbon atoms, six to eighteen carbon atoms, and more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons, twelve carbons, fourteen carbons, or eighteen carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, and naphthalene. Additionally, the aryl group can be further substituted or fused, such as, without limitation, fluorene.
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, Se, N, P, B, Si, Ge, and Se. In many instances, O, S, N, or B 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 aromatic 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. 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-four carbon atoms, three to eighteen carbon atoms, and more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, selenophenodipyridine, azaborine, borazine, 5λ2,9λ2-diaza-13b-boranaphtho[2,3,4-de]anthracene, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene; preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 5λ2,9λ2-diaza-13b-boranaphtho[2,3,4-de]anthracene, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene. Additionally, the heteroaryl group can be further substituted or fused.
Of the aryl and heteroaryl groups listed above, the groups of triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, benzimidazole, 5λ2,9λ2-diaza-13b-boranaphtho[2,3,4-de]anthracene, 5λ2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, and the respective aza-analogs of each thereof are of particular interest.
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, germyl, boryl, aryl, heteroaryl, nitrile, sulfanyl, and combinations thereof.
In some instances, the Even More Preferred General Substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof.
In yet other instances, the Most Preferred General Substituents are selected from the group consisting of deuterium, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
The terms “substituted” and “substitution” refer to a substituent other than H that is bonded to the relevant position, e.g., a carbon or nitrogen. For example, when R1 represents mono-substitution, then one R1 must be other than H (i.e., a substitution). Similarly, when R1 represents di-substitution, then two of R1 must be other than H. Similarly, when R1 represents zero or no substitution, R1, for example, can be a hydrogen for all 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[fh]quinoxaline and dibenzo[fh]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.
As used herein, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. includes undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also include undeuterated, partially deuterated, and fully deuterated versions thereof. Unless otherwise specified, atoms in chemical structures without valences fully filled by H or D should be considered to include undeuterated, partially deuterated, and fully deuterated versions thereof. For example, the chemical structure of
implies to include C6H6, C6D6, C6H3D3, and any other partially deuterated variants thereof. Some common basic partially or fully deuterated group include, without limitation, CD3, CD2C(CH3)3, C(CD3)3, and C6D5.
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 substituents in the molecule can be optionally joined or fused into a ring. The preferred ring is a five to nine-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. In yet other instances, a pair of adjacent substituents can be optionally joined or fused into a ring. 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.
The compounds disclosed herein exhibit improved properties when incorporated into an OLED. The improved properties include narrower emission spectra (full-width half maximum) and decreased transient lifetime.
In one aspect, the present disclosure provides a compound having a first ligand LA comprising a structure of Formula I,
In some embodiments, the compound is not
In some embodiments, moiety C is a polycyclic fused ring system, ring B or a ring formed by two R2 and moiety C collectively comprise at least two N ring atoms.
In some embodiments, moiety C comprises three or more fused 5- to 10-membered carbocyclic or heterocyclic rings, and ring B and moiety C collectively comprise at least one N ring atom.
In some embodiments, moiety A is a monocyclic 6-membered aromatic ring containing one or more N atoms, moiety C is a fused bicyclic structure consisting of a 6-membered ring and a heterocyclic ring with the 6-membered ring fused to ring B1, and with ring B or moiety C containing at least one N atom; or at least one R2 or R3 comprising an electron-withdrawing group.
In some embodiments, moiety A is a monocyclic 6-membered aromatic ring containing one or more N atoms, moiety C is a monocyclic ring, and two R2 are joined to form moiety I, wherein moiety I is a heterocyclic ring or a heterocyclic fused ring system, wherein the heterocyclic ring and each ring of the heterocyclic fused ring system is independently a 5-membered or 6-membered carbocyclic or heterocyclic ring.
In some embodiments, one of the following statements is true:
In some embodiments when moiety C is a benzimidazole bicyclic structure in which the benzo moiety of the benzimidazole bicyclic structure is fused to ring B1, then at least one of X1 to X4 is N. In some embodiments when moiety C is a benzimidazole bicyclic structure in which the benzo moiety of the benzimidazole bicyclic structure is fused to ring B1, then exactly one of X1 to X4 is N.
In some embodiments when moiety C is a benzimidazole bicyclic structure in which the benzo moiety of the benzimidazole bicyclic structure is fused to ring B1, then at least one RA is a substituent other than hydrogen. In some embodiments when moiety C is a benzimidazole bicyclic structure in which the benzo moiety of the benzimidazole bicyclic structure is fused to ring B1, then at least one RA is an alkyl, cycloalkyl, aryl, heteroaryl, silyl, germyl, an electron-withdrawing group, or a combination thereof.
In some embodiments when moiety C is a benzimidazole bicyclic structure in which the benzo moiety of the benzimidazole bicyclic structure is fused to ring B1, then the benzo group of the benzimidazole bicyclic structure is substituted with a substituent other than hydrogen. In some embodiments when moiety C is a benzimidazole bicyclic structure in which the benzo moiety of the benzimidazole bicyclic structure is fused to ring B1, then the benzo group of the benzimidazole bicyclic structure is substituted with an alkyl, cycloalkyl, aryl, heteroaryl, silyl, germyl, an electron-withdrawing group, or combinations thereof.
In some embodiments, moiety C is not a benzimidazole bicyclic structure in which the benzo moiety of the benzimidazole bicyclic structure is fused to ring B1,
In some embodiments when moiety C is a bicyclic fused ring structure, each ring of the bicyclic fused ring structure has at least one N ring atom.
In some embodiments when moiety C is s bicyclic fused ring structure, each ring of the bicyclic fused ring structure has exactly one N ring atom.
In some embodiments when moiety C is s bicyclic fused ring structure and each of X1 to X4 is independently C, then each ring of the bicyclic fused ring structure has at least one N ring atom.
In some embodiments when moiety C is s bicyclic fused ring structure and each of X1 to X4 is independently C, then each ring of the bicyclic fused ring structure has exactly one N ring atom.
In some embodiments, K is a direct bond. In some embodiments, K is O.
In some embodiments, if moiety C comprises two rings and the terminal ring comprises two N ring atoms, then moiety A is not imidazole. In some embodiments, moiety C comprises two rings and the terminal ring comprises two N ring atoms, and moiety A is not imidazole.
In some embodiments, a first ligand LA has a structure of Formula I. In some embodiments, a first ligand LA consists essentially of Formula I.
In some embodiments, at least one R1, R2, or R3 is selected from the group consisting of the General Substituents defined herein. In some embodiments, at least one R1 is selected from the group consisting of the General Substituents defined herein. In some embodiments, at least one R2 is selected from the group consisting of the General Substituents defined herein. In some embodiments, at least one R3 is selected from the group consisting of the General Substituents defined herein.
In some embodiments of Formula I, at least one R, R′, R1, R2, and R3 is partially or fully deuterated. In some embodiments, at least one R1 is partially or fully deuterated. In some embodiments, at least one R2 is partially or fully deuterated. In some embodiments, at least one R3 is partially or fully deuterated. In some embodiments, at least one R or R′ is partially or fully deuterated.
In some embodiments, moiety A is a monocyclic ring or a polycyclic fused ring system, wherein the monocyclic ring and each ring of the polycyclic fused ring system is independently 5-membered or 6-membered carbocyclic or heterocyclic ring. In some embodiments, moiety A is a monocyclic ring or a polycyclic fused ring system, wherein the monocyclic ring and each ring of the polycyclic fused ring system is independently 5-membered or 6-membered aryl or heteroaryl ring.
In some embodiments, moiety C is a polycyclic fused ring system, wherein each ring of the polycyclic fused ring system is independently 5-membered or 6-membered carbocyclic or heterocyclic ring. In some embodiments, moiety C is a polycyclic fused ring system, wherein each ring of the polycyclic fused ring system is independently 5-membered or 6-membered aryl and heteroaryl ring.
In some embodiments, each R, R′, R1, R2, and R3 is independently hydrogen, or a substituent selected from the group consisting of the Preferred General Substituents defined herein. In some embodiments, each R, R′, R1, R2, and R3 is independently hydrogen, or a substituent selected from the group consisting of the More Preferred General Substituents defined herein. In some embodiments, each R, R′, R1, R2, and R3 is independently hydrogen, or a substituent selected from the group consisting of the Most Preferred General Substituents defined herein.
In some embodiments, metal M is selected from the group consisting of Ir, Rh, Re, Ru, Os, Pt, Pd, Ag, Au, and Cu. In some embodiments, metal M is Ir. In some embodiments, metal M is Pt or Pd. In some embodiments, metal M is Pt. In some embodiments, metal M is Pd.
In some embodiments, Z1 is N and Z2 is C. In some embodiments, Z1 is carbene carbon and Z2 is N.
In some embodiments, Z1 and Z2 are both C.
In some embodiments, each of X1 to X4 is C. In some embodiments, at least one of X1 to X4 is N. In some embodiments, exactly one of X1 to X4 is N.
In some embodiments, the one of X1 to X4 bonded to moiety A is C.
In some embodiments, the one of X1 to X4 coordinated to the metal M is C. In some embodiments, the one of X1 to X4 coordinated to the metal M is N.
In some embodiments, moiety A is independently 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, phenanthro[3,2-b]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, benzobenzimidazole, aza-benzobenzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanathrene, anthracene, aza-anthracene, 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 Ir atom.
In some embodiments, moiety A is a monocyclic 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, and triazole. In some embodiments, moiety A is pyridine, imidazole derived carbene, or imidazole. In some embodiments, moiety A is pyridine. In some embodiments, moiety A is imidazole.
In some embodiments, moiety A is a polycyclic fused ring system. In some embodiments, moiety A is selected from the group consisting of naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, phenanthro[3,2-b]benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, benzimidazole derived carbene, aza-benzimidazole, aza-benzimidazole derived carbene, benzobenzimidazole, aza-benzobenzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanathrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene. In some embodiments, moiety A is quinoline, isoquinoline, or benzimidazole. In some embodiments, moiety A is quinoline. In some embodiments, moiety A is isoquinoline. In some embodiments, moiety A is benzimidazole.
In some embodiments, moiety A can be a polycyclic fused ring structure. In some embodiments, moiety A can be a polycyclic fused ring structure comprising at least two fused rings. In some embodiments, the polycyclic fused ring structure has one 6-membered ring and one 5-membered ring. In some such embodiments, either the 5-membered ring or the 6-membered ring can coordinate to the metal. In some embodiments, the polycyclic fused ring structure has two 6-membered rings. In some embodiments, moiety A can be selected from the group consisting of benzofuran, benzothiophene, benzoselenophene, naphthalene, and aza-variants thereof.
In some embodiments, moiety A can be 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 A can be selected from the group consisting of dibenzofuran, dibenzothiophene, dibenzoselenophene, and aza-variants thereof. In some such embodiments, moiety A can be further substituted at the ortho- or meta-position of 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 A can be 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 A can be 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 A can be an aza version of the polycyclic fused rings described above. In some such embodiments, moiety A can contain exactly one aza N atom. In some such embodiments, moiety A can contain 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 separated by at least two other rings from the metal M atom. In some such embodiments, the ring having aza N atom is separated by at least three other rings from the metal M atom. In some such embodiments, each of the ortho positions of the aza N atom is substituted.
In some embodiments, moiety C is a polycyclic fused ring system. In some embodiments, moiety C is selected from the group consisting of 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, benzimidazole derived carbene, aza-benzimidazole, aza-benzimidazole derived carbene, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanathrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene. In some embodiments, moiety C is quinoline, isoquinoline, or quinazoline.
In some embodiments, ring B and moiety C collectively comprise at least two N ring atoms. In some embodiments, ring B and moiety C collectively comprise at least three N ring atoms. In some embodiments, ring B comprises at least one N ring atom.
In some embodiments, moiety C comprises two fused rings.
In some embodiments, one of X1 to X4 is N and moiety C comprises at least one N ring atom. In some such embodiments, moiety C is quinoline or isoquinoline. In some embodiments, moiety C is quinazoline.
In some embodiments, moiety C comprises three or more 5- to 10-membered carbocyclic or heterocyclic rings, and ring B and moiety C collectively comprise at least one N ring atom. In some such embodiments, moiety C comprises three 5- to 10-membered carbocyclic or heterocyclic rings. In some embodiments, moiety C comprises four or more 5- to 10-membered carbocyclic or heterocyclic rings.
In some embodiments, moiety C comprises three or more 5- or 6-membered carbocyclic or heterocyclic rings. In some embodiments, moiety C comprises three or more 5- or 6-membered aryl or heteroaryl rings.
In some embodiments, moiety C is selected from the group consisting of carbazole, aza-carbazole, aza-dibenzofuran, aza-dibenzothiophene, quinoxaline, phthalazine, aza-phenanathrene, aza-anthracene, phenanthridine, and aza-fluorene.
In some embodiments, the ring of moiety C fused to the ring containing Y is benzene. In some embodiments, the ring of moiety C fused to the ring containing Y comprises at least one heteroatom. In some embodiments, the ring of moiety C fused to the ring containing Y comprises at least one N atom.
In some embodiments, moiety C comprises at least two N ring atoms. In some embodiments, moiety C comprises at least three N ring atoms.
In some embodiments, Y is selected from the group consisting of O, S, and Se. In some embodiments, Y is O. In some embodiments, Y is S. In some embodiments, Y is Se.
In some embodiments, Y is selected from the group consisting of BR, NR, and PR. In some embodiments, Y is selected from the group consisting of BRR′, CRR′, SiRR′, and GeRR′. In some embodiments, Y is selected from the group consisting of P(O)R, C═O, C═S, C═Se, C═NR, C═CRR′, S═O, and SO2. In some embodiments, Y is selected CR.
In some embodiments of Formula I, ring B, ring B1, and moiety C collectively comprise only one N ring atom. In some such embodiments, moiety C contains the only N atom and is on the ring fused to ring B1. In some such embodiments, moiety C contains the only N atom and is on the ring away from ring B1. In some such embodiments, moiety C contains two fused 6-membered rings and the only N atom is on the 6-membered ring fused to ring B1. In some such embodiments, moiety C contains two fused 6-membered rings and the only N atom is on the 6-membered ring away from ring B1.
In some embodiments of Formula I, moiety C comprises all 6-membered rings. In some embodiments, moiety C comprises only one 5-membered ring, and the rest are all 6-membered rings. In some embodiments, moiety C comprises two 6-membered rings. In some embodiments, moiety C comprises one 6-membered ring and one 5-membered ring. In some such embodiments, moiety C contains only one ring N atom, and neither ring B nor ring B1 contains any ring N atom. In some embodiments, moiety C comprises three 6-membered rings. In some embodiments, moiety C comprises two 6-membered rings and one 5-membered ring. In some such embodiments, moiety C contains only one ring N atom, and neither ring B nor ring B1 contains any ring N atom. In some such embodiments, the 6-membered moiety C ring fused to ring B1 contains the only ring N atom.
In some embodiments, the compound comprises an electron-withdrawing group. In some embodiments, the electron-withdrawing group has a Hammett constant larger than 0. In some embodiments, the electron-withdrawing group has a Hammett constant equal or larger than 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or 1.1.
In some embodiments, Formula I comprises an electron-withdrawing group selected from the group consisting of the following EWG1 LIST: F, CF3, CN, COCH3, CHO, COCF3, COOMe, COOCF3, NO2, SF3, SiF3, PF4, SF5, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC, +N(Rk2)3, (Rk2)2CCN, (Rk2)2CCF3, CNC(CF3)2, BRk3Rk2, 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 pyridoxine, 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,
In some embodiments, Formula I comprises an electron-withdrawing group selected from the group consisting of the structures of the following EWG2 List:
In some embodiments, Formula I comprises an electron-withdrawing group selected from the group consisting of the structures of the following EWG3 LIST:
In some embodiments, Formula I comprises an electron-withdrawing group selected from the group consisting of the structures of the following EWG4 LIST:
In some embodiments, Formula I comprises an electron-withdrawing group that is a π-electron deficient electron-withdrawing group. In some embodiments, the π-electron deficient electron-withdrawing group is selected from the group consisting of the structures of the following Pi-EWG LIST: CN, COCH3, CHO, COCF3, COOMe, COOCF3, NO2, SF3, SiF3, PF4, SF5, OCF3, SCF3, SeCF3, SOCF3, SeOCF3, SO2F, SO2CF3, SeO2CF3, OSeO2CF3, OCN, SCN, SeCN, NC, +N(Rk2)3, BRk2Rk3, 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 aryl, partially and fully fluorinated heteroaryl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate,
wherein the variables are the same as previously defined.
In some embodiments, the compound comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, the compound comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, the compound comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, the compound comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, the compound comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.
In some embodiments, at least one R1 is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, at least one R1 is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, at least one R1 is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, at least one R1 is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, at least one R1 is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.
In some embodiments, at least one R2 is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, at least one R2 is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, at least one R2 is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, at least one R2 is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, at least one R2 is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.
In some embodiments, at least one R3 is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, at least one R3 is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, at least one R3 is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, at least one R3 is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, at least one R3 is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.
In some embodiments, at least one R or R′ is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, at least one R or R′ is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, at least one R or R′ is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, at least one R or R′ is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, at least one R or R′ is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.
In some embodiments, at least one R1 is not H. In some embodiments, at least one R1 comprises at least one C atom. In some embodiments, at least one R1 comprises a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
In some embodiments, at least two R1 each independently comprise a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some embodiments, at least two R1 are independently alkyl. In some embodiments, at least two R1 each independently comprise at least two C atoms. In some embodiments, at least two R1 each independently comprise at least three C atoms.
In some embodiments, at least one R2 is not H. In some embodiments, at least one R2 comprises at least one C atom. In some embodiments, at least one R2 comprises a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
In some embodiments, at least one R3 is not H. In some embodiments, at least one R3 comprises at least one C atom. In some embodiments, at least one R3 comprises a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
In some embodiments, at least two R3 each independently comprise a substituent selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some such embodiments, at least one R3 comprises an aryl. In some such embodiments, at least one R3 is alkyl. In some embodiments, at least one R3 comprises aryl, and at least one R3 is alkyl.
In some embodiments, the ligand LA is selected from the group consisting of the structures of the following LIST 1:
wherein:
In some embodiments where ligand LA is selected from LIST 1, at least one of X5 to X20 in a structure is N. In some embodiments, exactly one of X5 to X20 in the bottom fused polycyclic system is N. In some such embodiments, exactly one of X9 to X12 in the bottom fused polycyclic system is N. In some such embodiments, exactly one of X13 to X16 in the bottom fused polycyclic system is N. In some such embodiments, exactly one of X1 to X20 in the bottom fused polycyclic system is N. In some embodiments, at least two of X5 to X20 in a structure are N. In some embodiments, one individual ring of a structure can contain one and only N. In some embodiments, one individual ring of a structure may contain up to 2 N atoms. In some embodiments, up to three of X1 to X20 can be N atoms in a structure. In some such embodiments, each N atom is in a separate and different ring. In some embodiments, X6 is carbon and RB attached to X6 is selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof. In some embodiments, X6 is carbon and RB attached to X6 is an alkyl, cycloalkyl, or silyl group. In some embodiments, X6 is carbon and RB attached to X6 is tertiary carbon. In some embodiments, X6 is carbon and RB attached to X6 is t-butyl, CH3, or CD3. In some embodiments, two RA are fused to form a ring or a fused ring system. In some such embodiments, the fused ring or the fused ring system may be benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, 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, benzimidazole derived carbene, aza-benzimidazole, aza-benzimidazole derived carbene, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanathrene, anthracene, aza-anthracene, phenanthridine, fluorene, or aza-fluorene. In some such embodiments, the fused ring or the fused ring system may be benzene or naphthalene. In some such embodiments, the fused ring may be benzene. In some such embodiments, the fused ring system may be naphthalene.
In some embodiments where ligand LA is selected from LIST 1, at least one RA, RB, or RC is selected from the group consisting of the General Substituents defined herein. In some embodiments, at least one RA is selected from the group consisting of the General Substituents defined herein. In some embodiments, at least one RB is selected from the group consisting of the General Substituents defined herein. In some embodiments, at least one RC is selected from the group consisting of the General Substituents defined herein.
In some embodiments where ligand LA is selected from LIST 1, at least one of R, R′, RA, RB, RC, or RN is partially or fully deuterated. In some embodiments, at least one RA is partially or fully deuterated. In some embodiments, at least one RB is partially or fully deuterated. In some embodiments, at least one RC is partially or fully deuterated. In some embodiments, at least one RN is partially or fully deuterated. In some embodiments, R or R′ if present is partially or fully deuterated.
In some embodiments where ligand LA is selected from LIST 1, at least one RA is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, at least one RA is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, at least one RA is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, at least one RA is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, at least one RA is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.
In some embodiments where ligand LA is selected from LIST 1, at least one RB is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, at least one RB is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, at least one RB is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, at least one RB is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, at least one RB is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.
In some embodiments where ligand LA is selected from LIST 1, at least one RC is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, at least one RC is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, at least one RC is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, at least one RC is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, at least one RC is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.
In some embodiments where ligand LA is selected from LIST 1, at least one RN is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, at least one RN is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, at least one RN is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, at least one RN is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, at least one RN is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.
In some embodiments where ligand LA is selected from LIST 1, at least one R or R′ is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, at least one R or R′ is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, at least one R or R′ is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, at least one R or R′ is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, at least one R or R′ is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.
In some embodiments, ligand LA is Selected from the group consisting of the structures of the following LIST 2:
wherein
In some embodiments, ligand LA is selected from the group consisting of the structures of the following LIST 2a:
wherein all the variables are the same as previously defined; and any two substituents may be optionally joined or fused to form a ring.
In some embodiments where ligand LA is selected from LIST 2 or LIST 2a, both X1 and X2 of the fused benzene ring of the benzimidazole in a structure are carbon, and two RA attached thereto respectively are fused to form a ring. Similarly, in some embodiments, both X2 and X3 of the fused benzene ring of the benzimidazole in a structure are carbon, and two RA attached thereto respectively are fused to form a ring. Likewise, in some embodiments, both X3 and X4 of the fused benzene ring of the benzimidazole in a structure are carbon, and two RA attached thereto respectively are fused to form a ring. In some such embodiments, the fused ring may be benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, or triazole. In some such embodiments, the fused ring may be benzene.
In some embodiments, the ligand LA is selected from the group consisting of the following structures (LIST 2b):
wherein each of X15 to X20 is independently C or N; and the remaining variables are the same as previously defined or as defined in this disclosure; and any two substituents may be optionally fused or joined to form a ring.
In some embodiments where ligand LA is selected from LIST 2, LIST 2a or LIST 2b, at least one RB is not H. In some embodiments, at least one RB is selected from the group consisting of the General Substituents defined herein. In some embodiments, at least one RB is selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof. In some embodiments, X6 is carbon and RB attached to X6 is selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof. In some embodiments, X6 is carbon and RBattached to X6 is an alkyl, cycloalkyl, or silyl group. In some embodiments, X6 is carbon and RB attached to X6 is tertiary carbon. In some embodiments, X6 is carbon and RB attached to X6 is t-butyl, CH3, or CD3. In some embodiments, at least one RC is not H. In some embodiments, at least one RC is selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof. In some embodiments, at least two RC is not H. In some embodiments, at least two RC are each independently selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof. In some embodiments, at least one RA is not H. In some embodiments, at least one RA is selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof. In some embodiments, at least two RA are not H. In some embodiments, at least two RA are each independently selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof. In some embodiments, two RA fused to form a ring. In some such embodiments, the fused ring may be benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, or triazole. In some such embodiments, the fused ring may be benzene. In some embodiments, only X12 is N. In some embodiments, only X9 is N. In some embodiments, RN is a substituted biphenyl. In some embodiments, RN is a carbocyclic substituted phenyl. In some embodiments, RNor RT is a heterocycle substituted phenyl.
In some embodiments where ligand LA is selected from LIST 2b, all the embodiments of RT can be equally applied to a structure of LIST 2a.
In some embodiments where ligand LA is selected from LIST 2 or LIST 2a or LIST 2b, at least one of X5 to X14 in a structure is N. In some embodiments, at least two of X5 to X14 in a structure are N. In some embodiments, one individual ring of a structure can contain one and only N. In some embodiments, one individual ring of a structure can contain up to 2 N atoms. In some embodiments, up to three of X1 to X14 can be N atoms in a structure. In some such embodiments, each N atom is in a separate and different ring.
In some embodiments where ligand LA is selected from LIST 2 or LIST 2a or LIST 2b, at least one RA, RB, or RC is selected from the group consisting of the General Substituents defined herein. In some embodiments, at least one RA is selected from the group consisting of the General Substituents defined herein. In some embodiments, at least one RB is selected from the group consisting of the General Substituents defined herein. In some embodiments, at least one RC is selected from the group consisting of the General Substituents defined herein.
In some embodiments where ligand LA is selected from LIST 2 or LIST 2a or LIST 2b, at least one of R, R′, RA, RB, RC, or RN is partially or fully deuterated. In some embodiments, at least one RA is partially or fully deuterated. In some embodiments, at least one RB is partially or fully deuterated. In some embodiments, at least one RC is partially or fully deuterated. In some embodiments, at least one RN is partially or fully deuterated. In some embodiments, R or R′ if present is partially or fully deuterated.
In some embodiments where ligand LA is selected from LIST 2 or LIST 2a or LIST 2b, at least one RA is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, at least one RA is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, at least one RA is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, at least one RA is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, at least one RA is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.
In some embodiments where ligand LA is selected from LIST 2 or LIST 2a or LIST 2b, at least one RB is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, at least one RB is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, at least one RB is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, at least one RB is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, at least one RB is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.
In some embodiments where ligand LA is selected from LIST 2 or LIST 2a or LIST 2b, at least one RC is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, at least one RC is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, at least one RC is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, at least one RC is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, at least one RC is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.
In some embodiments where ligand LA is selected from LIST 2 or LIST 2a or LIST 2b, at least one RN is or comprises an electron-withdrawing group from the EWG1 LIST as defined herein. In some embodiments, at least one RN is or comprises an electron-withdrawing group from the EWG2 LIST as defined herein. In some embodiments, at least one RN is or comprises an electron-withdrawing group from the EWG3 LIST as defined herein. In some embodiments, at least one RN is or comprises an electron-withdrawing group from the EWG4 LIST as defined herein. In some embodiments, at least one RN is or comprises an electron-withdrawing group from the Pi-EWG LIST as defined herein.
In some embodiments, ligand LA is selected from the group consisting of the structures of the following LIST 2c:
wherein X1 to X6 are each independently C or N; each of RA, RB, RC, and RD independently represents mono to the maximum allowable substitutions, or no substitutions; each RA, RB, RC, and RD is independently hydrogen or a substituent selected from the group consisting of the General Substituents defined herein; the remaining variables are the same; and at least one of X1 to X6 is N; and any two substituents may be optionally joined or fused to form a ring.
In some embodiments where ligand LA is selected from LIST 2c, at least one RA, RB, RC, or RD is selected from the group consisting of the General Substituents defined herein. In some embodiments, at least one RA is selected from the group consisting of the General Substituents defined herein. In some embodiments, at least one RB is selected from the group consisting of the General Substituents defined herein. In some embodiments, at least one RC is selected from the group consisting of the General Substituents defined herein. In some embodiments, at least one RD is selected from the group consisting of the General Substituents defined herein. In some embodiments, at least two of X1 to X6 are N.
In some embodiments, the ligand LA is selected from the group consisting of the following structures (LIST 2d):
wherein all the variables are the same as previously defined; and any two substituents may be optionally joined or use to form a ring.
In some embodiments where ligand LA is selected from LIST 2c or LIST 2d, at least one RB is not H. In some embodiments, at least one RB is selected from the group consisting of the General Substituents defined herein. In some embodiments, at least one RBis selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof. In some embodiments, at least one RA is not H. In some embodiments, at least one RA is selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof. In some embodiments, at least two RAare not H. In some embodiments, at least two RA are each independently selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof. In some embodiments, two RA fused to form a ring. In some such embodiments, the fused ring may be benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, imidazole derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, or triazole. In some such embodiments, the fused ring may be benzene. In some embodiments, only X1 is N. In some embodiments, only X2 is N. In some embodiments, only X3 is N. In some embodiments, X6 is carbon and RB attached to X6 is selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, silyl, aryl, heteroaryl, nitrile, and combinations thereof. In some embodiments, X6 is carbon and RB attached to X6 is an alkyl, cycloalkyl, or silyl group. In some embodiments, X6 is carbon and RB attached to X6 is tertiary carbon. In some embodiments, X6 is carbon and RBattached to X6 is t-butyl, CH3, or CD3. In some embodiments, at least one RD is a substituted or unsubstituted phenyl moiety. In some embodiments, at least one RD is a substituted or unsubstituted heteroaryl moiety.
In some embodiments, the ligand LA is selected from LAi, wherein i is an integer from 1 to 582, and each of LA1 to LA582 is defined in the following LIST 3:
In some embodiments, the ligand LA is selected from the group consisting of LAi′-(Rm)(Rn)(Ro)(Rp)(Rq), wherein i′ is an integer from 1 to 111, each of Rm, Rn, Ro, Rp, and Rq is independently selected from the group consisting of R1 to R130; wherein each of LA1(R1)(R1)(R1) (R1)(R1) to LA111 (R130)(R130)(R130)(R130)(R130) is defined in the following LIST 3a:
In some embodiments, the ligand LA is selected from the group consisting of LABg-(Rl)(Rm)(Rn)(Ro)(Rp)(Rq), wherein g is an integer from 1 to 103, each of Rl, Rm, Rn, Ro, Rp, and Rq is independently selected from the group consisting of R1 to R130; wherein each of LAB1(Rl)(Rl)(Rl)(Rl)(RI) to LAB103 (R130)(R130)(R130)(R130)(R130) is defined in the following LIST 3b:
In some embodiments, the ligand LA is selected from the group consisting of LACg′-(Rl′)(Rm′)(Rn′)(Ro′)(Rp′)(Rq′), wherein g′ is an integer from 1 to 13, each of Rl′, Rm′, Rn′, Ro′, and Rp′, and Rq′ is independently selected from the group consisting of R1 to R130; Rq′ is selected from E1 to E125 as defined herein, wherein each of LAC1-(R1)(R1)(R1)(R1)(R1)(E1) to LAC13-(R130)(R130)(R130)(R130)(R130)(E125) is defined in the following LIST 3c:
This application is a continuation-in-part of U.S. patent application Ser. No. 18/814,301, filed on Aug. 23, 2024, and Ser. No. 18/814,295, filed on Aug. 23, 2024, the entire contents of both applications are incorporated herein by reference. This application also claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Applications No. 63/664,204, filed on Jun. 26, 2024, No. 63/562,444, filed on Mar. 7, 2024, No. 63/620,548, filed on Jan. 12, 2024, No. 63/625,704, filed on Jan. 26, 2024, and No. 63/614,955, filed on Dec. 27, 2023, the entire contents of all the above referenced applications are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 63625704 | Jan 2024 | US | |
| 63620548 | Jan 2024 | US | |
| 63562444 | Mar 2024 | US | |
| 63664204 | Jun 2024 | US | |
| 63614955 | Dec 2023 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 18814301 | Aug 2024 | US |
| Child | 18985526 | US | |
| Parent | 18814295 | Aug 2024 | US |
| Child | 18985526 | US |
