Patent Application
20230083954
The present disclosure generally relates to organometallic compounds and formulations and their various uses including as hosts and 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 of Formula I:
wherein X1-X8 are each independently C or N; the maximum number of N atoms that can connect to each other within a ring is two; Y is selected from the group consisting of O, S, Se, NR, CRR′, BR, and SiRR′; RA and RB each independently represents zero, mono, or up to the maximum allowed number of substitutions to its associated ring; each of R1, R2, RA, and RB is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and any two adjacent R1, R2, RA, and RB can be joined or fused to form a ring, with the proviso that one of the following conditions is true: (1) at least one of X1-X8 forms a direct bond to a boron atom; (2) at least one of R1 and R2 comprises at least one boron atom; or (3) two atoms from Formula I are coordinated to a metal to form a metal complex.
In another aspect, the present disclosure provides a formulation of a compound of Formula I as described herein.
In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a compound 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 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, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group 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, selenyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.
In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, boryl, aryl, heteroaryl, sulfanyl, and combinations thereof.
In yet other instances, the more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
The terms “substituted” and “substitution” refer to a substituent other than H that is bonded to the relevant position, e.g., a carbon or nitrogen. For example, when R1 represents mono-substitution, then one R1 must be other than H (i.e., a substitution). Similarly, when R1 represents di-substitution, then two of R1 must be other than H. Similarly, when R1 represents 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 instance, a pair of adjacent substituents can be optionally joined or fused into a ring. The preferred ring is a five, six, or seven-membered carbocyclic or heterocyclic ring, includes both instances where the portion of the ring formed by the pair of substituents is saturated and where the portion of the ring formed by the pair of substituents is unsaturated. As used herein, “adjacent” means that the two substituents involved can be on the same ring next to each other, or on two neighboring rings having the two closest available substitutable positions, such as 2, 2′ positions in abiphenyl, 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 of Formula I:
wherein:
X1-X8 are each independently C or N;
the maximum number of N atoms that can connect to each other within a ring is two;
Y is selected from the group consisting of O, S, Se, NR, CRR′, BR, and SiRR′;
RA and RB each independently represent zero, mono, or up to the maximum allowed number of substitutions to its associated ring;
each of R, R′, R1, R2, RA, and RB is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and
any two adjacent R1, R2, RA, and RB can be joined or fused to form a ring, with the proviso that one of the following conditions is true:
(1) at least one of X1-X8 forms a direct bond to a boron atom;
(2) at least one of R1 and R2 comprises at least one boron atom; or
(3) two atoms from Formula I are coordinated to a metal to form a metal complex.
In some embodiments, each of R1, R2, RA, and RB can be independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.
In some embodiments, Y can be O. In some embodiments, Y can be NR. In these embodiments, R can be joined with one of RA or RB to form a ring. In these embodiments, the ring can be a 5-membered or 6-membered ring.
In some embodiments, R1 and R2 can be the same. In some embodiments, R1 and R2 can be different. In some embodiments, R1 and R2 can be each aryl. In some embodiments, R1 and R2 can be each independently benzene, pyridine, pyrimidine, triazine, carbazole, triphenylene, indolocarbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene.
In some embodiments, one of X1-X4 can be N. In some embodiments, X2 can be N, and X1, X3-X8 can be C. In some embodiments, X4 can be N, and X1-X3, and X5-X8 can be C. In some embodiments, one of X5-X8 can be N. In some embodiments, two of X1-X8 can be N. In some embodiments, one of X1-X4 can be N, and one of X5-X8 can be N. In some embodiments, two of X1-X4 can be N. In some embodiments, X2 and X4 can be N, and X1, X3, and X5-X8 can be C. In some embodiments, two of X5-X8 can be N.
In some embodiments, X2 can form a direct bond to the boron atom of BRB1RB2RB3 group, wherein each of RB1, RB2, and RB3 has the same definition of R1 for Formula I. In some embodiments, X4 can form a direct bond to the boron atom of BRB1RB2RB3 group. In some embodiments, X2 can form a direct bond to the boron atom of a first BRB1RB2RB3 group, and X4 can form a direct bond with the boron atom of a second BRB1RB2RB3 group. In some embodiments, X1-X8 can be each C, and X2 can form a direct bond to the boron atom of BRB1RB2RB3 group. In some embodiments, X2 can be N. In some embodiments, X4 can be N. In some embodiments, one of RB1, RB2, or RB3 of BRB1RB2RB3 and one of RA substituent can be joined to form a ring fused to ring B.
In some embodiments, two adjacent RA substituents can be joined to form a ring fused to ring A. In some embodiments, two adjacent RB substituents can be joined to form a ring fused to ring B.
In some embodiments, R1 can be a boron substituted aryl. In some embodiments, the boron atom of R1 can be joined with R2 to form a ring. In some embodiments, the boron atom of R1 can be joined with an aryl R2 to form a ring.
In some embodiments, the compound can be selected from the group consisting of the structures in the following LIST 1:
wherein each of X9-X18 is independently C or N; RD and RE each independently represent zero, mono, or up to the maximum allowed number of substitutions to its associated ring; each of R3-R6, R1, and RE is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; the remaining variables are the same as previously defined; and any two adjacent R1-R6, RA, RB, RD, and RE can be joined to form a ring.
In some embodiments, the compound can be selected from the group consisting of the structures in the following LIST 2:
wherein Yi, Yj, Yk, and Yl are each independently selected from the group consisting of N—Rg, B—Rg, O, S, Se, and CMe2; and Rg, Rm, Rn, Ro, Rp, Rq, and Rr are each independently defined as follows:
In some embodiments, the compound can be selected from the group consisting of the structures in the following LIST 3:
In some embodiments, the compound can form a part of a ligand LA of
wherein:
moiety C and D are each independently a monocyclic or polycyclic ring structure comprising 5-membered and/or 6-membered carbocyclic or heterocyclic rings;
moieties G and H are each independently a monocyclic or polycyclic ring structure respectively fused to the existing ring system;
Z1-Z8 are each independently C or N, with at least one of Z1, Z2, and Z3 being C;
any one of X1-X4 that connects to ring C is a carbon atom;
Z4 is N when Z5 is C; Z4 is C when Z5 is N;
L is a direct bond or a linker;
RC, RG, and RH each represents zero, mono, or up to the maximum allowed number of substitutions to its associated ring;
each of RC, RG, and RH is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and
any two adjacent R, R′, R1, R2, RA, RB, RC, RG, and RH can be joined or fused to form a ring,
wherein the ligand LA is coordinated through the two indicated dash lines to a metal M to form a 5-membered chelate ring;
wherein M is selected from the group consisting of Os, Ir, Pd, Pt, Cu, Ag, and Au;
wherein M can be coordinated to other ligands; and
wherein the ligand LA can be joined with other ligands to form a tridentate, tetradentate, pentadentate, or hexadentate ligand.
In some embodiments, R, R′, RA, RB, and RC can be each independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, O, S, SO, SO2, and combinations thereof.
In some embodiments, L is a direct bond. In some embodiments, L is a linker selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combination thereof.
In some embodiments, Y can be O, S, or NR. In these embodiments, R can be joined with one of RA or RB to form a ring.
In some embodiments, X1-X4 can be each C. In some embodiments, X5-X8 can be each C. In some embodiments, X1-X8 can be each C. In some embodiments, one of X1-X8 can be N. In some embodiments, one of X1-X4 can be N. In some embodiments, one of X5-X8 can be N. In some embodiments, X1-X4 can be each C, and one of X5-X8 can be N. In some embodiments, two of X1-X8 can be N. In some embodiments, one of X1-X4 can be N, and one of X5-X8 can be N.
In some embodiments, Z2 can be N, and Z1 and Z3 can be C. In some embodiments, Z2 can be C, and Z1 and Z3 can be N. In some embodiments, Z1 can be attached to X4, and M can be attached to X3. In some embodiments, Z1 can be attached to X3, and M can be attached to X2. In some embodiments, Z1 can be attached to X2, and M can be attached to X3.
In some embodiments, ring C can be a 6-membered aromatic ring. In some embodiments, ring C can be selected from the group consisting of pyridine, pyrimidine, pyridazine, and triazine. In some embodiments, ring C can be a 5-membered aromatic ring. In some embodiments, ring C can be selected from the group consisting of imidazole, pyrazole, oxazole, thiazole, triazole, and N-heterocyclic carbene.
In some embodiments, R1 and R2 can be the same. In some embodiments, R1 and R2 can be different. In some embodiments, R1 and R2 can be each independently alkyl, cycloalkyl, aryl, heteroaryl, or combinations thereof. In some embodiments, R1 and R2 can be each independently C1-C12 alkyl, C3-C8 cycloalkyl, benzene, pyridine, pyrimidine, pyridazine, pyrazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, or thiazole.
In some embodiments, two adjacent RA substituents can be joined to form a fused ring. In some embodiments, two adjacent RB substituents can be joined to form a fused ring. In some embodiments, R1 and R2 can be joined to form a ring.
In some embodiments, M can be Ir or Pt.
In some embodiments, the ligand LA can be selected from the group consisting of the structures in the following LIST 3a:
wherein ring
is selected from the group consisting of:
wherein X9-X18 are each independently C or N; R3, R4, R5, R6, and R7 each independently represent zero, mono, or up to the maximum allowed number of substitutions to its associated ring; each of R3, R4, R5, R6, R7, and RN is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and Q is C(R)2, BR, or Si(R)2; R and the remaining variables are the same as previously defined.
In some embodiments, the ligand LA can be selected from the group consisting of:
wherein ring
is selected from the group consisting of:
wherein Q is C(R)2, BR, or Si(R)2; R and the remaining variables are the same as previously defined.
In some embodiments, the ligand LA can be selected from the group consisting of the structures in the following LIST 4, wherein l, m, n, o, p, q, and r are each independently an integer from 1 to 134, k is an integer from 1 to 36, j is an integer from 1 to 36, and z is an integer from 1 to 63:
wherein R1 to R134 have the following structures:
wherein Y1 to Y36 have the following structures:
In some embodiments, the compound can have 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 can have 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, the compound can have a formula of Pt(LA)(LB); and wherein LA and LB can be same or different. In some embodiments, LA and LB can be connected to form a tetradentate ligand.
In some embodiments, LB and LC can be each independently selected from the group consisting of:
wherein:
each of Y1 to Y13 is independently selected from the group consisting of carbon and nitrogen;
Y′ is selected from the group consisting of BRe, NRe, PRe, O, S, Se, C═O, S═O, SO2, CReRf, SiReRf, and GeReRf;
Re and Rf can be fused or joined to form a ring;
each Ra, Rb, Rc, and Rd independently represent zero, mono, or up to the maximum allowed number of substitutions to its associated ring;
each of Ra1, Rb1, Rc1, Rd1, Ra, Rb, Rc, Rd, Re and Rf is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and two adjacent Ra, Rb, Rc, and Rd can be fused or joined to form a ring or form a multidentate ligand.
In some embodiments, LB and LC can be each independently selected from the group consisting of the following structures (LIST 5):
wherein:
Ra′, Rb′, and Rc′ each independently represent zero, mono, or up to the maximum allowed number of substitutions to its associated ring;
each of Ra1, Rb1, Rc1, RB, RN, Ra′, Rb′, and Rc′ is independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and two adjacent Ra′, Rb′, and Rc′ can be fused or joined to form a ring or form a multidentate ligand.
In some embodiments, the compound can be selected from the group consisting of Ir(LA)3, Ir(LA)(LBk)2, Ir(LA)2(LBk), Ir(LA)2(LCj-I), Ir(LA)2(LCj-II), Ir(LA) (LBk) (LCj-I), and Ir(LA) (LBk) (LCj-II),
wherein LA is selected from the structures defined herein;
wherein k is an integer from 1 to 560, and each LBk of LB1 to LB560 is defined below in LIST 6:
wherein each LCj-I has a structure based on formula
and
each LCj-II has a structure based on formula
wherein for each LCj in LCj-I and LCj-II, R201 and R202 are each independently defined in the following LIST 7:
wherein RD1 to RD246 have the following structures:
In some embodiments, the compound can have the formula Ir(LA)(LBk)2 or Ir(LA)2(LBk), wherein LB is selected from the group consisting of LB1 through LB560 with general numbering formula LBk (k is an integer from 1 to 560):
In some embodiments, LB is selected from the group consisting of:
In some embodiments, LB is selected from the group consisting of:
In some embodiments, the compound can have the formula Ir(LA)2(LCj-I) or Ir(LA)2(LCj-II), wherein for ligands LCj-I and LCj-II, the compound comprises only those LCj-I and LCj-II ligands whose corresponding R201 and R202 are defined to be one the following structures:
In some embodiments, the compound can have the formula Ir(LA)2(LCj-I) or Ir(LA)2(LCj-II), wherein for ligands LCj-I and LCj-II, the compound comprises only those LCj-I and LCj-II ligands whose the corresponding R201 and R202 are defined to be one of the following structures:
In some embodiments, the compound can have the formula Ir(LA)2(LCj-I), and the compound consists of only one of the following structures for the LCj-I ligand:
In some embodiments, the compound can be selected from the group consisting of the following structures in LIST 8:
In some embodiments, the compound can have a structure of
wherein:
moiety W is selected from the group consisting of Formula IIA, Formula IIB, Formula IIC, Formula IID, Formula IIE, Formula IIF, Formula IIG, and Formula IIH;
moieties F and E are each independently a monocyclic or polycyclic ring structure comprising a 5-membered and/or 6-membered carbocyclic or heterocyclic rings;
Z9 and Z10 are each independently C or N;
K1, K2, K3, and K4 are each independently selected from the group consisting of a direct bond, O, and S, wherein at least two of them are direct bonds;
L1, L2, and L3 are each independently selected from the group consisting of a single bond, absent a bond, O, S, SO, SO2, C═O, C═CR′R″, CR′R″, SiR′R″, BR′, and NR′, wherein at least one of L1 and L2 is present; X20-X22 are each independently C or N;
RF and RE each independently represent zero, mono, or up to the maximum allowed number of substitutions to its associated ring;
each of R′, R″, RF, and RE is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof;
the remaining variables are all the same as previously defined; and
any two adjacent groups can be joined or fused together to form a ring where chemically feasible.
In some embodiments, moiety F and moiety E can be both 6-membered aromatic rings. In some embodiments, moiety F can be a 5-membered or 6-membered heteroaromatic ring.
In some embodiments, Z9 can be N and Z10 can be C. In some embodiments, Z9 can be C and Z10 can be N.
In some embodiments, L1 can be O or CR′R″. In some embodiments, L2 can be a direct bond. In some embodiments, L2 can be NR′.
In some embodiments, one of K1, K2, K3, or K4 can be O. In some embodiments, one of K1, or K2 can be O. In some embodiments, one of K3, or K4 can be O. In some embodiments, K1 and K2 can be both direct bonds. In some embodiments, K1, K2, K3, and K4 can be all direct bonds.
In some embodiments, X20-X22 can be all C.
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 following structures (LIST 9a):
wherein each RE, RF, RG, RH, RO, RP, RQ, and RX is independently selected from the list consisting of:
wherein Ly is selected from the group consisting of the structures shown below (LIST 9):
wherein each RF, RF, RX, and RY is independently selected from the list consisting of:
wherein R, RE, RF, and RG each represents zero, mono, or up to the maximum allowed number of substitutions to its associated ring; each R1, R2, R3, R4, R, RE, RF and RG is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and two adjacent R1, R2, R3, R4, R, RE, RF and RG can be joined or fused to form a ring wherever chemically feasible.
In some embodiments, the compound can be selected from the group consisting of the compounds having the formula of Pt(LA′)(Ly), wherein LA′ is selected from the following table wherein l, m, n, o, p, q, and r are each independently an integer from 1 to 134, k is an integer from 1 to 36, j is an integer from 1 to 36, and z is an integer from 1 to 63 (LIST 10):
wherein Rl, Rm, Rn, Ro, Rp, Rq, Rr, Yj, Yk, and Lz are the same as previously defined; and wherein Ly is selected from the group consisting of the structures shown below (LIST 11):
wherein s, t, u, o, p, and q, are each independently an integer from 1 to 70, and
wherein R1 to R70 have the following structures:
In some embodiments, the compound can be selected from the group consisting of the following structures (LIST 12):
In some embodiments, the compound of Formula I described herein can be at least 30% denterated, at least 40% deuterated, at least 50% denterated, at least 60% denterated, at least 70% denterated, 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 or deuterium) that are replaced by deuterium atoms.
In another aspect, the present disclosure also provides an OLED device comprising an organic layer that contains a compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the organic layer may comprise a compound of Formula I:
wherein X1-X8 are each independently C or N; the maximum number of N atoms that can connect to each other within a ring is two; Y is selected from the group consisting of O, S, Se, NR, CRR′, BR, and SiRR′; RA and RB each independently represent zero, mono, or up to the maximum allowed number of substitutions to its associated ring; each of R1, R2, RA, and RB is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and any two adjacent R1, R2, RA, and RB can be joined or fused to form a ring, with the proviso that one of the following conditions is true: (1) at least one of X1-X8 forms a direct bond to a boron atom; (2) at least one of R1 and R2 comprises at least one boron atom; or (3) two atoms from Formula I are coordinated to a metal to form a metal complex.
In some embodiments, the compound may be a host, and the organic layer may be an emissive layer that comprises a phosphorescent emitter.
In some embodiments, the phosphorescent emitter may be a transition metal complex having at least one ligand or part of the ligand if the ligand is more than bidentate selected from the group consisting of:
wherein:
T is selected from the group consisting of B, Al, Ga, and In;
each of Y1 to Y13 is independently selected from the group consisting of carbon and nitrogen;
Y′ is selected from the group consisting of BRe, NRe, PRe, O, S, Se, C═O, S═O, SO2, CReRf, SiReRf, and GeReRf;
Re and Rf can be fused or joined to form a ring;
each Ra, Rb, Rc, and Rd independently represent zero, mono, or up to the maximum allowed number of substitutions to its associated ring;
each of Ra1, Rb1, Rc1, Rd1, Ra, Rb, Rc, Rd, Re and Rf is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and
and any two adjacent substituents of Ra, Rb, Rc, Rd, Re and Rf can be fused or joined to form a ring or form a multidentate ligand.
In some embodiments, the compound may be an acceptor, and the OLED may further comprise a sensitizer selected from the group consisting of a delayed fluorescence emitter, a phosphorescent emitter, and combination thereof.
In some embodiments, the compound may be a fluorescent emitter, a delayed fluorescence emitter, or a component of an exciplex that is a fluorescent emitter or a delayed fluorescence emitter.
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 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—CH2n+1, C≡CCnH2n+1, Ar1, Ar1-Ar2, CnH2n+1, or no substitution, wherein n is 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 may further comprise a host, wherein host comprises at least one chemical moiety selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene,
In some embodiments, the host may be selected from the 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 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 may comprise a compound of Formula I:
wherein X1-X8 are each independently C or N; the maximum number of N atoms that can connect to each other within a ring is two; Y is selected from the group consisting of O, S, Se, NR, CRR′, BR, and SiRR′; RA and RB each independently represent zero, mono, or up to the maximum allowed number of substitutions to its associated ring; each of R1, R2, RA, and RB is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and any two adjacent R1, R2, RA, and RB can be joined or fused to form a ring, with the proviso that one of the following conditions is true: (1) at least one of X1-X8 forms a direct bond to a boron atom; (2) at least one of R1 and R2 comprises at least one boron atom; or (3) two atoms from Formula I are coordinated to a metal to form a metal complex.
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 interventing 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 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 of Formula I:
wherein X1-X8 are each independently C or N; the maximum number of N atoms that can connect to each other within a ring is two; Y is selected from the group consisting of O, S, Se, NR, CRR′, BR, and SiRR′; RA and RB each independently represent zero, mono, or up to the maximum allowed number of substitutions to its associated ring; each of R1, R2, RA, and RB is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and any two adjacent R1, R2, RA, and RB can be joined or fused to form a ring, with the proviso that one of the following conditions is true: (1) at least one of X1-X8 forms a direct bond to a boron atom; (2) at least one of R1 and R2 comprises at least one boron atom; or (3) two atoms from Formula I are coordinated to a metal to form a metal complex.
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. 5,1344,363, 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. 5,1344,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
The simple layered structure illustrated in
Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in
Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and organic vapor jet printing (OVJP). Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons 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, EP26134932, 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.
HIL/HTL examples can be found in paragraphs [0111] through [0117] of Universal Display Corporation's US application publication number US2020/0,295,281A1, and the contents of these paragraphs and the whole publication are herein incorporated by reference in their entireties.
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.
Hosts examples can be found in paragraphs [0119] through [0125] of Universal Display Corporation's US application publication number US2020/0,295,281A1, and the contents of these paragraphs and the whole publication are herein incorporated by reference in their entireties.
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 in paragraphs [0126] through [0127] of Universal Display Corporation's US application publication number US2020/0,295,281A1, and the contents of these paragraphs and the whole publication are herein incorporated by reference in their entireties.
A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.
In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
In another aspect, compound used in HBL contains at least one of the following groups in the molecule:
wherein k is an integer from 1 to 20; L101 is another ligand, k′ is an integer from 1 to 3.
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 in paragraphs [0131] through [0134] of Universal Display Corporation's US application publication number US2020/0,295,281A1, and the contents of these paragraphs and the whole publication are herein incorporated by reference in their entireties.
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 ar. It is understood that various theories as to why the invention works are not intended to be limiting.
Diphenylborinic Acid
Phenylmagnesium bromide (1 M in THF) (100 ml, 100 mmol) was added dropwise to a solution of triisopropyl borate (11 ml, 47.4 mmol) in dry THF (100 ml) under nitrogen at −70° C. (internal temperature) over a period of circa 10 minutes. On completion of the addition the mixture was allowed to warm to ambient temperature overnight before partitioning with 1N HCl (300 ml) and TBME (300 ml). The organic layer was separated, dried (MgSO4), filtered and the solvent evaporated. The crude was purified by column chromatography to give diphenylborinic acid (6.5 g, 33.9 mmol, 71.6%) as a colourless gum which crystallised on standing.
Potassium Diphenyldifluoroborate
Diphenylborinic acid (8 g, 43.9 mmol) was dissolved in acetonitrile (200 ml), followed by addition of a 12 mL aqueous solution of potassium fluoride (7.66 g, 132 mmol). A 40 mL THF solution of (2R,3R)-2,3-dihydroxysuccinic acid (8.57 g, 57.1 mmol) was then added dropwise while stirring rapidly. After 5 days, the mixture was subjected to vacuum filtration and the precipitate washed twice with MeCN. The combined filtrates were concentrated by rotary evaporation (at no higher than 30° C.) and the solids were dried overnight under high vacuum. The solids were triturated with diethyl ether, collected by suction filtration, and dried in a vacuum oven to afford potassium diphenyldifluoroborate (10.59 g, 99.5%) as a colorless semicrystalline solid.
nBuLi, (2.5 M in hexanes, 56 mL, 140 mmol) was added over 5 minutes to a solution of TMEDA (21 mL, 140 mmol) and diphenyl ether (8.0 g, 47 mmol) in THF (100 mL) at −78° C. The mixture was stirred at room temperature (RT) for 3 hours, then cooled to −78° C. Trimethyl borate (16 mL, 140 mmol) was added over a 1 minute period, then the mixture was stirred at RT for 17 hours, diluted with sat. NH4Cl(aq) (300 mL) and extracted with EtOAc (3×150 mL). The combined organic phases were washed with brine (100 mL), dried over Na2SO4, filtered and concentrated to give an off-white solid. The material was stirred in MeOH (300 mL) at room temperature, water (100 mL) was added and the mixture was stirred at RT for 1 hour. The solid was collected by filtration, rinsed with 3:1 MeOH/water (50 mL) then with isohexane (30 mL) and dried under vacuum to give 10H-dibenzo[b,e][1,4]oxaborinin-10-ol (4.0 g, 20 mmol, 43% yield) as a colorless solid.
A solution of potassium fluoride (5.2 g, 89 mmol) in water (9 mL) was added to a solution of 10H-dibenzo[b,e][1,4]oxaborinin-10-ol (5.8 g, 30 mmol) in MeCN (145 mL) and THF (45 mL). A solution of L-(+)-tartaric acid (5.8 g, 39 mmol) in THF (40 mL) was added and the mixture was stirred at RT for 3 days. The solid was removed by filtration, rinsed with MeCN (2×70 mL), and the combined filtrate was concentrated at 30° C. to give a colorless solid. This material was suspended in 2:3 THF:isohexane (60 mL) and stirred at RT for 16 hours. The solid was collected by filtration, rinsed with 1:2 THF:isohexane (30 mL) then isohexane (20 mL) and dried under vacuum to give potassium 10,10-difluoro-10H-dibenzo[b,e][1,4]oxaborinin-10-uide (4.55 g, 17.4 mmol, 59% yield) as a colourless solid.
Potassium carbonate (71.5 g, 518 mmol) was added to a mixture of resorcinol (19.0 g, 173 mmol) and 2-fluropyridine (67.0 g, 690 mmol) in dry DMF (198 mL). The mixture was sparged with nitrogen for 20 minutes then heated at reflux for 20 hours. The reaction mixture was cooled to RT, diluted with water (800 mL) and extracted with dichloromethane (2×600 mL). The combined organic layers were dried over sodium sulfate (30 g), filtered and concentrated under reduced pressure. The yellow residue was loaded onto Celite (diatomaceous earth) and purified by column chromatography to give 1,3-bis(pyridin-2-yloxy)benzene (32 g, 70% yield) as a white solid.
1,3-bis(pyridin-2-yloxy)benzene (10.5 g, 39.7 mmol) was added to a suspension of potassium 10,10-difluoro-10H-dibenzo[b,e][1,4]oxaborinin-10-uide (24.4 g, 95 mmol) in dry m-xylene (210 mL) and the mixture was sparged with nitrogen for 15 minutes. Tetrachlorosilane (11.0 mL, 95.0 mmol) and Hunig's base (49.8 mL, 286 mmol) were added at room temperature and the reaction was heated 155° C. for 3 days. After cooling to room temperature, the reaction mixture was diluted with dichloromethane (1 L) and water (500 mL). The layers were separated and the aqueous layer was extracted with dichloromethane (500 mL). The combined organic layers were concentrated, the resultant solid was filtered, then dissolved in hot THF and passed through a pad of silica gel which was washed with excess THF, triturated in hot THF and filtered to give Compound H1 (3.0 g, 12% yield) as a white solid.
A 40 mL reaction vial containing 1,3-bis(pyridin-2-yloxy)benzene (0.50 g, 1.89 mmol) and potassium difluorodiphenylborate (1.1 g, 4.54 mmol) was charged with m-xylene (12.0 mL), perchlorosilane (0.52 mL, 4.54 mmol) and N,N-diisopropylethylamine (2.4 mL, 13.62 mmol) inside a glove box. The vial was sealed with a screw cap and taken out of the glovebox. The reaction mixture was heated at 145° C. The crude product was diluted with dichloromethane (5 mL), loaded onto Celite and purified by column chromatography to obtain Compound H2 (90 mg, 8% yield) as a white solid.
A pre-dried 4-necked 500 mL flask was charged with 1,3-bis(pyridin-2-yloxy)benzene (8.0 g, 30.3 mmol) and 2,2′-bis(trifluoro-14-boraneyl)-1,1′-biphenyl, dipotassium salt (26.6 g, 72.6 mmol) followed by m-xylene (160 mL) and the flask was purged with nitrogen for 15 minutes. Perchlorosilane (6.95 ml, 60.5 mmol) and N,N-diisopropylethylamine (38.0 ml, 218 mmol) were added at RT. The reaction mixture was then heated at 150° C. The reaction mixture was diluted with dichloromethane, filtered and concentrated under reduced pressure. The mixture was purified by column chromatography to give an off-white solid. Dichloromethane was added to form a suspension which was sonicated and filtered to give Compound H3 (3.87 g, 21% yield) as an off-white solid.
A suspension of (6-chloropyridin-3-yl)boronic acid (26 g, 170 mmol), Pd(dppf)Cl2.CH2Cl2 (6.0 g, 7.4 mmol) and potassium phosphate (50 g, 240 mmol) in toluene (250 mL) was charged with 2-bromopyridine (20 mL, 210 mmol). The reaction mixture was stirred at 100° C. (block temp) for 1 hour. The mixture was cooled to RT, diluted with EtOAc (250 mL), washed with 1:1 brine/water (500 mL, then 250 mL) and brine (250 mL), dried over MgSO4, filtered and concentrated. Purification by column chromatography gave 6′-chloro-2,3′-bipyridine (26 g, 130 mmol, 78%) as a pale pink solid.
A suspension of 6′-chloro-2,3′-bipyridine (1) (7.0 g, 37 mmol), 2-iodophenol (12 g, 55 mmol) and cesium carbonate (25 g, 77 mmol) in NMP (60 mL) was stirred at 140° C. for 24 hours. The mixture was cooled to RT, diluted with EtOAc (200 mL), washed with 1:1 water/brine (2×200 mL) and brine (100 mL), dried over MgSO4, filtered and concentrated. Purification by column chromatography gave 6′-(2-iodophenoxy)-2,3′-bipyridine (9.6 g, 24 mmol, 66%) as a white solid.
A 1.0 L three neck flask was charged with potassium carbonate (2 M, 124 ml, 248 mmol, 1.33 eq), (2-chloropyridin-3-yl)boronic acid (30.0 g, 187 mmol, 1 eq), tetrahydrofuran (934 ml), and Pd(PPh3)4 (8.48 g, 7.19 mmol, 0.0385 eq) and the mixture was sparged with nitrogen for 10 minutes. Then added 2-bromopyridine (45.2 g, 280 mmol, 1.5 eq) and sparged with nitrogen for 10 minutes. Then the reaction mixture was stirred at 80° C. (internal) for 50 hours. It was cooled to RT, diluted with ethyl acetate (630 ml), 10% aq. brine (150 ml), and added ˜10 g of Celite. Stirred for 30 minutes, filtered through a Celite plug, that was washed with ethyl acetate (3×50 ml). Separated the organic layer, the aqueous layer was extracted with ethyl acetate (3×150 ml). The combined organic layers were dried over Na2SO4, filtered and the solvent was removed under the reduced pressure to give the crude product (57.2 g). The crude product was chromatographed on a silica gel to give 2′-chloro-2,3′bipyridine (18 g, 51%).
In a 1.0 L round bottom flask a suspension of 2′-chloro-2,3′bipyridine (25.0 g, 126 mmol, 1 eq), 2-iodophenol (45.2 g, 201 mmol, 1.6 eq) and cesium carbonate (79 g, 239 mmol) in anhydrous N-Methyl-2-pyrrolidinone (210 ml) was prepared, the headspace was flushed with nitrogen. Then it was stirred at 140° C. for 24 hours. Cooled the reaction mixture to RT, diluted with ethyl acetate (215 ml), filtered through celite plug, that was washed with ethyl acetate (3×150 ml). To the combined organic layers was added 10% brine (300 ml), separated the organic layer, the aqueous layer was extracted with ethyl acetate (3×550 ml). The combined organics were washed with 10% aq. brine (350 ml), dried over Na2SO4, filtered and the solvent was removed under reduced pressure to give the crude product which was purified by chromatography to afford 2′-(2-iodophenoxy)-2,3′-bipyridine as a colorless solid (37.1 g, 75.7%).
To a solution of 6′-(2-iodophenoxy)-2,3′-bipyridine (9.6 g, 25.7 mmol) in THF (100 mL) at −70° C. in a dry ice/acetone bath was added isopropylmagnesium(II) chloride, lithium chloride complex (1.3 M in THF) (25 mL, 32.5 mmol) dropwise over ca 8 min. The mixture was stirred in the cryogenic bath for 45 min (temperature reached −73° C.). diethyl(methoxy)borane (1 M in THF) (35 mL, 35.0 mmol) was added over ca 10. The reaction was removed from the cryogenic bath and stirred for 2 hours. The reaction mixture was diluted with EtOAc (300 mL), washed with sat. NH4Cl(aq) (300 mL) and brine (20 mL), dried over MgSO4, filtered and concentrated. The crude was suspended in PhMe (50 mL), briefly sonicated, and the solid was removed by filtration. The filtrate was concentrated and purification by flash column chromatography to afford 6,6-diethyl-3-(pyridin-2-yl)-6H-514,614-benzo[e]pyrido[2,1-b][1,3,4]oxazaborinine (6.9 g, 21.38 mmol, 83% yield) as a white solid.
2′-(2-iodophenoxy)-2,3′-bipyridine (4.2 g, 11.22 mmol) charged to a schlenk flask and dissolved in 50 mL THF followed by cooling to −78° C. Isopropylmagnesium(II) lithium chloride (5.80 ml, 11.60 mmol) soln added dropwise, and the yellow soln stirred @−78 deg for 30 min. During this time, lithium chloride (0.710 g, 16.75 mmol) was charged to a separate shlenk tube and heated in vacuo with heat gun for ˜ 5 min followed by cooling to RT. difluorodiphenyl-14-borane, potassium salt (3.2 g, 13.22 mmol) was added followed by 50 mL THF, and the slurry was stirred at RT for 30 minutes followed by addition to the anion (still at −78° C.) via cannula. The mixture was warmed to RT and stirred for 1 hour, followed by quenching with sat aq. NH4Cl and extraction with DCM 3×. Organics were combined, dried over Na2SO4 and solvent was removed by rotary evaporation to afford white solids, which were purified by column chromatography to afford 6,6-diphenyl-1-(pyridin-2-yl)-6H-514,614-benzo[e]pyrido[2,1-b][1,3,4]oxazaborinine (3.00 g, 64.8%) as a colorless semicrystalline solid after drying on high vacuum.
6′-(2-iodophenoxy)-2,3′-bipyridine (5.00 g, 13.36 mmol) charged to a Schlenk flask and dissolved in 50 mL THF followed by cooling to −78° C. Isopropylmagnesium(II) lithium chloride (10.5 ml, 13.65 mmol) solution was added dropwise by syringe and the solution stirred at −78° C. for 30 min. During this time, a separate Schlenk flask was charged wit lithium chloride (1.00 g, 23.59 mmol) and heated with a heat gun in vacuo for 5 minutes followed by cooling to RT. 10,10-difluoro-10H-1014-dibenzo[b,e][1,4]oxaborinine, potassium salt (4.20 g, 16.40 mmol) was then added followed by 50 mLTHF and the resulting slurry was rapidly stirred at RT for 30 min then transferred via a cannula to the anion solution (still at −78° C.). Upon complete addition of the BF2K/LiCl mixture, the cooling bath was removed and the mixture was stirred at RT for 16 hours. The reaction was quenched with sat. aq. NH4Cl and extracted with DCM 3×. Organics were combined, dried over Na2SO4, and concentrated to afford a residue that was purified by column chromatography to afford 3-(pyridin-2-yl)-514,614-spiro[benzo[e]pyrido[2,1-b][1,3,4]oxazaborinine-6,10′-dibenzo[b,e][1,4]oxaborinine] (1.24 g, 21.8%) as colorless solids.
3-(pyridin-2-yl)-514,614-spiro[benzo[e]pyrido[2,1-b][1,3,4]oxazaborinine-6,10′-dibenzo[b,e][1,4]oxaborinine](546 mg, 1.282 mmol) charged to a Schlenk flask followed by 10 mL chlorobenzene and the heterogenous mixture sparged with N2 for 15 min before the addition of solid [Ir(COD)Cl]2 (205 mg, 0.305 mmol). The mixture was sparged with N2 for 5 minutes and placed in an oil bath at 120° C. for 16 hours. The mixture was then cooled to RT and 40 mL ether was added. The yellow precipitate was collected by suction filtration and washed with ether 3 times followed by drying in a vacuum oven to afford the desired iridium dimer (643 mg, 98%) as a yellow solid.
Iridium dimer (101 mg, 0.048 mmol), (2,2,2-trifluoroacetoxy)silver (32.4 mg, 0.147 mmol), and 3-(pyridin-2-yl)benzonitrile (18.20 mg, 0.101 mmol) charged to a Schlenk tube followed by 2 mL dioxane. The mixture was sparged with N2 for 15 minutes followed by heating to 100° C. for 16 hours. The reaction was cooled to RT and quenched with sat. aq. NaHCO3 followed by extraction with DCM 3 times. Organics were combined, dried over Na2SO4, and passed through a silica plug to afford pale yellow solids after removal of solvent. The solids were dissolved in 15 mL THF and sparged with N2 for 15 minutes followed by irradiation with 350 nm UV for 24 hours. Solvent was removed by rotary evaporation and the residue was purified by column chromatography to afford the desired iridium complex (37 mg, 32.2%) as a pale yellow solid.
(2,2,2-trifluoroacetoxy)silver (481 mg, 2.179 mmol), 3-(pyridin-2-yl)-514,614-spiro[benzo[e]pyrido[2,1-b][1,3,4]oxazaborinine-6,10′-dibenzo[b,e][1,4]oxaborinine] (678 mg, 1.643 mmol), and Dichlorotetrakis(2-(2-pyridinyl)phenyl)diiridium(III) (766 mg, 0.714 mmol) were charged to Schlenk tube followed by 12 mL dioxane. The mixture was sparged with N2 for 10 mm followed heating to 100° C. for 24 hours. The reaction was cooled to RT and quenched with sat. aq. NaHCO3 followed by extraction with DCM 3 times. Organics were combined, dried over Na2SO4, and passed through a silica plug to afford yellow solids after removal of solvent. The solids were dissolved in 30 mL THF and sparged with N2 for 15 minutes followed by irradiation with 350 nm UV for 24 hours. Solvent was removed by rotary evaporation and the residue was purified by column chromatography to afford the desired iridium complex (211 mg, 16.2%) as a yellow solid.
Freshly ground potassium carbonate (40 g, 289 mmol) was added to a solution of 2-iodophenol (20 g, 91 mmol) and 5-chloro-2,3-difluoropyridine (15 ml, 145 mmol) in acetonitrile (400 ml) and the mixture refluxed for 10 hours. The reaction was cooled, filtered and the solvent evaporated. The crude was purified by chromatography to give 5-chloro-3-fluoro-2-(2-iodophenoxy)pyridine (32 g, 90 mmol, 99% yield) as a colourless oil.
5-chloro-3-fluoro-2-(2-iodophenoxy)pyridine (7 g, 20.03 mmol) was added to a suspension of 9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-ol (5.8 g, 18.33 mmol) and cesium carbonate (15 g, 46.0 mmol) in NMP (100 ml) and the reaction heated at 138° C. for 1 hour. The solid was filtered off and the filtrate was partitioned with 20% w/w NaCl solution (500 ml) and TBME (250 ml). The organic was separated and preabsorbed onto silica (15 g) for purification by chromatography then triturated with n-heptane to give 9-(4-(tert-butyl)pyridin-2-yl)-2-((5-chloro-2-(2-iodophenoxy)pyridin-3-yl)oxy)-9H-carbazole (9 g, 13.38 mmol, 73.0% yield) as a colorless glass.
Potassium difluorodiphenylborate (3.75 g, 15.49 mmol) was dissolved in lithium chloride (0.5 M in THF) (35 ml, 17.50 mmol) in a dry flask under nitrogen. In a separate flask iPrMgCl.LiCl (1.3 M in THF) (12 ml, 15.60 mmol) was added dropwise to a solution of 9-(4-(tert-butyl)pyridin-2-yl)-2-((5-chloro-2-(2-iodophenoxy)pyridin-3-yl)oxy)-9H-carbazole (7.5 g, 11.61 mmol) in dry tetrahydrofuran (100 ml) under nitrogen at −10° C. (internal temperature) over 20 minutes maintaining the temperature below −5° C. Both mixtures were stirred at their respective temperatures for 30 minute, then the lithium chloride/potassium difluorodiphenylborate suspension was added dropwise to the solution at −10° C., maintaining the temperature below −5° C. over 10 minutes. On completion of the addition the reaction was allowed to warm to RT overnight then partitioned with sat. NH4Cl (200 ml) and TBME (200 ml). The organic layer was separated, dried (MgSO4), filtered and the solvent evaporated. The crude was purified by chromatography to give 1-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-3-chloro-6,6-diphenyl-6H-514,614-benzo[e]pyrido[2,1-b][1,3,4]oxazaborinine (5.6 g, 8.10 mmol, 69.8% yield) as a colourless glass.
Inside a 40 mL amber vial, aryl chloride (217 mg), diamine (100 mg), and cesium carbonate (470 mg) were mixed with dried toluene (3 mL) at RT. The reaction mixture was sparged under nitrogen and stirred for 20 minutes. In a separate 20 mL vial, Pd2(dba)3 (13 mg) and X-Phos (28 mg) were flushed with nitrogen for 10 minutes, and mixed with dried toluene (3 mL). The catalyst mixture was sparged under nitrogen for 15 minutes and stirred at room temperature. The pre-mixed, sparged catalyst mixture (purple solution) was added into the sparged reaction mixture of reactants, and then heated to 80° C. for 17 hours. The reaction mixture was cooled to RT, and then filtered through a pad of Celite (12 g). The Celite pad was rinsed with dichloromethane (50 mL). The collected filtrate was concentrated to give a crude foam, which was purified by column chromatography to afford the desired diamine (330 mg, 81.1%) as a brown foam.
Inside a 20 mL vial, the diamine (134 mg) was dissolved in 1.9 mL acetonitrile and sparged under nitrogen for 15 minutes. To the sparged reaction solution was added Vilsmeier Reagent (138 mg) and the reaction mixture was stirred at RT for 2 hours. Triethylamine (0.150 mL) was then added and the reaction mixture was then stirred at 70° C. for 70 hours. The reaction mixture was cooled to RT and concentrated under reduced pressure to give crude solids, which were purified by column chromatography to afford the desired benzimidazolium salt (84.3 mg, 38.6%) as a red-brown foam.
Inside a 40 mL amber vial, ligand (160 mg), potassium tetrachloroplatinate (64 mg), and 1,2-dichlorobenzene (6.16 mL) were mixed and then sparged under argon for 40 minutes. To the sparged reaction mixture was added 2,6-lutidine (0.066 mL). The reaction mixture was heated at 160° C. with a pre-heated heating mentle for 17 hours. The reaction mixture was cooled to RT and then concentrated under reduced pressure to give a brown oil, which was purified by column chromatography to afford the desired platinum complex (70 mg, 36.0%) as a yellow solid.
The structures of the compounds listed in Table 1 are shown below:
b) Preparation of Exemplary Devices of the Present Disclosure
OLEDs were grown on a glass substrate pre-coated with an indium-tin-oxide (ITO) layer having a sheet resistance of 15-Q/sq. Prior to any organic layer deposition or coating, the substrate was degreased with solvents and then treated with an oxygen plasma for 1.5 minutes with 50 W at 100 mTorr and with UV ozone for 5 minutes. 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. Doping percentages are in volume percent.
The devices in Table 2 were fabricated in high vacuum (<10−6 Torr) by thermal evaporation. The anode electrode was 750 Å of indium tin oxide (ITO). The device example had organic layers consisting of, sequentially, from the ITO surface, 100 Å thick Compound 1 (HIL), 250 Å layer of Compound 2 (HTL), 50 Å of Compound 3 (EBL), 300 Å of Compound 3 doped with 50% Compound 4 and 12% of emitter compound (EML), 50 Å of Compound 4 (BL), 300 Å of Compound 5 doped with 35% Compound 6, 10 Å of Compound 5 followed by 1,000 Å of Al (Cathode).
As the data in Table 2 shows, the inventive iridium compounds exhibited superior electroluminescent efficiencies compared to Comparative Compound 1 in an OLED device, and these observed differences are beyond any value that could be attributed to experimental error and the observed improvement is significant. Furthermore, these desirable electroluminescent properties can be concomitant with up to 34 nm of blue shift in λmax, making the inventive compounds more suited to display applications targeting a more saturated deep blue color point.
This application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 63/112,103, filed on Nov. 10, 2020, and to U.S. Provisional Application No. 63/167,371, filed on Mar. 29, 2021, the entire contents of both applications are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 63112103 | Nov 2020 | US | |
| 63167371 | Mar 2021 | US |
