Patent Application
20220310944
The present disclosure generally relates to organometallic compounds and formulations and their various uses including as emitters in devices such as organic light emitting diodes and related electronic devices.
Opto-electronic devices that make use of organic materials are becoming increasingly desirable for various reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials.
OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting.
One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Alternatively, the OLED can be designed to emit white light. In conventional liquid crystal displays emission from a white backlight is filtered using absorption filters to produce red, green and blue emission. The same technique can also be used with OLEDs. The white OLED can be either a single emissive layer (EML) device or a stack structure. Color may be measured using CIE coordinates, which are well known to the art.
In one aspect, the present disclosure provides a compound comprising a ligand LA of Formula I
wherein:
wherein the ligand LA is coordinated to a metal M through the indicated dashed lines;
wherein M is selected from the group consisting of Ir, Pt, and Pd, and 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, with the proviso that when M is Pt or Pd and YB is a direct bond and A is a 6-membered carbocyclic or heterocyclic ring, then R1 comprises at least two aromatic rings, each of which is not directly fused to the other aromatic ring.
In another aspect, the present disclosure provides a formulation of the compound of the present disclosure.
In yet another aspect, the present disclosure provides an OLED having an organic layer comprising the compound of the present disclosure.
In yet another aspect, the present disclosure provides a consumer product comprising an OLED with an organic layer comprising the compound of the present disclosure.
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, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, selenyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, boryl, and combinations thereof.
In some instances, the more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, boryl, aryl, heteroaryl, sulfanyl, and combinations thereof.
In yet other instances, the most preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
The terms “substituted” and “substitution” refer to a substituent other than H that is bonded to the relevant position, e.g., a carbon or nitrogen. For example, when R1 represents mono-substitution, then one 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[fh]quinoxaline and dibenzo[fh]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.
As used herein, “deuterium” refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400, Patent Pub. No. WO 2006/095951, and U.S. Pat. Application Pub. No. US 2011/0037057, which are hereby incorporated by reference in their entireties, describe the making of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan, et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65, which are incorporated by reference in their entireties, describe the deuteration of the methylene hydrogens in benzyl amines and efficient pathways to replace aromatic ring hydrogens with deuterium, respectively.
It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.
In some instance, a pair of adjacent substituents can be optionally joined or fused into a ring. The preferred ring is a five, six, or seven-membered carbocyclic or heterocyclic ring, includes both instances where the portion of the ring formed by the pair of substituents is saturated and where the portion of the ring formed by the pair of substituents is unsaturated. As used herein, “adjacent” means that the two substituents involved can be on the same ring next to each other, or on two neighboring rings having the two closest available substitutable positions, such as 2, 2′ positions in a biphenyl, or 1, 8 position in a naphthalene, as long as they can form a stable fused ring system.
In one aspect, the present disclosure provides a compound comprising a ligand LA of
Formula I
wherein:
wherein the ligand LA is coordinated to a metal M through the indicated dashed lines;
wherein M is selected from the group consisting of Ir, Pt, and Pd, and 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, with the proviso that when M is Pt or Pd and YB is a direct bond and A is a 6-membered carbocyclic or heterocyclic ring, then R1 comprises at least two aromatic rings, each of which is not directly fused to the other aromatic ring.
It should be understood that a structure of Formula I is also contemplated to cover the following structure of Formula IA
since the shown YA and YB and the corresponding parts of Formula I can be rotated 180 degree, and then fused to form Formula IA where the definitions of all of the variables are the same as in Formula I.
In some embodiments of the compound, each of R, R′, R1, RA, and RB is independently a hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein.
In some embodiments of the compound, M is Pt. In some embodiments of the compound, M can be Ir.
In some embodiments of the compound, the moiety A is a 6-membered carbocyclic ring. In some embodiments, the moiety A is a 6-membered heterocyclic ring. In some embodiments, the moiety A can be a monocyclic 6-membered aromatic ring, while YB is not a direct bond. In some embodiments, the moiety A can be a monocyclic 6-membered aromatic ring, while YB is selected from the group consisting of BR, BRR′, NR, PR, P(O)R, O, S, Se, C═O, C═S, C═Se, C═NR, C═CRR′, S═O, SO2, C═R, CRR′, SiRR′, and GeRR′. In some embodiments, the moiety A is a 6-membered heterocyclic ring with at least one ring atom being N. In some embodiments, the moiety A is a 5-membered heterocyclic ring. In some embodiments, the moiety A can be a 5-membered heterocyclic ring with YB being a direct bond. In some embodiments, the moiety A is a polycyclic ring structure. In some embodiments, the moiety A can be a polycyclic ring structure comprising at least one 5-membered heterocyclic ring. In some embodiments, the moiety A is a benzimidazole.
In some embodiments, moiety A can be a 5-membered ring when YB is a direct bond. In some embodiments, moiety A can be a polycyclic ring structure when YB is a direct bond. In some embodiments, the metal M may not be Pd or Pt when YB is a direct bond and moiety A is a 6-membered ring. In some embodiments, when YB is a direct bond and moiety A is a 6-membered carbocyclic or heterocyclic ring, then R1 comprises at least two aromatic rings, each of which is not directly fused to the other aromatic ring. In some embodiments, when YB is a direct bond and moiety A is a 6-membered carbocyclic or heterocyclic ring, then R1 comprises at least two aromatic rings, each of which may be partially or fully deuterated or fluorinated. In some embodiments, when YB is a direct bond and moiety A is a 6-membered carbocyclic or heterocyclic ring, then R1 comprises at least one group which is partially or fully deuterated or fluorinated. In some embodiments, when YB is a direct bond and moiety A is a 6-membered carbocyclic or heterocyclic ring, then Formula I may be partially or fully deuterated or fluorinated.
In some embodiments, when YB is a direct bond and moiety A is a 6-membered carbocyclic or heterocyclic ring, then moiety A may be partially or fully deuterated or fluorinated. In some embodiments, when YB is a direct bond and moiety A is a 6-membered carbocyclic or heterocyclic ring, then at least one RA may comprise a partially or fully deuterated or fluorinated group. In some embodiments, Formula I comprises a 5 or more fused polycyclic ring structure when YB is a direct bond.
In some embodiments of the compound, X1—X4 are C. In some embodiments, X1—X9 are C. In some embodiments, one of X1—X8 is N. In some embodiments, one of X1—X4 is N. In some embodiments, one of X5—X8 is N.
In some embodiments of the compound, R1 is an alkyl, cycloalkyl, aryl heteroaryl, or combinations thereof. In some embodiments, R1 is at least one ortho-substituted aryl or heteroaryl. In some embodiments, R1 is both ortho-substituted aryl or heteroaryl. In some embodiments, R1 comprises a chemical group containing at least three 6-membered aromatic rings that are not fused next to each other. In some embodiments, R1 is selected from the group consisting of 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, cyclopentyl, cyclohexyl, phenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diisopropylphenyl, biphenyl, terphenyl, and combinations thereof; and wherein each group is optionally partially or fully deuterated. In some embodiments, R1 may be fully or partially deuterated.
In some embodiments of the compound, R1 is terphenyl. In some embodiments, R1 is phenyl.
In some embodiments of the compound, YA or YB is O. In some embodiments, one of YA and YB is 0 and the other is BR. In some embodiments, one of YA is O and YB is a direct bond. In some embodiments, one of YA and YB is NR and the other is BR. In some embodiments, YA and YB are each NR.
In some embodiments of the compound, M is Ir. In some embodiments of the compound where M is Ir, RB represents zero substitution. In some embodiments of the compound, YA or YB is O.
In some embodiments of the compound where M is Ir, YA is O and YB is a direct bond.
In any of the embodiments of the compound, two RA can be joined to form a ring.
In any of the embodiments of the compound, two RB are joined to form a ring.
In some embodiments of the compound, wherein the ligand LA is selected from the group consisting of:
X1-X12 are each independently C or N;
YC is selected from the group consisting of BR, BRR′, N, NR, PR, P(O)R, O, S, Se, C═O, C═S, C═Se, C═NR, C═CRR′, S═O, SO2, C═R, CRR′, SiRR′, and GeRR′;
In some embodiments of the compound, the ligand LA is selected from the group consisting of the structures in the following LIST 1:
where YA and YB are selected from O, S, CMe2, SiMe2, CPh2, SiPh2, N—R, and B—R;
where R1, R2, R3, and R are each independently selected from the group consisting of:
In some embodiments of the compound, the ligand LA is selected from the group consisting of the structures in the following LIST 2:
wherein R1 to R70 for Ri, Rj, and Rk are defined as:
In some embodiments of the compound, the ligand LA is selected from the group consisting of the structures in the following LIST 3:
In some embodiments of the compound, the compound has a formula M(LA)p(LB)q(LC)r, where 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 of the compound having the formula M(LA)p(LB)q(LC)r, the compound has a formula selected from the group consisting of Ir(LA)3, Ir(LA)(LB)2, Ir(LA)2(LB), Ir(LA)2(LC), and Ir(LA)(LB)(LC); and wherein LA, LB, and LC are different from each other.
In some embodiments of the compound having the formula M(LA)p(LB)q(LC)r, LB is a substituted or unsubstituted phenylpyridine, and LC is a substituted or unsubstituted acetylacetonate.
In some embodiments of the compound having the formula M(LA)p(LB)q(LC)r, the compound has a formula of Pt(LA)(LB); and LA and LB can be same or different. In some embodiments, LA and LB are connected to form a tetradentate ligand.
In some embodiments of the compound having the formula M(LA)p(LB)q(LC)r, LB and LC are each independently 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, BReRf, NRe, PRe, P(O)Re, O, S, Se, C═O, C═S, C═Se, C═NRe, C═CReRf, 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 represents zero, mono, or up to a 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
any two adjacent Ra, Rb, Rc, Rd, Re and Rf can be fused or joined to form a ring or form a multidentate ligand.
In some embodiments of the compound having formula M(LA)p(LB)q(LC)r, LB and LC are each independently selected from the group consisting of:
wherein:
Ra′, Rb′, and Rc′ each independently represents zero, mono, or up to a maximum allowed substitution to its associated ring;
each of Ra1, Rb1, Rc1, Ra, Rb, Rc, Rd, Re, Rf, Rg, 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 of the compound having formula M(LA)p(LB)q(LC)r, when the compound has formula Ir(LAx-(i)(j)(k))3, wherein x is an integer from 1 to 30, i, j, and k are each independently an integer from 1 to 70, and the compound is selected from the group consisting of Ir(LA1-(1)(1)(1))3 to Ir(LA30-(70)(70)(70))3;
when the compound has formula Ir(LAx-(i),)(k))(LBm)2, wherein x is an integer from 1 to 30, i, j, and k are each independently an integer from 1 to 70, m is an integer from 1 to 554, and the compound is selected from the group consisting of Ir(LA1-(1)(1)(1))(LB1)2 to Ir(LA30-(70)(70)(70))(LB554)2;
when the compound has formula Ir(LAx-(i)(j)(k))2(LBm), wherein x is an integer from 1 to 30, i, j, and k are each independently an integer from 1 to 70, m is an integer from 1 to 554, and the compound is selected from the group consisting of Ir(LA1-(1)(1)(1))2(LB1) to Ir(LA30-(70)(70)(70))2(LB554);
when the compound has formula Ir(LAx-(i)(j)(k))2(LCn-I), wherein x is an integer from 1 to 30, i, j, and k are each independently an integer from 1 to 70, n is an integer from 1 to 1416, and the compound is selected from the group consisting of Ir(LA1-(1)(1)(1))2(LCI-I) to Ir(LA30-(70)(70)(70))2(LC1416-I); and
when the compound has formula Ir(LAx-(i)(j)(k))2(LCn-II), wherein x is an integer fro 1 to 30, i, j, and k are each independently an integer from 1 to 70, n is an integer from 1 to 1416, and the compound is selected from the group consisting of Ir(LA1-(1)(1)(1))2(LC1-II) to Ir(LA30-(70)(70)(70))2(LC1416-II);
wherein LB1 to LB554 for LBm have the structures defined in the following LIST 4:
wherein each LCn-I has a structure based on formula
and
each LCn-II has a structure based on formula
wherein for each LCn in LCn-I and LCn-II, R201 and R202 are each independently defined as provided in the following LIST 5:
wherein RD1 to RD246 have the following structures:
In some embodiments of the compound having formula M(LA)p(LB)q(LC)r, the compound has the formula Ir(LAx-(i)(j)(k))(LBm)2 or Ir(LAx-(i)(j)(k))2(LBm), wherein x is an integer from 1 to 30, i, j, and k are each independently an integer from 1 to 70, and m is an integer from 1 to 554, wherein the compound is selected from the group consisting of only those compounds whose LBm ligand corresponds to one of the following structures:
In some embodiments of the compound having formula M(LA)p(LB)q(LC)r, the compound has the formula Ir(LAx-(i)(j)(k))(LBm)2 or Ir(LAx-(i)(j)(k))2(LBm), wherein x is an integer from 1 to 30, i, j, and k are each independently an integer from 1 to 70, and m is an integer from 1 to 554, wherein the compound is selected from the group consisting of only those compounds whose LBm ligand corresponds to one of the following structures:
In some embodiments of the compound formula M(LA)p(LB)q(LC)r, the compound has the formula Ir(LAx-(i)(j)(k))2(LCn-I) or Ir(LAx-(i))(j)(k))2(LCn-II), wherein x is an integer from 1 to 30, i, j, and k are each independently an integer from 1 to 70, and n is an integer from 1 to 1416, wherein the compound is selected from the group consisting of only those compounds having LCn-I and LCn-II ligands whose corresponding R201 and R202 are defined to be one the following structures:
In some embodiments of the compound having formula M(LA)p(LB)q(LC)r, the compound has the formula Ir(LAx-(i)(j)(k))2(LCn-I) or Ir(LAx-(i)(j)(k))2(LCn-II), wherein the compound is selected from the group consisting of only those compounds having LCn-I and LCn-II ligands whose corresponding R201 and R202 are defined to be one the following structures:
In some embodiments of the compound having formula M(LA)p(LB)q(LC)r, the compound has the formula Ir(LAx-(i)(j)(k))2(LCn-I), and the compound is selected from the group consisting of only those compounds having one of the following structures for the LCn-I ligand:
In some embodiments of the compound having 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 LA, LB, and LC are different from each other, the compound is selected from the group consisting of the structures in the following LIST 6:
In some embodiments of the compound having 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); LA, LB, and LC are different from each other,
In some embodiments, the compound has a structure of
wherein:
M1 is Pd or Pt;
moieties E and F are each independently a monocyclic or polycyclic ring structure comprising 5-membered and/or 6-membered carbocyclic or heterocyclic rings;
Z1 and Z2 are each independently C or N;
K1 and K2 are each independently selected from the group consisting of a direct bond, O, and S, wherein at least one of K1 and K2 is a direct bond;
L1 and L2 are each independently selected from the group consisting of a single bond, absent a bond, O, Se, S, SO, SO2, C═O, C═CR″R′″, C═NR″, CR″R′″, SiR″R′″, BR″, P(O)R″, and NR″, wherein at least one of L1 and L2 is present;
X10-X11 are each independently C or N;
RE and RF each independently represents zero, mono, or up to a maximum allowed substitution to its associated ring;
each of R″, R′″, RE, and RF is independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and
any two substituents can be joined or fused together to form a ring where chemically feasible.
In some embodiments of the compound having Formula II, moiety E and moiety F are both 6-membered aromatic rings. In some embodiments, moiety F is a 5-membered or 6-membered heteroaromatic ring.
In some embodiments of the compound having Formula II, L1 is O or CR″R′″.
In some embodiments of the compound having Formula II, Z2 is N and Z1 is C. In some embodiments, Z2 is C and Z is N.
In some embodiments of the compound having Formula II, L2 is a direct bond. In some embodiments, L2 is NR″.
In some embodiments of the compound having Formula II, K1 and K2 are both direct bonds.
In some embodiments of the compound having Formula II, X10-X11 are all C.
In some embodiments of the compound having Formula II, the compound is selected from the group consisting of:
wherein:
Rx and Ry are each selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof; and
RG for each occurrence 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.
In some embodiments of the compound having 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 may have a structure of Formula III
wherein LA is selected from the group consisting of the structures in the following LIST 7:
wherein LB is selected from the group consisting of the structures in the following LIST 8:
wherein R1 to R70 for Ri, Rj, and Rk are defined as:
In some embodiments of the compound having the structure of Formula III, the ligand LA can be selected from the group consisting of the structures in the following LIST 9:
wherein YA and YB may each be independently selected from O, S, CMe2, SiMe2, CPh2, SiPh2, N—R, and B—R, wherein R1, R2, R3, and R are each independently selected from the group consisting of:
In some embodiments of the compound, the compound is selected from the group consisting of the structures in the following LIST 10:
In some embodiments, the compound having a ligand LA of Formula I described herein can be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, percent deuteration has its ordinary meaning and includes the percent of possible hydrogen atoms (e.g., positions that are hydrogen, deuterium, or halogen) that are replaced by deuterium atoms.
In another aspect, the present disclosure also provides an OLED device comprising a organic layer that contains a compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the first organic layer may comprise a compound comprising a ligand LA of
Formula I
wherein:
wherein the ligand LA is coordinated to a metal M through the indicated dashed lines;
wherein M is selected from the group consisting of Ir, Pt, and Pd, and 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, with the proviso that when M is Pt or Pd and YB is a direct bond and A is a 6-membered carbocyclic or heterocyclic ring, then R1 comprises at least two aromatic rings, each of which is not directly fused to the other aromatic ring.
In some embodiments of the OLED, the organic layer is an emissive layer and the compound can be an emissive dopant or a non-emissive dopant. In some embodiments of the OLED, the organic layer further comprises a host, wherein the host comprises a metal complex.
In some embodiments of the OLED, the compound is a sensitizer, and the OLED further comprises an acceptor selected from the group consisting of a fluorescent emitter, a delayed fluorescence emitter, and combination thereof.
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—CnH2n+1, C≡CCnH2n+1, Ar1, Ar1-Ar2, CnH2n—Ar1, 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 group selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5,2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, triazine, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5,2-benzo[d]benzo[4,5]imidazo[3,2-a]imidazole, and aza-(5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene).
In some embodiments, the host may be selected from the HOST Group consisting of:
and combinations thereof.
In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.
In some embodiments, the compound as described herein may be a sensitizer; wherein the device may further comprise an acceptor; and wherein the acceptor may be selected from the group consisting of fluorescent emitter, delayed fluorescence emitter, and combination thereof.
In yet another aspect, the OLED of the present disclosure may also comprise an emissive region containing a compound as disclosed in the above compounds section of the present disclosure.
In some embodiments, the emissive region can comprise a compound comprising a ligand LA of
Formula I
wherein:
wherein the ligand LA is coordinated to a metal M through the indicated dashed lines;
wherein M is selected from the group consisting of Ir, Pt, and Pd, and 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, with the proviso that when M is Pt or Pd and YB is a direct bond and A is a 6-membered carbocyclic or heterocyclic ring, then R1 comprises at least two aromatic rings, each of which is not directly fused to the other aromatic ring.
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 OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer can comprise the compound of Formula I as described herein.
In some embodiments, the consumer product can be one of a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign.
Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
The simple layered structure illustrated in
Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in
Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP, also referred to as organic vapor jet deposition (OVJD)), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and organic vapor jet printing (OVJP). Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons are a preferred range. Materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
Devices fabricated in accordance with embodiments of the present disclosure may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. A consumer product comprising an OLED that includes the compound of the present disclosure in the organic layer in the OLED is disclosed. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays (displays that are less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, a light therapy device, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present disclosure, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25° C.), but could be used outside this temperature range, for example, from −40 degree C. to +80° C.
More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.
The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
In some embodiments, the OLED has one or more characteristics selected from the group consisting of being flexible, being rollable, being foldable, being stretchable, and being curved. In some embodiments, the OLED is transparent or semi-transparent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.
In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED comprises a RGB pixel arrangement or white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a hand held device, or a wearable device. In some embodiments, the OLED is a display panel having less than 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a display panel having at least 10 inch diagonal or 50 square inch area. In some embodiments, the OLED is a lighting panel.
In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence; see, e.g., U.S. application Ser. No. 15/700,352, which is hereby incorporated by reference in its entirety), triplet-triplet annihilation, or combinations of these processes. In some embodiments, the emissive dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from others). When there are more than one ligand coordinated to a metal, the ligands can all be the same in some embodiments. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, every ligand can be different from each other. This is also true in embodiments where a ligand being coordinated to a metal can be linked with other ligands being coordinated to that metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligands. Thus, where the coordinating ligands are being linked together, all of the ligands can be the same in some embodiments, and at least one of the ligands being linked can be different from the other ligand(s) in some other embodiments.
In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED where one or multiple layers in the OLED contains an acceptor in the form of one or more fluorescent and/or delayed fluorescence emitters. In some embodiments, the compound can be used as one component of an exciplex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor and the acceptor will emit the energy or further transfer energy to a final emitter. The acceptor concentrations can range from 0.001% to 100%. The acceptor could be in either the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission can arise from any or all of the sensitizer, acceptor, and final emitter.
According to another aspect, a formulation comprising the compound described herein is also disclosed.
The OLED disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.
In yet another aspect of the present disclosure, a formulation that comprises the novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, electron blocking material, hole blocking material, and an electron transport material, disclosed herein.
The present disclosure encompasses any chemical structure comprising the novel compound of the present disclosure, or a monovalent or polyvalent variant thereof. In other words, the inventive compound, or a monovalent or polyvalent variant thereof, can be a part of a larger chemical structure. Such chemical structure can be selected from the group consisting of a monomer, a polymer, a macromolecule, and a supramolecule (also known as supermolecule). As used herein, a “monovalent variant of a compound” refers to a moiety that is identical to the compound except that one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a “polyvalent variant of a compound” refers to a moiety that is identical to the compound except that more than one hydrogen has been removed and replaced with a bond or bonds to the rest of the chemical structure. In the instance of a supramolecule, the inventive compound can also be incorporated into the supramolecule complex without covalent bonds.
The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.
Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.
A hole injecting/transporting material to be used in the present disclosure is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:
Each of Ar1 to Ar9 is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each Ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, Ar1 to Ar9 is independently selected from the group consisting of:
wherein k is an integer from 1 to 20; X101 to X108 is C (including CH) or N; Z101 is NAr1, O, or S; Ar1 has the same group defined above.
Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:
wherein Met is a metal, which can have an atomic weight greater than 40; (Y101-Y102) is a bidentate ligand, Y101 and Y102 are independently selected from C, N, O, P, and S; L101 is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
In one aspect, (Y101-Y102) is a 2-phenylpyridine derivative. In another aspect, (Y101-Y102) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc+/Fc couple less than about 0.6 V.
Non-limiting examples of the HIL and HTL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, U.S. Ser. No. 06/517,957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, U.S. Pat. Nos. 5,061,569, 5,639,914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018.
An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and/or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.
The light emitting layer of the organic EL device of the present disclosure preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied.
Examples of metal complexes used as host are preferred to have the following general formula:
wherein Met is a metal; (Y103-Y104) is a bidentate ligand, Y103 and Y104 are independently selected from C, N, O, P, and S; L101 is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
In one aspect, the metal complexes are:
wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.
In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y103-Y104) is a carbene ligand.
In one aspect, the host compound contains at least one of the following groups selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each option within each group may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, the host compound contains at least one of the following groups in the molecule:
wherein R101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. k is an integer from 0 to 20 or 1 to 20. X101 to X108 are independently selected from C (including CH) or N. Z101 and Z102 are independently selected from NR101, or S.
Non-limiting examples of the host materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, U.S. Pat. No. 7,154,114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, U.S. Pat. No. 9,466,803,
One or more additional emitter dopants may be used in conjunction with the compound of the present disclosure. Examples of the additional emitter dopants are not particularly limited, and any compounds may be used as long as the compounds are typically used as emitter materials. Examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
Non-limiting examples of the emitter materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, U.S. Ser. No. 06/699,599, U.S. Ser. No. 06/916,554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930, US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US20100244004, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US2014103305, U.S. Pat. Nos. 6,303,238, 6,413,656, 6,653,654, 6,670,645, 6,687,266, 6,835,469, 6,921,915, 7,279,704, 7,332,232, 7,378,162, 7,534,505, 7,675,228, 7,728,137, 7,740,957, 7,759,489, 7,951,947, 8,067,099, 8,592,586, 8,871,361, WO06081973, WO06121811, WO07018067, WO07108362, WO07115970, WO07115981, WO08035571, WO2002015645, WO2003040257, WO2005019373, WO2006056418, WO2008054584, WO2008078800, WO2008096609, WO2008101842, WO2009000673, WO2009050281, WO2009100991, WO2010028151, WO2010054731, WO2010086089, WO2010118029, WO2011044988, WO2011051404, WO2011107491, WO2012020327, WO2012163471, WO2013094620, WO2013107487, WO2013174471, WO2014007565, WO2014008982, WO2014023377, WO2014024131, WO2014031977, WO2014038456, WO2014112450.
A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.
In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
In another aspect, compound used in HBL contains at least one of the following groups in the molecule:
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 below together with references that disclose those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, U.S. Pat. Nos. 6,656,612, 8,415,031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,
In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.
In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. The minimum amount of hydrogen of the compound being deuterated is selected from the group consisting of 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99%, and 100%. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. may be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof.
It is understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.
Synthesis of Pt(LA4-(52)(1)(1))(LB31-(5)(1)(1))
Synthesis of 9-(4-tert-Butylpyridin-2-yl)-2-methoxy-9H-carbazole
Toluene (8.1 L) was sparged with nitrogen for 10 minutes. SPhos (33.4 g, 0.081 mol, 0.05 equiv) was added and the mixture was stirred until fully dissolved. Tris(dibenzylideneacetone)dipalladium(0) (37.2 g, 0.041 mol, 0.025 equiv) was added and the mixture was sparged with nitrogen for 5 minutes and stirred at room temperature for 1 hour. 2-chloro-4-tert-butylpyridne (317 g, 1.63 mol, 1.0 equiv), 2-methoxy-9H-carbazole (353 g, 1.79 mol, 1.1 equiv) and sodium tert-butoxide (328 g, 3.41 mol, 2.1 equiv) were sequentially added and the mixture was sparged with nitrogen for 5 minutes. After refluxing for 16 hours, the mixture was cooled to room temperature, poured into water (4.0 L), and the layers were separated. The aqueous layer was extracted with ethyl acetate (3×1.4 L). The combined organic layers were washed with saturated brine (1.0 L), dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by column chromatography on silica to give 9-(4-tert-Butylpyridin-2-yl)-2-methoxy-9H-carbazole (509 g, 95% yield) as an amber oil.
Synthesis of 9-(4-(tert-Butyl)pyridin-2-yl)-9H-carbazol-2-ol
A mixture of compound 9-(4-(tert-Butyl)pyridin-2-yl)-9H-carbazol-2-ol (34.8 g, 105 mmol, 1.0 equiv) and 48% hydrobromic acid (0.6 L) was heated at reflux under nitrogen for 2 hours. After cooling to room temperature, the mixture was poured into water (1.8 L) and extracted with dichloromethane (3×0.3 L). The combined organic layers were washed with saturated sodium bicarbonate (0.3 L) and saturated brine (0.3 L), dried over sodium sulfate, filtered and concentrated under reduced pressure to give 9-(4-(tert-Butyl)pyridin-2-yl)-9H-carbazol-2-ol (27.4 g, 82% yield) as a brown solid.
Synthesis of 2-(3-Bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole
A mixture of 9-(4-(tert-Butyl)pyridin-2-yl)-9H-carbazol-2-ol (39.9 g, 126 mmol, 1.0 equiv), potassium phosphate (54.0 g, 255 mmol, 2.0 equiv), copper (I) iodide (3.67 g, 19.3 mmol, 0.15 equiv) and picolinic acid (4.72 g, 38.4 mmol, 0.30 equiv) in DMSO (650 mL) was sparged nitrogen for 15 minutes. 1,3-Dibromobenzene (76 mL, 629 mmol, 5 equiv) was added and the mixture was sparged with nitrogen for another 5 minutes. After heating at 110° C. for 1.5 days, the mixture was cooled to room temperature and concentrated. The crude material was diluted with ethyl acetate (4 L) and saturated sodium bicarbonate (2 L). The layers were separated and the organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by column chromatography on silica to give 2-(3-Bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (41.28 g, 69% yield) as a white powder.
Synthesis of N2-([1,1′:3′,1″-Terphenyl]-2′-yl)-N3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)dibenzo[b,d]furan-2,3-diamine
A mixture of 2-(3-Bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (2.31 g, 4.90 mmol, 1.0 equiv) and N2-([1,1′:3′,1″-terphenyl]-2′-yl)dibenzo[b,d]furan-2,3-diamine in toluene (30 mL) was sparged with nitrogen for 45 minutes. In a second flask a mixture of di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl) phosphine (0.370 g, 1.05 mmol, 0.2 equiv) and allyl palladium chloride dimer (0.110 g, 0.30 mmol, 0.06 equiv) in toluene (30 mL) was sparged with nitrogen for 45 minutes. The contents of the first flask (reagents) were transferred to the second flask (catalyst) via syringe. Sodium tert-butoxide (1.01 g, 10.54 mmol, 2.2 equiv) was added and the mixture was heated at 110° C. for 1.5 hours. The mixture was cooled to room temperature and filtered through a Celite pad, which was rinsed with dichloromethane (3×75 mL). The filtrate was concentrated under reduced pressure to give crude N2-([1,1′:3′,1″-Terphenyl]-2′-yl)-N3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)dibenzo[b,d]furan-2,3-diamine (5.3 g) as a dark purple solid.
Synthesis of 1-([1,1′:3′,1″-Terphenyl]-2′-yl)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3H-benzo[2,3]benzofuro[5,6-d]imidazol-1-ium Chloride
A mixture of crude N2-([1,1′:3′,1″-Terphenyl]-2′-yl)-N3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)dibenzo[b,d]furan-2,3-diamine (3.98 g, 4.87 mmol, 1 equiv, assumes 100% yield in the previous step) in triethyl orthoformate (75 mL, 301 mmol, 38 equiv) was sparged with nitrogen for 10 minutes. Concentrated HCl (0.9 mL, 10.4 mmol, 2.1 equiv) was added and the mixture was heated at 90° C. for 2 hours. The mixture was cooled to room temperature and directly absorbed onto Celite (60 g). The crude product was purified by column chromatography on silica. The resulting solid was triturated with diethyl ether (500 mL) to give 1-([1,1′:3′,1″-Terphenyl]-2′-yl)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3H-benzo[2,3]benzofuro[5,6-d]imidazol-1-ium chloride (2.52 g, 59% yield over two steps) as a brown solid.
Synthesis of Pt(LA4-(52)(1)(1))(LB31-(5)(1)(1))
A mixture of 1-([1,1′:3′,1″-Terphenyl]-2′-yl)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3H-benzo[2,3]benzofuro[5,6-d]imidazol-1-ium chloride (1.89 g, 2.19 mmol, 1 equiv) in a solvent (50 mL) was sparged with nitrogen for 60 minutes. A platinum precursor (1.1 equiv) and a base (3 equiv) were added and the flask was wrapped with aluminum foil to prevent light exposure. After heating at reflux for 24 hours, the reaction mixture was cooled to room temperature and poured into water (500 mL). The aqueous mixture was extracted with dichloromethane (4×125 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by column chromatography to give Pt(LA4-(52)(1)(1))(LB31-(5)(1)(1)) (1.83 g, 77% yield) in four portions as a yellow solid.
Synthesis of Pt(LA4-(53)(1)(1))(LB31-(5)(1)(1))
Synthesis of N-(5-Bromo-4-fluoro-2-nitrophenyl)-[1,1′:3′,1″-terphenyl]-2,2″,3,3″,4,4″,5,5″,6,6″-d10-2′-amine
A mixture of compound [1,1′:3′,1″-terphenyl]-2,2″,3,3″,4,4″,5,5″,6,6″-d10-2′-amine (10.0 g, 39.2 mmol, 1.0 equiv) and compound 1-bromo-2,5-difluoro-4-nitrobenzene (12.1 g, 50.9 mmol, 1.3 equiv) in THF (392 mL) was sparged with nitrogen for 20 minutes and cooled to 0° C. 1 M Lithium bis(trimethylsilyl)amide in THF (98 mL, 98 mmol, 2.5 equiv) was added over 30 minutes. The reaction was stirred at room temperature for 3 hours. The reaction was quenched with saturated ammonium chloride (500 mL) and diluted water (150 mL). The mixture was extracted with dichloromethane (2×1.0 L). The combined organic layer was washed with saturated brine (1.0 L), dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by column chromatography on silica to give N-(5-Bromo-4-fluoro-2-nitrophenyl)-[1,1′:3′,1″-terphenyl]-2,2″,3,3″,4,4″,5,5″,6,6″-d10-2′-amine (13.6 g, 71% yield) as an orange solid.
Synthesis of 5′-(([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)amino)-2′-fluoro-4′-nitro-[1,1′-biphenyl]-2-ol
A mixture of compound N-(5-Bromo-4-fluoro-2-nitrophenyl)-[1,1′:3′,1″-terphenyl]-2,2″,3,3″,4,4″,5,5″,6,6″-d10-2′-amine (13.6 g, 28.9 mmol, 1.0 equiv), (2-hydroxyphenyl)boronic acid (4.38 g, 31.7 mmol, 1.1 equiv), and potassium carbonate (9.97 g, 72.1 mmol, 2.5 equiv) in dioxane (579 mL) and water (382 mL) was sparged with nitrogen for 30 minutes. Tetrakis(triphenylphosphine)palladium(0) (1.00 g, 0.866 mmol, 0.03 equiv) was added and the reaction was heated at 100° C. under nitrogen for 24 hours. The reaction was diluted with water (500 mL) and ethyl acetate (1.0 L). The layers were separated aqueous phase was separated and the aqueous layer was extracted with ethyl acetate (3×300 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by column chromatography on silica to give 5′-(([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)amino)-2′-fluoro-4′-nitro-[1,1′-biphenyl]-2-ol (11.9 g, 83% yield) as a red solid.
Synthesis of N-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-nitrodibenzo[b,d]furan-2-amine
A mixture of compound 5′-(([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)amino)-2′-fluoro-4′-nitro-[1,1′-biphenyl]-2-ol (10.5 g, 21.6 mmol, 1.0 equiv) and potassium carbonate (8.95 g, 64.7 mmol, 3.0 equiv) in N-methyl-2-pyrrolidinone (216 ml) was sparged with nitrogen for 30 minutes. The reaction was heated at 120° C. for 16 hours. The reaction was cooled to room temperature. Saturated ammonium chloride (50 mL) and water (50 mL) were added to give a slurry which was filtered. The solid was rinsed with water (3×50 mL) and dried under vacuum at room temperature for 3 hours. The solid was dissolved in dichloromethane (50 mL) and concentrated under reduced pressure. The crude material was purified by column on silica to give N-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-nitrodibenzo[b,d]furan-2-amine (8.68 g, 85% yield) as a red solid.
Synthesis of N2-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)dibenzo[b,d]furan-2,3-diamine
A mixture of compound N-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-nitrodibenzo[b,d]furan-2-amine (4.0 g, 8.57 mmol, 1.0 equiv) and 10 palladium on carbon (0.91 g, 0.43 mmol, 0.05 equiv, 50% wet) in ethyl acetate (107 mL) was hydrogenated at 40 psi for 4 hours. The reaction mixture was purged with nitrogen. The solid was filtered through Celite pad, which was washed with ethyl acetate (5×25 mL) under nitrogen. The filtrate was concentrated under reduced pressure to give N2-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)dibenzo[b,d]furan-2,3-diamine (3.57 g, 93% yield) as a grey solid.
Synthesis of N2-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-N3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)dibenzo[b,d]furan-2,3-diamine
A mixture of N2-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)dibenzo[b,d]furan-2,3-diamine (2.41 g, 4.69 mmol, 1.01 equiv) and compound N2-([1,1′:3′,1″-terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)dibenzo[b,d]furan-2,3-diamine (2.07 g, 4.65 mmol, 1.0 equiv) in toluene (29 mL) was sparged with nitrogen for 45 minutes. In a second flask a mixture of di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl) phosphine (cBRIDP) (0.328 g, 0.93 mmol, 0.2 equiv) and allyl palladium chloride dimer (0.102 g, 0.28 mmol, 0.06 equiv) in toluene (29 mL) was sparged with nitrogen for 45 minutes. The contents of the first flask (reagents) were transferred to the second flask (catalyst) via syringe. Sodium tert-butoxide (0.98 g, 10.22 mmol, 2.2 equiv) was added and the mixture was heated at 110° C. for 1.5 hours. The mixture was cooled to room temperature and filtered through a Celite pad, which was rinsed with dichloromethane (3×75 mL). The filtrate was concentrated under reduced pressure to give crude N2-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-N3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)dibenzo[b,d]furan-2,3-diamine (5.0 g, quantitative yield) as a dark purple solid.
Synthesis of 1-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3H-benzo[2,3]benzofuro[5,6-d]imidazol-1-ium
A mixture of crude N2-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-N3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)dibenzo[b,d]furan-2,3-diamine (5.0 g, 4.65 mmol, 1 equiv, assumes 100% yield in the previous step) in triethyl orthoformate (50 mL, 303 mmol, 50 equiv) was sparged with nitrogen for 10 minutes. Hydrochloric acid (35% in water, 1.0 mL, 12.7 mmol, 2.1 equiv) was added and the mixture was heated at 90° C. for 2 hours. The mixture was cooled to room temperature and concentrated under reduced pressure to give crude 1-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3H-benzo[2,3]benzofuro[5,6-d]imidazol-1-ium (5.49 g, 91% yield) as a dark brown solid, which was used subsequently.
Synthesis of Pt(LA4-(53)(1)(1))(LB31-(5)(1)(1))
A mixture of 1-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3H-benzo[2,3]benzofuro[5,6-d]imidazol-1-ium (5.0 g, 5.72 mmol, 1.0 equiv) in a solvent (114 mL) was sparged with nitrogen for 30 minutes. A platinum precursor (1.1 equiv) and a base (3.0 equiv) were added and the flask was wrapped with aluminum foil to prevent light exposure. After heating at 127° C. for 16 hours, the reaction mixture was cooled to room temperature and poured into water (500 mL). The aqueous mixture was extracted with dichloromethane (4×125 mL). The combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. The residue was absorbed onto Celite (100 g) and purified by column chromatography. The solid was triturated with methanol (20 mL) and dried under vacuum at 50° C. for 16 h to give Pt(LA4-(53)(1)(1))(LB31-(5)(1)(1)) (1.64 g, 28% yield) as a light yellow solid.
Synthesis of Pt(LA3-(53)(1)(1))(LB31-(5)(1)(1))
Synthesis of N-(3-Bromo-2-fluoro-6-nitrophenyl)-[1,1′:3′,1″-terphenyl]-2,2″,3,3″,4,4″,5,5″,6,6″-d10-2′-amine
A mixture of compound 2 (5.0 g, 19.6 mmol, 1.0 equiv) and compound 1-bromo-2,3-difluoro-4-nitrobenzene (6.6 g, 25.5 mmol, 1.3 equiv) in THF (196 mL) was sparged with nitrogen for 20 minutes and cooled to 0° C. 1 M Lithium bis(trimethylsilyl)amide in THF (58.7 mL, 58.7 mmol, 2.5 equiv) was added over 30 minutes. The reaction was stirred at room temperature for 3 hours. The reaction was quenched with saturated ammonium chloride (500 mL) then diluted with water (150 mL). The mixture was extracted with dichloromethane (2×1.0 L). The combined organic layers were washed with saturated brine (1.0 L), dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by column chromatography to give N-(3-Bromo-2-fluoro-6-nitrophenyl)-[1,1′:3′,1″-terphenyl]-2,2″,3,3″,4,4″,5,5″,6,6″-d10-2′-amine (9.07 g, 97% yield) as a light brown solid.
Synthesis of 3′-(([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)amino)-2′-fluoro-4′-nitro-[1,1′-biphenyl]-2-ol
A mixture of N-(3-Bromo-2-fluoro-6-nitrophenyl)-[1,1′:3′,1″-terphenyl]-2,2″,3,3″,4,4″,5,5″,6,6″-d10-2′-amine (9.07 g, 19.2 mmol, 1.0 equiv), (2-hydroxyphenyl)boronic acid (3.44 g, 24.9 mmol, 1.3 equiv) and potassium carbonate (7.94 g, 57.5 mmol, 3.0 equiv) in dioxane (385 mL) and water (254 mL) was sparged with nitrogen for 30 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.89 g, 0.77 mmol, 0.04 equiv) was added and the reaction was heated at 100° C. under nitrogen for 24 hours. The reaction mixture was diluted with water (500 mL) and ethyl acetate (1.0 L). The layers were separated and the aqueous layer was extracted with ethyl acetate (3×300 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by column chromatography system to give 3′-(([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)amino)-2′-fluoro-4′-nitro-[1,1′-biphenyl]-2-ol (8.74 g, 92% yield) as a red solid.
Synthesis of N-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-nitrodibenzo[b,d]furan-4-amine
A mixture of 3′-(([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)amino)-2′-fluoro-4′-nitro-[1,1′-biphenyl]-2-ol (8.74 g, 18.0 mmol, 1.0 equiv) and potassium carbonate (7.45 g, 53.9 mmol, 3.0 equiv) in N-methyl-2-pyrrolidinone (180 ml) was sparged with nitrogen for 30 minutes. The reaction was heated at 120° C. for 16 hours. The reaction was cooled to room temperature. Saturated ammonium chloride (200 mL) and water (200 mL) were added to give a slurry which was filtered, rinsed with water (3×300 mL). The solid was dried under vacuum at room temperature for 3 hours. The solid was dissolved in dichloromethane (50 mL) and concentrated under reduced pressure. The crude material was purified by column chromatography system to give N-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-nitrodibenzo[b,d]furan-4-amine (8.68 g, 98% yield) as a light orange solid.
Synthesis of N4-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)dibenzo[b,d]furan-3,4-diamine
A mixture of N-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-nitrodibenzo[b,d]furan-4-amine (3.41 g, 7.31 mmol, 1.0 equiv) and 10% palladium on carbon (0.78 g, 0.36 mmol, 0.05 equiv, 50% wet) in ethyl acetate (91 mL) was hydrogenated at 40 psi for 4 hours. The reaction mixture was purged with nitrogen 3 times. The solid was filtered and washed with ethyl acetate (5×60 mL) under nitrogen. The filtrate was concentrated under reduced pressure to give crude N4-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)dibenzo[b,d]furan-3,4-diamine (3.17 g, 97% yield) as a grey solid which was used subsequently.
Synthesis of N4-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-N3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)dibenzo[b,d]furan-3,4-diamine
A mixture of crude N4-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)dibenzo[b,d]furan-3,4-diamine (3.17 g, 6.73 mmol, 1.1 equiv), sodium tert-butoxide (1.18 g, 12.2 mmol, 2.0 equiv) and N4-([1,1′:3′,1″-terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)dibenzo[b,d]furan-3,4-diamine (2.67 g, 6.12 mmol, 1.0 equiv) in toluene (30 mL) was sparged with nitrogen for 15 minutes. BINAP Pd G3 (0.30 g, 0.30 mmol, 0.05 equiv) was added and the mixture was heated at 110° C. for 15 hours. The mixture was cooled to room temperature and filtered through a Celite pad, which was rinsed with dichloromethane (3×75 mL). The filtrate was concentrated under reduced pressure. The crude material was purified by column chromatography system to give N4-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-N3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)dibenzo[b,d]furan-3,4-diamine (4.3 g, 95% yield) as an off-white solid.
Synthesis of 1-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3H-benzo[2,3]benzofuro[6,7-d]imidazol-1-ium
A mixture of N4-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-N3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H- carbazol-2-yl)oxy)phenyl)dibenzo[b, d]furan-3,4-diamine (4.3 g, 5.24 mmol, 1.0 equiv) in triethyl orthoformate (44 mL, 262 mmol, 50 equiv) was sparged with nitrogen for 10 minutes. Hydrochloric acid (35% in water, 0.92 mL, 11.0 mmol, 2.1 equiv) was added and the mixture was heated at 90° C. for 2 hours. The mixture was cooled to room temperature and concentrated under reduced pressure to give crude 1-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3H-benzo[2,3]benzofuro[6,7-d]imidazol-1-ium (4.95 g, 100% yield) as a dark brown solid.
Synthesis of Pt(LA3-(53)(1)(1))(LB31-(5)(1)(1))
A mixture of 1-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3H-benzo[2,3]benzofuro[6,7-d]imidazol-1-ium (4.95 g, 5.21 mmol, 1.0 equiv) in a solvent (104 mL) was sparged with nitrogen for 30 minutes. A platinum precursor (2.38 g, 5.73 mmol, 1.1 equiv) and a base (1.80 mL, 15.6 mmol, 3.0 equiv) were added and the flask was wrapped with aluminum foil to prevent light exposure. After heating at 120° C. for 16 hours, the reaction mixture was cooled to room temperature and poured into water (500 mL). The aqueous mixture was extracted with dichloromethane (4×125 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was absorbed onto Celite (100 g) and purified by column chromatography system. The solid was triturated with methanol (20 mL) and dried under vacuum at 50° C. for 16 h to give Pt(LA3-(53)(1)(1))(LB31-(5)(1)(1)) (960 mg, 18% yield) as a light yellow solid.
Synthesis of Pt(LA4-(53)(1)(1))(LB31-(5)(64)(1))
Synthesis of N-(9-(4-(tert-Butyl)pyridin-2-yl)-2-methoxy-9H-carbazol-3-yl)acetamide
A solution of 3-bromo-9-(4-(tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole (18.0 g, 44.0 mmol, 1.0 equiv) in toluene (440 mL) was sparged with nitrogen for 20 minutes. Acetamide (13.0 g, 221 mmol, 5.0 equiv), potassium carbonate (13.7 g, 99.0 mmol, 2.3 equiv), cyclohexane-1,2-diamine (2.6 ml, 22.0 mmol, 0.5 equiv) and copper(I) iodide (1.26 g, 6.6 mmol, 0.15 equiv) were added and the mixture was sparged with nitrogen for 5 additional minutes. The mixture was stirred at 110° C. for 4 days. The reaction mixture was cooled to room temperature, diluted with water (500 mL) and filtered through a pad of Celite (0.5″). The filter cake was washed with ethyl acetate (1.5 L) and water (500 mL). The layers were separated and the aqueous layer was extracted with ethyl acetate (500 mL). The combined organic layers were washed with 10% ammonium hydroxide (2×300 mL), water (500 mL) and saturated brine (500 mL). The organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by column chromatography to give N-(9-(4-(tert-Butyl)pyridin-2-yl)-2-methoxy-9H-carbazol-3-yl)acetamide (10.1 g, 58% yield) as an off-white solid.
Synthesis of 9-(4-(tert-Butyl)pyridin-2-yl)-2-methoxy-9H-carbazol-3-amine:
A solution of potassium hydroxide (157 g, 2.80 mol, 42 equiv) in water (75 mL was added to a solution of N-(9-(4-(tert-Butyl)pyridin-2-yl)-2-methoxy-9H-carbazol-3-yl)acetamide (25.6 g, 66.1 mmol, 1.00 equiv) in 2-propanol (600 mL). After heating at 80° C. for 22 hours, the mixture was cooled to room temperature and the layers were separated. The aqueous layer was extracted with ethyl acetate (500 mL). The combined organics were washed with saturated brine (400 mL), dried over sodium sulfate (60 g), and concentrated under reduced pressure. The residue was absorbed onto Celite (60 g) and purified by column chromatography system to give 9-(4-(tert-Butyl)pyridin-2-yl)-2-methoxy-9H-carbazol-3-amine (20.3 g, 83% yield) as a brown solid.
Synthesis of 9-(4-(tert-Butyl)pyridin-2-yl)-2-methoxy-9H-carbazol-3-amine
A mixture of 9-(4-(tert-Butyl)pyridin-2-yl)-2-methoxy-9H-carbazol-3-amine (20.0 g, 57.9 mmol, 1.00 equiv) and 2,2′-dibromo-1,1′-biphenyl (19.9 g, 63.8, 1.10 equiv) in xylenes (1.1 L) was sparged with nitrogen for 20 minutes at room temperature. The mixture was treated with sodium tert-butoxide (11.8 g, 123 mmol, 2.10 equiv) and sparged with nitrogen for another 20 minutes while heating to 90° C. Separately, a mixture of tris(dibenzylideneacetone)dipalladium(0) (3.18 g, 3.47 mmol, 0.06 equiv) and dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphane (SPhos, 2.87 g, 6.99 mmol, 0.12 equiv) in xylenes (100 mL) was sparged with nitrogen for 30 minutes while heating to 90° C. The catalyst mixture (at 90° C.) was poured directly into the reagent mixture (at 90° C.), which was sparged with nitrogen for another 10 minutes, then heated at 111° C. overnight. The mixture was cooled to room temperature and diluted with water (1 L) with vigorous stirring. The biphasic mixture was filtered through Celite (100 g), which was washed with ethyl acetate (1 L). The layers of the filtrate were separated. The organic layer was washed with saturated brine (1 L), dried over sodium sulfate (100 g) and concentrated under reduced pressure. The residue was absorbed onto Celite (56 g) and purified by column chromatography to give 9-(4-(tert-Butyl)pyridin-2-yl)-2-methoxy-9H-carbazol-3-amine (27.2 g, 92% yield) as a red oil.
Synthesis of 9-(4-(tert-Butyl)pyridin-2-yl)-9H-[3,9′-bicarbazol]-2-ol
A solution of 9-(4-(tert-Butyl)pyridin-2-yl)-2-methoxy-9H-carbazol-3-amine (27 g, 55 mmol, 1.00 equiv) and sodium ethanethiolate (13.8 g, 163 mmol, 3.0 equiv) in N-methyl-2-pyrrolidinone (400 mL) was heated at 130° C. for 18 hours. The reaction mixture was cooled to room temperature and diluted with saturated ammonium chloride (400 mL) and ethyl acetate (250 mL). The layers were separated and the aqueous layer was extracted with ethyl acetate (250 mL). The combined organic layers were washed with saturated sodium bicarbonate (2×250 mL) and saturated brine (500 mL), dried over sodium sulfate (50 g) and concentrated under reduced pressure. The crude product was absorbed onto Celite (50 g) and purified by column chromatography to give 9-(4-(tert-Butyl)pyridin-2-yl)-9H-[3,9′-bicarbazol]-2-ol (24.6 g, 92% yield) as a light brown solid. (GMW2020-1-63)
Synthesis of 2-(3-Bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-3,9′-bicarbazole
A mixture of 9-(4-(tert-Butyl)pyridin-2-yl)-9H-[3,9′-bicarbazol]-2-ol (24.9 g, 51.7 mmol, 1.00 equiv) and 1,3-dibromobenzene (24.0 g, 102 mmol, 1.97 equiv) in dimethyl sulfoxide (300 mL) was sparged with nitrogen for 30 minutes while picolinic acid (0.75 g, 6.1 mmol, 0.12 equiv), tribasic potassium phosphate (22.7 g, 107 mmol, 2.07 equiv), and copper(I) iodide (0.58 g, 3.1 mmol, 0.06 equiv) were added. After heating at 120° C. for 47 hours, the reaction mixture was cooled to room temperature and diluted with methyl tert-butyl ether (250 mL) and 10% ammonium hydroxide (250 mL). The layers were separated and the organic layer was washed with 10% ammonium hydroxide (2×250 mL). The combined aqueous layers were extracted with methyl tert-butyl ether (250 mL). The combined organic layers were washed with saturated brine (500 mL), dried over sodium sulfate (100 g) and concentrated under reduced pressure. The residue was absorbed onto Celite (51 g) and purified by column chromatography to give 2-(3-Bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-3,9′-bicarbazole (18.6 g, 49% yield) as a dull yellow solid.
Synthesis of N2-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-N3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9′-bicarbazol]-2-yl)oxy)phenyl)dibenzo[b,d]furan-2,3-diamine
A mixture of give 2-(3-Bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-3,9′-bicarbazole (1.13 g, 1.8 mmol, 1.05 equiv), compound N2-([1,1′:3′,1″-terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)dibenzo[b,d]furan-2,3-diamine (0.75 g, 1.7 mmol, 1.0 equiv), and sodium tert-butoxide (0.32 g, 3.4 mmol, 2.0 equiv) in anhydrous toluene (8.5 mL) was sparged with nitrogen for 15 minutes. BINAP Pd G3 (0.084 g, 0.084 mmol, 0.05 equiv) was added and the mixture was sparged for another 5 minutes. The resulting solution was stirred at 110° C. for 16 hours. The reaction was cooled to room temperature and the solvent was removed under reduced pressure to give a crude N2-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-N3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9′-bicarbazol]-2-yl)oxy)phenyl)dibenzo[b,d]furan-2,3-diamine (1.9 g, 97% yield) as a dark solid which was used subsequently.
Synthesis of 1-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9′-bicarbazol]-2-yl)oxy)phenyl)-1H-benzo[2,3]benzofuro[5,6-d]imidazol-3-ium Chloride
A mixture of N2-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-N3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9′-bicarbazol]-2-yl)oxy)phenyl)dibenzo[b,d]furan-2,3-diamine (2.3 g, 2.4 mmol, 1.0 equiv) in triethyl orthoformate (19.7 mL, 118 mmol, 50.0 equiv) was sparged with nitrogen for 15 minutes. Concentrated hydrochloric acid (0.4 mL, 4.9 mmol, 2.1 equiv) was added to the mixture under nitrogen. The reaction was heated at 100° C. for 3 hours. The solvent was removed under reduced pressure to give 1-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9′-bicarbazol]-2-yl)oxy)phenyl)-1H-benzo[2,3]benzofuro[5,6-d]imidazol-3-ium chloride (2.48 g, 98% yield) as a dark solid which was used subsequently.
Synthesis of Pt(LA4-(53)(1)(1))(LB31-(5)(64)(1))
A mixture of 1-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9′-bicarbazol]-2-yl)oxy)phenyl)-1H-benzo[2,3]benzofuro[5,6-d]imidazol-3-ium chloride (2.48 g, 2.38 mmol, 1.0 equiv) and a base (3.3 equiv) in a solvent (47.8 mL) was sparged with nitrogen for 30 minutes. A platinum precursor (1.1 equiv) was added and the mixture was sparged with nitrogen for another 10 minutes. The reaction mixture was heated at 120° C. for 2 days. The reaction was cooled to room temperature. Water (50 mL) was added to give a suspension which was filtered and the collected solid was rinsed with water (150 mL). The solid was dissolved in dichloromethane (50 mL) and concentrated under reduced pressure. The crude material was purified by column chromatography system to give Pt(LA4-(53)(1)(1))(LB31-(5)(64)(1)) (1.9 g, 63% yield) as a yellow solid.
Synthesis of Pt(LA4-(53)(1)(1))(LB31-(5)(1)(7))
Synthesis of N-(5-Bromo-4-fluoro-2-nitrophenyl)-[1,1′:3′,1″-terphenyl]-2,2″,3,3″,4,4″,5,5″,6,6″-d10-2′-amine
A mixture of compound 2 (10.0 g, 39.2 mmol, 1.0 equiv) and compound 1-bromo-2,5-difluoro-4-nitrobenzene (12.1 g, 50.9 mmol, 1.3 equiv) in THF (392 mL) was sparged with nitrogen for 20 minutes and cooled to 0° C. 1 M Lithium bis(trimethylsilyl)amide in THF (98 mL, 98 mmol, 2.5 equiv) was added over 30 minutes. The reaction was stirred at room temperature for 3 hours. The reaction was quenched with saturated ammonium chloride (500 mL) and water (150 mL). The mixture was extracted with dichloromethane (2×1.0 L). The combined organic layers were washed with saturated brine (1.0 L), dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by column chromatography system to give N-(5-Bromo-4-fluoro-2-nitrophenyl)-[1,1′:3′,1″-terphenyl]-2,2″,3,3″,4,4″,5,5″,6,6″-d10-2′-amine (13.6 g, 71% yield) as an orange solid.
Synthesis of 5′-(([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)amino)-2′-fluoro-4′-nitro-[1,1′-biphenyl]-2-ol
A mixture of compound N-(5-Bromo-4-fluoro-2-nitrophenyl)-[1,1′:3′,1″-terphenyl]-2,2″,3,3″,4,4″,5,5″,6,6″-d10-2′-amine (13.6 g, 28.9 mmol, 1.0 equiv), (2-hydroxyphenyl)boronic acid (4.38 g, 31.7 mmol, 1.1 equiv), and potassium carbonate (9.97 g, 72.1 mmol, 2.5 equiv) in dioxane (579 mL) and water (382 mL) was sparged with nitrogen for 30 minutes. Tetrakis(triphenylphosphine)palladium(0) (1.00 g, 0.866 mmol, 0.03 equiv) was added and the reaction was heated at 100° C. for 24 hours. The reaction was diluted with water (500 mL) and ethyl acetate (1.0 L). The aqueous layer was separated and extracted with ethyl acetate (3×300 mL). The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by column chromatography to give 5′-(([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)amino)-2′-fluoro-4′-nitro-[1,1′-biphenyl]-2-ol (11.9 g, 83% yield) as a red solid.
Synthesis of N-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-nitrodibenzo[b,d]furan-2-amine:
A mixture of compound 5′-(([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)amino)-2′-fluoro-4′-nitro-[1,1′-biphenyl]-2-ol (10.5 g, 21.6 mmol, 1.0 equiv) and potassium carbonate (8.95 g, 64.7 mmol, 3.0 equiv) in N-methyl-2-pyrrolidinone (216 mL) was sparged with nitrogen for 30 minutes. The reaction was heated at 120° C. for 16 hours. The reaction was cooled to room temperature. A solution of saturated ammonium chloride (50 mL) and water (50 mL) was added to give a suspension which was filtered. The collected solid was rinsed with water (3×50 mL) and dried under vacuum at room temperature for 3 hours. The solid was dissolved in dichloromethane (50 mL) and concentrated under reduced pressure. The crude material was purified by column chromatography to give N-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-nitrodibenzo[b,d]furan-2-amine (8.68 g, 85% yield) as a red solid.
Synthesis of N2-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)dibenzo[b,d]furan-2,3-diamine
A mixture of compound N-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-nitrodibenzo[b,d]furan-2-amine (4.0 g, 8.57 mmol, 1.0 equiv) and 10% palladium on carbon (0.91 g, 0.43 mmol, 0.05 equiv, 50% wet) in ethyl acetate (107 mL) was hydrogenated at 40 psi for 4 hours. The reaction mixture was purged with nitrogen and filtered. The solid was washed with ethyl acetate (5×25 mL) under a blanket of nitrogen. The filtrate was concentrated under reduced pressure to give N2-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)dibenzo[b, d]furan-2,3-diamine (3.57 g, 93% yield) as a grey solid which was used subsequently.
Synthesis of Pt(LA4-(53)(1)(1))(LB31-(5)(1)(7))
Synthesis of N2-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-N3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)dibenzo[b,d]furan-2,3-diamine
A solution of compound 6 (1.50 g, 3.37 mmol, 1.0 equiv), 2-(3-bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazole (1.87 g, 3.70 mmol, 1.1 equiv) and sodium tert-butoxide (0.65 g, 6.73 mmol, 2.0 equiv) in anhydrous toluene (16.8 mL) was sparged with nitrogen for 15 minutes. BINAP Pd G3 (0.17 g, 0.17 mmol, 0.05 equiv) was added and the reaction was sparged with nitrogen for another 10 minutes. The resulting dark brown solution was stirred at 110° C. for 16 hours under nitrogen. The reaction was cooled to room temperature and filtered through a pad of Celite (0.5″). The filter cake was washed with dichloromethane (3×20 mL). The filtrate was dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by column chromatography on silica to give N2-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-N3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)dibenzo[b,d]furan-2,3-diamine (2.16 g, 73% yield) as an off-white solid.
Synthesis of 1-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-3H-benzo[2,3]benzofuro[5,6-d]imidazol-1-ium
A mixture of N2-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-N3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)dibenzo[b,d]furan-2,3-diamine (2.16 g, 2.50 mmol, 1.0 equiv) in triethyl orthoformate (20.8 mL, 125 mmol, 50.0 equiv) was sparged with nitrogen for 15 minutes. Concentrated hydrochloric acid (0.44 mL, 5.27 mmol, 2.1 equiv) was added to the mixture under nitrogen. The reaction was heated at 100° C. under nitrogen for 2 hours. After cooling to room temperature, the mixture was concentrated under reduced pressure to give 1-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-3H-benzo[2,3]benzofuro[5,6-d]imidazol-1-ium (2.37 g, 100% yield) as a dark solid.
Synthesis of Pt(LA4-(53)(1)(1))(LB31-(5)(1)(7))
A mixture of 1-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-3H-benzo[2,3]benzofuro[5,6-d]imidazol-1-ium (2.37 g, 2.56 mmol, 1.0 equiv) and a base (3.0 equiv) in a solvent (51.2 mL) was sparged with nitrogen for 30 minutes. A platinum precursor (1.1 equiv) was added and the mixture was sparged with nitrogen for another 10 minutes. The reaction was heated at 120° C. for 24 hours. The reaction was cooled to room temperature. Water (50 mL) was added to give a slurry which was filtered and rinsed with water (150 mL). The dried solid was dissolved in dichloromethane (50 mL) and concentrated under reduced pressure. The crude material was purified by chromatography on silica to give Pt(LA4-(53)(1)(1))(LB31-(5)(1)(7)) (2.44 g, 89% yield) as a yellow solid.
OLEDs were grown on a glass substrate pre-coated with an indium-tin-oxide (ITO) layer having a sheet resistance of 15-Ω/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. The devices were fabricated in high vacuum (<10−6 Torr) by thermal evaporation. The anode electrode was 750 Å of indium tin oxide (ITO). 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 were grown using the following materials:
For Examples 1-4 and Comparison 1, devices had organic layers consisting of, sequentially, from the ITO surface, 100 Å of Compound 1 (HIL), 250 Å of Compound 2 (HTL), 50 Å of HH1 (EBL), 300 Å of HH1 doped with 50% of HH2, 12% of Dopant (EML), 50 Å of HH2 (BL), 300 Å of Compound 3 doped with 35% of Compound 4 (ETL), 10 Å of Compound 3 (EIL) followed by 1,000 Å of Al (Cathode). Device Structure 2 had organic layers consisting of, sequentially, from the ITO surface, 100 Å of Compound 1 (HIL), 250 Å of Compound 2 (HTL), 50 Å of HH1 (EBL), 300 Å of DH1 doped with a fixed percentage of DH2, X % of Dopant (EML), 50 Å of HH2 (BL), 300 Å of Compound 3 doped with 35% of Compound 4 (ETL), 10 Å of Compound 3 (EIL) followed by 1,000 Å of Al (Cathode). The external quantum efficiency (EQE), voltage (V), peak wavelength (λmax), and CIE coordinates are measured at 10 mA/cm2 and are recorded in Table 1. The voltage and EQE are shown relative to Comparison 1.
The above data shows that device Examples 1-4 each exhibited a larger EQE than Comparison 1. The 10%-43% increase in EQE is beyond any value that could be attributed to experimental error and the observed improvement is significant. Based on the fact that the devices have the same structure with the only difference being the fused ring structure on the carbene of the dopants, the significant performance improvement observed in the above data was unexpected. Without being bound by any theories, this improvement may be attributed to the improved molecular alignment in the emissive layer as a result of the extended conjugation of the carbene.
This application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Application No. 63/160,010, filed on Mar. 12, 2021, the entire contents of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 63160010 | Mar 2021 | US |
