Patent Grant
11725022
The present invention relates to compounds for use as emitters, and devices, such as organic light emitting diodes, including the same.
Opto-electronic devices that make use of organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials. For example, the wavelength at which an organic emissive layer emits light may generally be readily tuned with appropriate dopants.
OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting. Several OLED materials and configurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
One application for phosphorescent emissive molecules is a full color display. Industry standards for such a display call for pixels adapted to emit particular colors, referred to as “saturated” colors. In particular, these standards call for saturated red, green, and blue pixels. Alternatively the OLED can be designed to emit white light. In conventional liquid crystal displays emission from a white backlight is filtered using absorption filters to produce red, green and blue emission. The same technique can also be used with OLEDs. The white OLED can be either a single EML device or a stack structure. Color may be measured using CIE coordinates, which are well known to the art.
One example of a green emissive molecule is tris(2-phenylpyridine) iridium, denoted Ir(ppy)3, which has the following structure:
In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.
As used herein, the term “organic” includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic opto-electronic devices. “Small molecule” refers to any organic material that is not a polymer, and “small molecules” may actually be quite large. Small molecules may include repeat units in some circumstances. For example, using a long chain alkyl group as a substituent does not remove a molecule from the “small molecule” class. Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone or as a part of the backbone. Small molecules may also serve as the core moiety of a dendrimer, which consists of a series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fluorescent or phosphorescent small molecule emitter. A dendrimer may be a “small molecule,” and it is believed that all dendrimers currently used in the field of OLEDs are small molecules.
As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from substrate. There may be other layers between the first and second layer, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.
As used herein, “solution processable” means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.
A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.
As used herein, and as would be generally understood by one skilled in the art, a first “Highest Occupied Molecular Orbital” (HOMO) or “Lowest Unoccupied Molecular Orbital” (LUMO) energy level is “greater than” or “higher than” a second HOMO or LUMO energy level if the first energy level is closer to the vacuum energy level. Since ionization potentials (IP) are measured as a negative energy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level corresponds to an electron affinity (EA) having a smaller absolute value (an EA that is less negative). On a conventional energy level diagram, with the vacuum level at the top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. A “higher” HOMO or LUMO energy level appears closer to the top of such a diagram than a “lower” HOMO or LUMO energy level.
As used herein, and as would be generally understood by one skilled in the art, a first work function is “greater than” or “higher than” a second work function if the first work function has a higher absolute value. Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “higher” work function is more negative. On a conventional energy level diagram, with the vacuum level at the top, a “higher” work function is illustrated as further away from the vacuum level in the downward direction. Thus, the definitions of HOMO and LUMO energy levels follow a different convention than work functions.
More details on OLEDs, and the definitions described above, can be found in U.S. Pat. No. 7,279,704, which is incorporated herein by reference in its entirety.
Tetradentate platinum complexes comprising an imidazole/benzimidazole carbene are disclosed. These platinum carbenes with the specific substituents disclosed herein are novel and provides phosphorescent emissive compounds that exhibit physical properties that can be tuned, such as sublimation temperature, emission color, and device stability. These compounds are useful in OLED applications.
A compound having the following formula
is disclosed. The variables in Formula I are defined in detail below.
An OLED comprising the compound having the Formula I in one of its organic layers is also disclosed.
A consumer product comprising the OLED is also disclosed.
Generally, an OLED comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and hole localize on the same molecule, an “exciton,” which is a localized electron-hole pair having an excited energy state, is formed. Light is emitted when the exciton relaxes via a photoemissive mechanism. In some cases, the exciton may be localized on an excimer or an exciplex. Non-radiative mechanisms, such as thermal relaxation, may also occur, but are generally considered undesirable.
The initial OLEDs used emissive molecules that emitted light from their singlet states (“fluorescence”) as disclosed, for example, in U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescent emission generally occurs in a time frame of less than 10 nanoseconds.
More recently, OLEDs having emissive materials that emit light from triplet states (“phosphorescence”) have been demonstrated. Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices,” Nature, vol. 395, 151-154, 1998; (“Baldo-I”) and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence,” Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), are incorporated by reference in their entireties. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporated by reference.
More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Patent Application Publication No. 2003/0230980, which is incorporated by reference in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entireties, disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers is described in more detail in U.S. Pat. No. 6,097,147 and U.S. Patent Application Publication No. 2003/0230980, which are incorporated by reference in their entireties. Examples of injection layers are provided in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers may be found in U.S. Patent Application Publication No. 2004/0174116, which is incorporated by reference in its entirety.
The simple layered structure illustrated in
Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated by reference in its entirety. By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in U.S. Pat. No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in
Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For the organic layers, preferred methods include thermal evaporation, ink-jet, such as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, which are incorporated by reference in their entireties, organic vapor phase deposition (OVPD), such as described in U.S. Pat. No. 6,337,102 to Forrest et al., which is incorporated by reference in its entirety, and deposition by organic vapor jet printing (OVJP), such as described in U.S. Pat. No. 7,431,968, which is incorporated by reference in its entirety. Other suitable deposition methods include spin coating and other solution based processes. Solution based processes are preferably carried out in nitrogen or an inert atmosphere. For the other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pat. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in their entireties, and patterning associated with some of the deposition methods such as ink-jet and organic vapor jet printing (OVJP). Other methods may also be used. The materials to be deposited may be modified to make them compatible with a particular deposition method. For example, substituents such as alkyl and aryl groups, branched or unbranched, and preferably containing at least 3 carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having 20 carbons or more may be used, and 3-20 carbons is a preferred range. Materials with asymmetric structures may have better solution processability than those having symmetric structures, because asymmetric materials may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
Devices fabricated in accordance with embodiments of the present invention may further optionally comprise a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from damaging exposure to harmful species in the environment including moisture, vapor and/or gases, etc. The barrier layer may be deposited over, under or next to a substrate, an electrode, or over any other parts of a device including an edge. The barrier layer may comprise a single layer, or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include compositions having a single phase as well as compositions having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate an inorganic or an organic compound or both. The preferred barrier layer comprises a mixture of a polymeric material and a non-polymeric material as described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos. PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporated by reference in their entireties. To be considered a “mixture”, the aforesaid polymeric and non-polymeric materials comprising the barrier layer should be deposited under the same reaction conditions and/or at the same time. The weight ratio of polymeric to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be created from the same precursor material. In one example, the mixture of a polymeric material and a non-polymeric material consists essentially of polymeric silicon and inorganic silicon.
Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of electronic component modules (or units) that can be incorporated into a variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices such as discrete light source devices or lighting panels, etc. that can be utilized by the end-user product manufacturers. Such electronic component modules can optionally include the driving electronics and/or power source(s). Devices fabricated in accordance with embodiments of the invention can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. A consumer product comprising an OLED that includes the compound of the present disclosure in the organic layer in the OLED is disclosed. Such consumer products would include any kind of products that include one or more light source(s) and/or one or more of some type of visual displays. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, mobile phones, tablets, phablets, personal digital assistants (PDAs), wearable devices, laptop computers, digital cameras, camcorders, viewfinders, micro-displays (displays that are less than 2 inches diagonal), 3-D displays, virtual reality or augmented reality displays, vehicles, video walls comprising multiple displays tiled together, theater or stadium screen, a light therapy device, and a sign. Various control mechanisms may be used to control devices fabricated in accordance with the present invention, including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfortable to humans, such as 18 degrees C. to 30 degrees C., and more preferably at room temperature (20-25 degrees C.), but could be used outside this temperature range, for example, from −40 degree C. to +80 degree C.
The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices, such as organic transistors, may employ the materials and structures.
The terms “halo,” “halogen,” and “halide” are used interchangeably and refer to fluorine, chlorine, bromine, and iodine.
The term “acyl” refers to a substituted carbonyl radical (C(O)—Rs).
The term “ester” refers to a substituted oxycarbonyl (—O—C(O)—Rs or —C(O)—O—Rs) radical.
The term “ether” refers to an —ORs radical.
The terms “sulfanyl” or “thio-ether” are used interchangeably and refer to a —SRs radical.
The term “sulfinyl” refers to a —S(O)—Rs radical.
The term “sulfonyl” refers to a —SO2—Rs radical.
The term “phosphino” refers to a —P(Rs)3 radical, wherein each Rs can be same or different.
The term “silyl” refers to a —Si(Rs)3 radical, wherein each Rs can be same or different.
In each of the above, Rs can be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combination thereof. Preferred Rs is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combination thereof.
The term “alkyl” refers to and includes both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing from one to fifteen carbon atoms and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group is optionally substituted.
The term “cycloalkyl” refers to and includes monocyclic, polycyclic, and spiro alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, and the like. Additionally, the cycloalkyl group is optionally substituted.
The terms “heteroalkyl” or “heterocycloalkyl” refer to an alkyl or a cycloalkyl radical, respectively, having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si and Se, preferably, O, S or N. Additionally, the heteroalkyl or heterocycloalkyl group is optionally substituted.
The term “alkenyl” refers to and includes both straight and branched chain alkene radicals. Alkenyl groups are essentially alkyl groups that include at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl groups are essentially cycloalkyl groups that include at least one carbon-carbon double bond in the cycloalkyl ring. The term “heteroalkenyl” as used herein refers to an alkenyl radical having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group is optionally substituted.
The term “alkynyl” refers to and includes both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group is optionally substituted.
The terms “aralkyl” or “arylalkyl” are used interchangeably and refer to an alkyl group that is substituted with an aryl group. Additionally, the aralkyl group is optionally substituted.
The term “heterocyclic group” refers to and includes aromatic and non-aromatic cyclic radicals containing at least one heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Hetero-aromatic cyclic radicals may be used interchangeably with heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino, and the like, and cyclic ethers/thio-ethers, such as tetrahydropyran, tetrahydropyran, tetrahydrothiophene, and the like. Additionally, the heterocyclic group may be optionally substituted.
The term “aryl” refers to and includes both single-ring aromatic hydrocarbyl groups and polycyclic aromatic ring systems. The polycyclic rings may have two or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is an aromatic hydrocarbyl group, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Preferred aryl groups are those containing six to thirty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Especially preferred is an aryl group having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group is optionally substituted.
The term “heteroaryl” refers to and includes both single-ring aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. The heteroatoms include, but are not limited to O, S, N, P, B, Si, and Se. In many instances, O, S, or N are the preferred heteroatoms. Hetero-single ring aromatic systems are preferably single rings with 5 or 6 ring atoms, and the ring can have from one to six heteroatoms. The hetero-polycyclic ring systems can have two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. The hetero-polycyclic aromatic ring systems can have from one to six heteroatoms per ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group is optionally substituted.
Of the aryl and heteroaryl groups listed above, the groups of triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and the respective aza-analogs of each thereof are of particular interest.
The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclic group, aryl, and heteroaryl, as used herein, are independently unsubstituted, or independently substituted, with one or more general substituents.
In many instances, the general substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfanyl, sulfonyl, phosphino, and combinations thereof.
In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.
In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, sulfanyl, and combinations thereof.
In yet other instances, the more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
The terms “substituted” and “substitution” refer to a substituent other than H that is bonded to the relevant position, e.g., a carbon or nitrogen. For example, when R1 represents mono-substitution, then one R1 must be other than H (i.e., a substitution). Similarly, when R1 represents di-substitution, then two of R1 must be other than H. Similarly, when R1 represents no substitution, R1, for example, can be a hydrogen for available valencies of ring atoms, as in carbon atoms for benzene and the nitrogen atom in pyrrole, or simply represents nothing for ring atoms with fully filled valencies, e.g., the nitrogen atom in pyridine. The maximum number of substitutions possible in a ring structure will depend on the total number of available valencies in the ring atoms.
As used herein, “combinations thereof” indicates that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can envision from the applicable list. For example, an alkyl and deuterium can be combined to form a partial or fully deuterated alkyl group; a halogen and alkyl can be combined to form a halogenated alkyl substituent; and a halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl. In one instance, the term substitution includes a combination of two to four of the listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituent groups are those that contain up to fifty atoms that are not hydrogen or deuterium, or those which include up to forty atoms that are not hydrogen or deuterium, or those that include up to thirty atoms that are not hydrogen or deuterium. In many instances, a preferred combination of substituent groups will include up to twenty atoms that are not hydrogen or deuterium.
The “aza” designation in the fragments described herein, i.e. aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H groups in the respective fragment can be replaced by a nitrogen atom, for example, and without any limitation, azatriphenylene encompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.
As used herein, “deuterium” refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. Pat. No. 8,557,400, Patent Pub. No. WO 2006/095951, and U.S. Pat. Application Pub. No. US 2011/0037057, which are hereby incorporated by reference in their entireties, describe the making of deuterium-substituted organometallic complexes. Further reference is made to Ming Yan, et al., Tetrahedron 2015, 71, 1425-30 and Atzrodt et al., Angew. Chem. Int. Ed. (Reviews) 2007, 46, 7744-65, which are incorporated by reference in their entireties, describe the deuteration of the methylene hydrogens in benzyl amines and efficient pathways to replace aromatic ring hydrogens with deuterium, respectively.
It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g. phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g. benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.
A compound having the following formula
is disclosed. In Formula I, A and B are each independently a 5- or 6-membered aromatic ring; Z1 and Z2 are each independently selected from the group consisting of C and N; L1 and L2 are each independently selected from the group consisting of a direct bond, BR′, NR′, PR′, O, S, Se, C═O, S═O, SO2, CR′R″, SiR′R″, GeR′R″, alkyl, cycloalkyl, and combinations thereof; RA, RB, RC, and RD, each represents mono to a maximum possible number of substitutions, or no substitution; each of R′, R″, RA, RB, RC, and RD is independently a 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, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R is selected from the group consisting of deuterium, alkyl, cycloalkyl, heteroalkyl, arylalkyl, silyl, aryl, heteroaryl, and combinations thereof; any substitutions in RA, RB, RC, and RD may be joined or fused into a ring; RA or RB may be fused with L2 to form a ring; wherein at least one of the following conditions (a), (b), and (c) is true:
(a) at least one of RA and RC is present and is a 5- or 6-membered aromatic ring attached to a carbon atom;
(b) RA is present and is an alkyl or cycloalkyl attached to a carbon atom, and each RC is independently H or aryl; and
(c) both RA and RC are present and are an alkyl or cycloalkyl attached to a carbon atom, and R has a molecular weight equal to or greater than 16.0 grams per mole.
In some embodiments of the compound, each of R′, R″, RA, RB, RC, and RD is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, sulfanyl, nitrile, isonitrile, and combinations thereof.
In some embodiments, RA is a 6-membered aromatic ring. In some embodiments, RC is a 6-membered aromatic ring.
In some embodiments, Z2 is N, and A is selected from the group consisting of pyridine, pyrazole, imidazole, and triazole. In some embodiments, Z1 is C, and A is benzene. In some embodiments, Z1 is N, Z2 is C. In some further embodiment, both Z1 and Z2 is C, and one of them is a carbene carbon.
In some embodiments of the compound, RA contains substituents selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, partially or fully fluorinated alkyl or cycloalkyl, and combinations thereof.
In some embodiments of the compound where RA is a 6-membered aromatic ring, RC contains substituents selected from the group consisting of hydrogen, deuterium, alkyl, cycloalkyl, partially or fully fluorinated alkyl or cycloalkyl, and combinations thereof.
In some embodiments of the compound, two adjacent RD substituents are joined to form a fused 6-membered aromatic ring. In some embodiments of the compound, L1 is an oxygen atom. In some embodiments of the compound, L2 is NAr; and Ar is a 6-membered aromatic group.
In some embodiments of the compound, R is a 6-membered aromatic ring. In some embodiments of the compound, R is an alkyl group. In some embodiments of the compound, at least one of RA and RC is a tert-butyl group.
In some embodiments of the compound, the compound is selected from the group consisting of:
wherein R′ is selected from the group consisting of deuterium, alkyl, cycloalkyl, heteroalkyl, arylalkyl, silyl, aryl, heteroaryl, and combinations thereof; wherein RE represents mono to a maximum possible number of substitutions, or no substitution; wherein RE is 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, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In some embodiments of the compound, the compound is selected from the group consisting of Compound x having the formula Pt(LAy)(LBz), wherein x is an integer defined by x=7320(z−1)+y, wherein y is an integer from 1 to 7320 and z is an integer from 1 to 17795,
or x=41580(z−17796)+(y−7320)+130259400, wherein y is an integer from 7321 to 48900 and z is an integer from 17796 to 40673,
or x=7320(z−17796)+y+1081526640, wherein y is an integer from 1 to 7320 and z is an integer from 17796 to 40673,
or x=41580(z−1)+(y−7320)+1248993600, wherein y is an integer from 7321 to 48900 and z is an integer from 1 to 17795, provided that when k=1 in the structures for LAy listed below, i is an integer from 1 to 10, or j is an integer from 1 to 10, wherein LAy has the following structures:
in one embodiment, when k=1 in the formulas for LAy listed above, i is an integer from 1 to 10, or j is an integer from 1 to 10, wherein LBz has the following structures:
wherein A1 to A30 have the following structures:
and wherein R1 to R100 have the following structures:
An organic light emitting device (OLED) is also disclosed. The OLED comprises: an anode; a cathode; and an organic layer, disposed between the anode and the cathode, comprising a compound having the formula:
wherein Formula I is defined as provided above.
In some embodiments of the OLED, each of R′, R″, RA, RB, RC, and RD is independently selected from the group consisting of hydrogen, deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, sulfanyl, nitrile, isonitrile, and combinations thereof.
A consumer product comprising the OLED is also disclosed, wherein the organic layer in the OLED comprises the compound having the Formula I.
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.
An emissive region in an OLED is also disclosed. The emissive region comprises a compound having the formula:
In Formula I, A and B are each independently a 5- or 6-membered aromatic ring; Z1 and Z2 are each independently selected from the group consisting of C and N; L1 and L2 are each independently selected from the group consisting of a direct bond, BR′, NR′, PR′, O, S, Se, C═O, S═O, SO2, CR′R″, SiR′R″, GeR′R″, alkyl, cycloalkyl, and combinations thereof; RA, RB, RC, and RD, each represents mono to a maximum possible number of substitutions, or no substitution; each of R′, R″, RA, RB, RC, and RD is independently a 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, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; R is selected from the group consisting of deuterium, alkyl, cycloalkyl, heteroalkyl, arylalkyl, silyl, aryl, heteroaryl, and combinations thereof, any substitutions in RA, RB, RC, and RD may be joined or fused into a ring; RA or RB may be fused with L2 to form a ring;
wherein at least one of the following conditions (a), (b), and (c) is true:
(a) at least one of RA and RC is present and is a 5- or 6-membered aromatic ring attached to a carbon atom;
(b) RA is present and is an alkyl or cycloalkyl attached to a carbon atom, and each RC is independently H or aryl; and
(c) both RA and RC are present and are an alkyl or cycloalkyl attached to a carbon atom, and R has a molecular weight equal to or greater than 16.0 grams per mole.
In some embodiments of the emissive region, each of R′, R″, RA, RB, RC, and RD is independently a hydrogen or a substituent selected from the group consisting of hydrogen, deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, sulfanyl, nitrile, isonitrile, and combinations thereof.
In some embodiments of the emissive region, the compound is an emissive dopant or a non-emissive dopant.
In some embodiments of the emissive region, the emissive region further comprises a host, wherein the host comprises at least one selected from the group consisting of metal complex, triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, aza-triphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene.
In some embodiments of the emissive region, the emissive region further comprises a host, wherein the host is selected from the group consisting of:
and combinations thereof.
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.
According to another aspect, a formulation comprising the compound described herein is also disclosed.
The OLED disclosed herein can be incorporated into one or more of a consumer product, an electronic component module, and a lighting panel. The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments, while the compound can be a non-emissive dopant in other embodiments.
The organic layer can also include a host. In some embodiments, two or more hosts are preferred. In some embodiments, the hosts used maybe a) bipolar, b) electron transporting, c) hole transporting or d) wide band gap materials that play little role in charge transport. In some embodiments, the host can include a metal complex. The host can be a triphenylene containing benzo-fused thiophene or benzo-fused furan. Any substituent in the host can be an unfused substituent independently selected from the group consisting of CnH2n+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═CH—CnH2n+1, C≡C—CnH2n+1, Ar1, Ar1-Ar2, and CnH2n—Ar1, or the host has no substitutions. In the preceding substituents n can range from 1 to 10; and Ar1 and Ar2 can be independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof. The host can be an inorganic compound. For example a Zn containing inorganic material e.g. ZnS.
The host can be a compound comprising at least one chemical group selected from the group consisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. The host can include a metal complex. The host can be, but is not limited to, a specific compound selected from the group consisting of:
and combinations thereof.
Additional information on possible hosts is provided below.
In yet another aspect of the present disclosure, a formulation that comprises the novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, electron blocking material, hole blocking material, and an electron transport material, disclosed herein.
Combination with Other Materials
The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device. For example, emissive dopants disclosed herein may be used in conjunction with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The materials described or referred to below are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.
Conductivity Dopants:
A charge transport layer can be doped with conductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity. The conductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved. Hole-transporting layer can be doped by p-type conductivity dopants and n-type conductivity dopants are used in the electron-transporting layer.
Non-limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047, and US2012146012.
HIL/HTL:
A hole injecting/transporting material to be used in the present invention is not particularly limited, and any compound may be used as long as the compound is typically used as a hole injecting/transporting material. Examples of the material include, but are not limited to: a phthalocyanine or porphyrin derivative; an aromatic amine derivative; an indolocarbazole derivative; a polymer containing fluorohydrocarbon; a polymer with conductivity dopants; a conducting polymer, such as PEDOT/PSS; a self-assembly monomer derived from compounds such as phosphonic acid and silane derivatives; a metal oxide derivative, such as MoOx; a p-type semiconducting organic compound, such as 1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.
Examples of aromatic amine derivatives used in HIL or HTL include, but not limit to the following general structures:
Each of Ar1 to Ar9 is selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each Ar may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, Ar1 to Ar9 is independently selected from the group consisting of:
wherein k is an integer from 1 to 20; X101 to X108 is C (including CH) or N; Z101 is NAr1, O, or S; Ar1 has the same group defined above.
Examples of metal complexes used in HIL or HTL include, but are not limited to the following general formula:
wherein Met is a metal, which can have an atomic weight greater than 40; (Y101-Y102) is a bidentate ligand, Y101 and Y102 are independently selected from C, N, O, P, and S; L101 is an ancillary ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
In one aspect, (Y101-Y102) is a 2-phenylpyridine derivative. In another aspect, (Y101-Y102) is a carbene ligand. In another aspect, Met is selected from Ir, Pt, Os, and Zn. In a further aspect, the metal complex has a smallest oxidation potential in solution vs. Fc+/Fc couple less than about 0.6 V.
Non-limiting examples of the HIL and HTL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN102702075, DE102012005215, EP01624500, EP01698613, EP01806334, EP01930964, EP01972613, EP01997799, EP02011790, EP02055700, EP02055701, EP1725079, EP2085382, EP2660300, EP650955, JP07-073529, JP2005112765, JP2007091719, JP2008021687, JP2014-009196, KR20110088898, KR20130077473, TW201139402, U.S. Ser. No. 06/517,957, US20020158242, US20030162053, US20050123751, US20060182993, US20060240279, US20070145888, US20070181874, US20070278938, US20080014464, US20080091025, US20080106190, US20080124572, US20080145707, US20080220265, US20080233434, US20080303417, US2008107919, US20090115320, US20090167161, US2009066235, US2011007385, US20110163302, US2011240968, US2011278551, US2012205642, US2013241401, US20140117329, US2014183517, U.S. Pat. Nos. 5,061,569, 5,639,914, WO05075451, WO07125714, WO08023550, WO08023759, WO2009145016, WO2010061824, WO2011075644, WO2012177006, WO2013018530, WO2013039073, WO2013087142, WO2013118812, WO2013120577, WO2013157367, WO2013175747, WO2014002873, WO2014015935, WO2014015937, WO2014030872, WO2014030921, WO2014034791, WO2014104514, WO2014157018.
EBL:
An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and/or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.
Host:
The light emitting layer of the organic EL device of the present invention preferably contains at least a metal complex as light emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complexes or organic compounds may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied.
Examples of metal complexes used as host are preferred to have the following general formula:
wherein Met is a metal; (Y103-Y104) is a bidentate ligand, Y103 and Y104 are independently selected from C, N, O, P, and S; L101 is an another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k′+k″ is the maximum number of ligands that may be attached to the metal.
In one aspect, the metal complexes are:
wherein (O—N) is a bidentate ligand, having metal coordinated to atoms O and N.
In another aspect, Met is selected from Ir and Pt. In a further aspect, (Y103-Y104) is a carbene ligand.
In one aspect, the host compound contains at least one of the following groups selected from the group consisting of aromatic hydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; the group consisting of aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and the group consisting of 2 to 10 cyclic structural units which are groups of the same type or different types selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom, chain structural unit and the aliphatic cyclic group. Each option within each group may be unsubstituted or may be substituted by a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, the host compound contains at least one of the following groups in the molecule:
wherein R101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. k is an integer from 0 to 20 or 1 to 20. X101 to X108 are independently selected from C (including CH) or N. Z101 and Z102 are independently selected from NR101, O, or S.
Non-limiting examples of the host materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: EP2034538, EP2034538A, EP2757608, JP2007254297, KR20100079458, KR20120088644, KR20120129733, KR20130115564, TW201329200, US20030175553, US20050238919, US20060280965, US20090017330, US20090030202, US20090167162, US20090302743, US20090309488, US20100012931, US20100084966, US20100187984, US2010187984, US2012075273, US2012126221, US2013009543, US2013105787, US2013175519, US2014001446, US20140183503, US20140225088, US2014034914, U.S. Pat. No. 7,154,114, WO2001039234, WO2004093207, WO2005014551, WO2005089025, WO2006072002, WO2006114966, WO2007063754, WO2008056746, WO2009003898, WO2009021126, WO2009063833, WO2009066778, WO2009066779, WO2009086028, WO2010056066, WO2010107244, WO2011081423, WO2011081431, WO2011086863, WO2012128298, WO2012133644, WO2012133649, WO2013024872, WO2013035275, WO2013081315, WO2013191404, WO2014142472, US20170263869, US20160163995, U.S. Pat. No. 9,466,803,
Additional Emitters:
One or more additional emitter dopants may be used in conjunction with the compound of the present disclosure. Examples of the additional emitter dopants are not particularly limited, and any compounds may be used as long as the compounds are typically used as emitter materials. Examples of suitable emitter materials include, but are not limited to, compounds which can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
Non-limiting examples of the emitter materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103694277, CN1696137, EB01238981, EP01239526, EP01961743, EP1239526, EP1244155, EP1642951, EP1647554, EP1841834, EP1841834B, EP2062907, EP2730583, JP2012074444, JP2013110263, JP4478555, KR1020090133652, KR20120032054, KR20130043460, TW201332980, U.S. Ser. No. 06/699,599, U.S. Ser. No. 06/916,554, US20010019782, US20020034656, US20030068526, US20030072964, US20030138657, US20050123788, US20050244673, US2005123791, US2005260449, US20060008670, US20060065890, US20060127696, US20060134459, US20060134462, US20060202194, US20060251923, US20070034863, US20070087321, US20070103060, US20070111026, US20070190359, US20070231600, US2007034863, US2007104979, US2007104980, US2007138437, US2007224450, US2007278936, US20080020237, US20080233410, US20080261076, US20080297033, US200805851, US2008161567, US2008210930, US20090039776, US20090108737, US20090115322, US20090179555, US2009085476, US2009104472, US20100090591, US20100148663, US20100244004, US20100295032, US2010102716, US2010105902, US2010244004, US2010270916, US20110057559, US20110108822, US20110204333, US2011215710, US2011227049, US2011285275, US2012292601, US20130146848, US2013033172, US2013165653, US2013181190, US2013334521, US20140246656, US2014103305, U.S. Pat. Nos. 6,303,238, 6,413,656, 6,653,654, 6,670,645, 6,687,266, 6,835,469, 6,921,915, 7,279,704, 7,332,232, 7,378,162, 7,534,505, 7,675,228, 7,728,137, 7,740,957, 7,759,489, 7,951,947, 8,067,099, 8,592,586, 8,871,361, WO06081973, 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.
HBL:
A hole blocking layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies and/or longer lifetime as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (further from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.
In one aspect, compound used in HBL contains the same molecule or the same functional groups used as host described above.
In another aspect, compound used in HBL contains at least one of the following groups in the molecule:
wherein k is an integer from 1 to 20; L101 is an another ligand, k′ is an integer from 1 to 3.
ETL:
Electron transport layer (ETL) may include a material capable of transporting electrons. Electron transport layer may be intrinsic (undoped), or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complexes or organic compounds may be used as long as they are typically used to transport electrons.
In one aspect, compound used in ETL contains at least one of the following groups in the molecule:
wherein R101 is selected from the group consisting of hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acids, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof, when it is aryl or heteroaryl, it has the similar definition as Ar's mentioned above. Ar1 to Ar3 has the similar definition as Ar's mentioned above. k is an integer from 1 to 20. X101 to X108 is selected from C (including CH) or N.
In another aspect, the metal complexes used in ETL contains, but not limit to the following general formula:
wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L101 is another ligand; k′ is an integer value from 1 to the maximum number of ligands that may be attached to the metal.
Non-limiting examples of the ETL materials that may be used in an OLED in combination with materials disclosed herein are exemplified below together with references that disclose those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, U.S. Pat. Nos. 6,656,612, 8,415,031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,
Charge Generation Layer (CGL)
In tandem or stacked OLEDs, the CGL plays an essential role in the performance, which is composed of an n-doped layer and a p-doped layer for injection of electrons and holes, respectively. Electrons and holes are supplied from the CGL and electrodes. The consumed electrons and holes in the CGL are refilled by the electrons and holes injected from the cathode and anode, respectively; then, the bipolar currents reach a steady state gradually. Typical CGL materials include n and p conductivity dopants used in the transport layers.
In any above-mentioned compounds used in each layer of the OLED device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. may be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof.
A mixture of (2,4,6-triisopropylphenyl)boronic acid (8.46 g, 34.1 mmol), SPhos-Pd-G2 (0.818 g, 1.136 mmol), SPhos (0.467 g, 1.136 mmol), and potassium phosphate (18.09 g, 85 mmol) was vacuum and back-filled with nitrogen. 4-bromo-2-fluoropyridine (2.92 ml, 28.4 mmol), toluene (80 ml), and water (16 ml) were added to the reaction mixture and refluxed for 18 hrs then partitioned between ethyl acetate (EA) and brine and collected the organic portion. The aqueous layer was extracted with dichloromethane (DCM) and the combined organic extracts were dried with MgSO4 and coated on celite. The product was chromatographed on silica (EA/Hep=1/6) and obtained white solid product (84% yield).
A mixture of 2-bromo-9H-carbazole (3 g, 12.19 mmol), 2-fluoro-4-(2,4,6-triisopropylphenyl)pyridine (4.02 g, 13.41 mmol), and potassium carbonate (5.05 g, 36.6 mmol) in DMSO (60 ml) was heated at 150° C. for 48 hrs. The reaction mixture was cooled down and water (80 mL) was added. The solid product was collected by filtration and washed with water. The solid was triturated in EA/MeOH (1/10) and filtered. The off-white solid was dried in the vacuum oven (89% yield).
A mixture of (3-chloro-5-methoxyphenyl)boronic acid (5 g, 26.8 mmol), Pd(PPh3)4 (1.240 g, 1.073 mmol), and sodium carbonate (5.69 g, 53.6 mmol) was vacuum and back-filled with nitrogen. 2-bromo-1,3,5-triisopropylbenzene (6.80 ml, 26.8 mmol), Dioxane (75 ml), and water (15 ml) were added to the reaction mixture and refluxed for 18 hrs. The mixture was cooled down, most of dioxane was evaporated and extracted with DCM/brine. The product was chromatographed on silica (DCM/Hep=1/3) and the solvent was evaporated to afford a off-white solid product (66% yield).
tribromoborane (29.8 ml, 29.8 mmol) was added to a solution of 3′-chloro-2,4,6-triisopropyl-5′-methoxy-1,1′-biphenyl (3.43 g, 9.94 mmol) under nitrogen in dry DCM (30 ml) at 0° C. and stirred at room temperature (R.T.) for 5 hrs. The reaction was quenched with water slowly. After removing DCM, the white solid was stirred in water/MeOH (10/1) for 3 hrs and filtered (96% yield).
A mixture of 5-chloro-2′,4′,6′-triisopropyl-[1,1′-biphenyl]-3-ol (1.322 g, 4.00 mmol), 2-bromo-9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazole (2 g, 3.81 mmol), copper(I) iodide (0.145 g, 0.761 mmol), picolinic acid (0.187 g, 1.522 mmol), and potassium phosphate (1.616 g, 7.61 mmol) was vacuum and back-filled with nitrogen. DMSO (20 ml) was added to the reaction mixture and heated at 140° C. for 18 hrs. The mixture was cooled down and water (30 mL) was added. The resulting solid was collected by filtration and washed with water and dissolved in DCM. The product was chromatographed on silica (DCM/Hep=3/1) and the solvent was evaporated to obtain the product (77% yield).
A mixture of N1-phenylbenzene-1,2-diamine (0.591 g, 3.21 mmol), 2-((5-chloro-2′,4′,6′-triisopropyl-[1,1′-biphenyl]-3-yl)oxy)-9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazole (2.26 g, 2.91 mmol), (allyl)PdCl-dimer (0.032 g, 0.087 mmol), cBRIDP (0.123 g, 0.350 mmol), and sodium 2-methylpropan-2-olate (0.700 g, 7.29 mmol) was vacuumed and back-filled with nitrogen several times. Toluene (15 ml) was added to the reaction mixture and refluxed for 3 hrs. The reaction mixture was coated on celite and chromatographed on silica (DCM/Hep=2/1) to afford product (75% yield).
N1-phenyl-N2-(2′,4′,6′-triisopropyl-5-((9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-[1,1′-biphenyl]-3-yl)benzene-1,2-diamine (2 g, 2.166 mmol) was dissolved in triethoxymethane (18.01 ml, 108 mmol) and hydrogen chloride (0.213 ml, 2.60 mmol) was added. The reaction mixture was heated at 80° C. for 18 hrs. About half the amount of triehoxymethane was removed by distillation under vacuum until solid appeared. The solid was washed with diethyl ether and filtered (89% yield).
A mixture of 3-phenyl-1-(2′,4′,6′-triisopropyl-5-((9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-[1,1′-biphenyl]-3-yl)-1H-benzo[d]imidazol-3-ium chloride (1.83 g, 1.887 mmol) and silver oxide (0.219 g, 0.944 mmol) was stirred in 1,2-dichloroethane (25 ml) at R.T. for 18 hrs. After removing 1,2-dichloroethane, Pt(COD)Cl2 (0.706 g, 1.887 mmol) was added and the reaction mixture was vacuumed and back-filled with nitrogen. 1,2-dichlorobenzene (25 ml) was added and heated at 190° C. for 48 hrs. The solvent was removed and coated on celite and chromatographed on silica (DCM/Hep=1/1). The product was triturated in MeOH (81% yield).
A mixture of 3-(1H-imidazol-1-yl)phenol (0.274 g, 1.708 mmol), 2-bromo-9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazole (0.88 g, 1.674 mmol), copper(I) iodide (0.064 g, 0.335 mmol), picolinic acid (0.082 g, 0.670 mmol), and potassium phosphate (0.711 g, 3.35 mmol) was vacuumed and back-filled with nitrogen several times. DMSO (10 ml) was added to the reaction mixture and heated at 140° C. for 18 hrs. The mixture was cooled down and water (15 mL) was added. The resulting solid was collected by filtration and dissolved in DCM and dried with MgSO4. The product was chromatographed on silica (DCM/EA=3/1) to afford product (63% yield).
2-(3-(1H-imidazol-1-yl)phenoxy)-9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazole (622 mg, 1.028 mmol) was dissolved in EA (10 ml) and iodomethane-d3 (0.320 ml, 5.14 mmol) was added. The reaction mixture was stirred at R.T. for 3 days. The resulting off-white solid was collected by filtration and washed with EA and diethyl ether and dried under vacuum. (77% yield).
A mixture of 3-(methyl-d3)-1-(3-((9-(4-(2,4,6-triisopropylphenyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1H-imidazol-3-ium iodide (0.59 g, 0.787 mmol) and silver oxide (0.091 g, 0.393 mmol) was stirred in 1,2-dichloroethane (12 ml) at R.T. for 18 hrs. After removing 1,2-dichloroethane, Pt(COD)Cl2 (0.294 g, 0.787 mmol) was added and the reaction mixture was vacuumed and back-filled with nitrogen. 1,2-dichlorobenzene (12 ml) was added and heated at 190° C. for 24 hrs. The solvent was removed and coated on celite and chromatrographed on silica (DCM/Hep=2/1). The product was triturated in MeOH and dried in the vacuum oven (57% yield).
A mixture of 2-bromo-4-(tert-butyl)pyridine (5.65 g, 26.4 mmol), 2-bromo-9H-carbazole (5 g, 20.32 mmol), copper(I) iodide (1.548 g, 8.13 mmol), 1-methyl-1H-imidazole (1.612 ml, 20.32 mmol), and lithium 2-methylpropan-2-olate (3.25 g, 40.6 mmol) was vacuumed and back-filled with nitrogen several times. Toluene (60 ml) was added to the reaction mixture and heated at reflux for 4 hrs. The moisture was cooled down and partitioned between EA and water with ˜30 mL 30% NH4OH(aq). The organic layer was separated and the aqueous layer was extracted with DCM. Chromatographed on silica (DCM) (89% yield).
A mixture of 2-bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.5 g, 3.95 mmol), copper(I) iodide (0.151 g, 0.791 mmol), picolinic acid (0.195 g, 1.582 mmol), and potassium carbonate (1.679 g, 7.91 mmol) was vacuum and back-filled with nitrogen. 5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-ol (1.199 g, 4.15 mmol) and DMSO (15 ml) was added to the reaction mixture and heated at 140° C. for 18 hrs. The mixture was cooled down and water (20 mL) was added. The resulting solid was collected by filtration and washed with water and dissolved in DCM. The product was coated on celite and chromatographed on silica (DCM/Hep=4/1) (82% yield).
A mixture of (3-chloro-5-methoxyphenyl)boronic acid (6 g, 32.2 mmol), Pd(PPh3)4 (1.488 g, 1.288 mmol), and sodium carbonate (6.82 g, 64.4 mmol) was vacuum and back-filled with nitrogen. 2-bromo-1,3-diisopropylbenzene (6.63 ml, 32.2 mmol), dioxane (75 ml), and water (15 ml) were added to the reaction mixture and refluxed for 16 hrs. The mixture was cooled down and dioxane was removed and extracted with DCM/brine. The product was chromatographed on silica (DCM/Hep=2/3) to obtain a colorless liquid which solidified under vacuum (67% yield).
tribromoborane (42.9 ml, 42.9 mmol) was added to a solution of 3′-chloro-2,6-diisopropyl-5′-methoxy-1,1′-biphenyl (6.5 g, 21.46 mmol) under nitrogen in dry dichloromethane (40 ml) at 0° C. and stirred at R.T. for 5 hrs. The reaction mixture was quenched in an ice bath until some solid appeared. After removing DCM, the resulting white solid was stirred in water for 1 hr and filtered. The product was dried in the vacuum oven overnight (100% yield).
A mixture of N1-phenylbenzene-1,2-diamine (0.327 g, 1.774 mmol), 9-(4-(tert-butyl)pyridin-2-yl)-2-((5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)oxy)-9H-carbazole (0.947 g, 1.613 mmol), (allyl)PdCl-dimer (0.018 g, 0.048 mmol), cBRIDP (0.068 g, 0.194 mmol), and sodium 2-methylpropan-2-olate (0.387 g, 4.03 mmol) was vacuumed and back-filled with nitrogen several times. Toluene (10 ml) was added to the reaction mixture and refluxed for 3 hrs. The reaction mixture was coated on celite and chromatographed on silica (DCM/Hep=5/1 to 8/1) (75% yield).
N1-(5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)-N2-phenylbenzene-1,2-diamine (0.89 g, 1.211 mmol) was dissolved in triethoxymethane (10.07 ml, 60.5 mmol) and hydrogen chloride (0.119 ml, 1.453 mmol) was added. The reaction mixture was heated at 80° C. for 16 hrs. The mixture was cooled down and the solid was washed with diethyl ether and filtered and dried in the vacuum oven (85% yield).
A mixture of 1-(5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)-3-phenyl-1H-benzo[d]imidazol-3-ium chloride (0.8 g, 1.024 mmol) and silver oxide (0.119 g, 0.512 mmol) was stirred in 1,2-dichloroethane (10 ml) at R.T. for 16 hrs. After removing 1,2-dichloroethane, Pt(COD)Cl2 (0.383 g, 1.024 mmol) was added and the reaction mixture was vacuumed and back-filled with nitrogen. 1,2-dichlorobenzene (10 ml) was added and heated at 190° C. for 5 days. The solvent was removed and coated on celite and chromatographed on silica (DCM/Hep=1/1). The product was triturated in MeOH and dried in the vacuum oven (62% yield).
A mixture of 4-(tert-butyl)-2-chloropyridine (1.720 g, 10.14 mmol), 2-methoxy-9H-carbazole (2 g, 10.14 mmol), (allyl)PdCl-dimer (0.074 g, 0.203 mmol), and cBRIDP (0.286 g, 0.811 mmol) was vacuumed and back-filled with nitrogen several times. Toluene (30 ml) was added and the reaction mixture was refluxed for 4 hrs, partitioned between EA/water and extracted. The aqueous layer was extracted with DCM, then coated on celite and chromatographed on silica (DCM/EA=30/1) (81% yield).
9-(4-(tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole (2.72 g, 8.23 mmol) was heated in hydrogen bromide (46.6 ml, 412 mmol) at 140° C. (oil temp) for 1 hr. The mixture was cooled down and partitioned between DCM and water and extracted with DCM. The DCM layer was washed with NaHCO3(sat). Evaporation of organic solvent to obtain light yellow solid (86% yield).
A mixture of 1H-benzo[d]imidazole (3 g, 25.4 mmol), 1-bromo-3-iodobenzene (3.89 ml, 30.5 mmol), copper(I) iodide (0.484 g, 2.54 mmol), 1,10-phenanthroline (0.458 g, 2.54 mmol), and potassium carbonate (4.21 g, 30.5 mmol) was heated in DMF (70 ml) at 150° C. for 16 hrs. The mixture was cooled down and poured in cold water and extracted with DCM (insoluble salts were removed by filtration). Chromatographed on silica (EA/DCM=2/1) to obtain pale yellow tacky oil which solidified under vacuum overnight (59% yield).
A mixture of 1-(3-bromophenyl)-1H-benzo[d]imidazole (1.295 g, 4.74 mmol), 9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-ol (1.5 g, 4.74 mmol), copper(I) iodide (0.181 g, 0.948 mmol), picolinic acid (0.233 g, 1.896 mmol), and potassium phosphate (2.013 g, 9.48 mmol) was vacuumed and back-filled with nitrogen several times. DMSO (15 ml) was added to the reaction mixture and heated at 140° C. for 16 hrs. The mixture was cooled down and water (20 mL) was added. The resulting solid was collected by filtration and dissolved in DCM and dried with MgSO4. Chromatographed on silica (EA/DCM=1/1) (71% yield).
A mixture of 2-(3-(1H-benzo[d]imidazol-1-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (0.75 g, 1.475 mmol) and iodomethane-d3 (0.459 ml, 7.37 mmol) was refluxed in Acetonitrile (15 ml) for 3 days. The solvent was removed and triturated in EA (100% yield).
A mixture of 1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-3-(methyl-d3)-1H-benzo[d]imidazol-3-ium iodide (1 g, 1.530 mmol) and silver oxide (0.177 g, 0.765 mmol) was stirred in 1,2-dichloroethane (15 ml) at R.T. for 16 hrs. After removing 1,2-dichloroethane, Pt(COD)Cl2 (0.572 g, 1.530 mmol) was added and the reaction mixture was vacuumed and back-filled with nitrogen. 1,2-dichlorobenzene (15 ml) was added and heated at 190° C. for 3 days. The solvent was removed and coated on celite and chromatrographed on silica (DCM/Hep=2/1). The product was triturated in MeOH and dried in the vacuum oven (7% yield).
A mixture of 2-bromo-9H-carbazole (8 g, 32.5 mmol), 2-fluoropyridine (5.59 ml, 65.0 mmol), and potassium carbonate (13.48 g, 98 mmol) in DMSO (80 ml) was heated at 140° C. for 16 hrs. The mixture was cooled down, then the reaction mixture was extracted with EA and water and the organic portion was washed with brine and concentrated. The product solidified under vacuum (100% yield).
A mixture of 2-bromo-9-(pyridin-2-yl)-9H-carbazole (2.05 g, 6.34 mmol), copper(I) iodide (0.242 g, 1.269 mmol), picolinic acid (0.312 g, 2.54 mmol), and potassium carbonate (2.69 g, 12.69 mmol) was vacuum and back-filled with nitrogen. 3-chlorophenol (0.703 ml, 6.66 mmol) and DMSO (30 ml) was added to the reaction mixture and heated at 140° C. for 16 hrs. The mixture was cooled down and partitioned between EA and water and extracted with EA. The organic extracts were washed with brine and concentrated, then chromatographed on silica (DCM) (75% yield).
A mixture of N1-phenylbenzene-1,2-diamine (0.820 g, 4.45 mmol), 2-(3-chlorophenoxy)-9-(pyridin-2-yl)-9H-carbazole (1.5 g, 4.04 mmol), (allyl)PdCl-dimer (0.044 g, 0.121 mmol), cBRIDP (0.171 g, 0.485 mmol), and sodium 2-methylpropan-2-olate (0.972 g, 10.11 mmol) was vacuumed and back-filled with nitrogen several times. Toluene (15 ml) was added to the reaction mixture and refluxed for 3 hrs. The product was coated on celite and chromatographed on silica (EA/Hep=1/2) (66% yield).
N1-phenyl-N2-(3-((9-(pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine (1.4 g, 2.70 mmol) was dissolved in triethoxymethane (22.45 ml, 135 mmol) and hydrogen chloride (0.266 ml, 3.24 mmol) was added. The reaction mixture was heated at 80° C. for 30 min. The mixture was cooled down and diethyl ether (˜50 mL, solid appeared) was added to the reaction mixture and stirred for 5 hrs. The product was collected by filtration and was washed with diethyl ether and dried in the vacuum oven (75% yield).
A mixture of 3-phenyl-1-(3-((9-(pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium chloride (1.14 g, 2.017 mmol) and silver oxide (0.234 g, 1.009 mmol) was stirred in 1,2-dichloroethane (25 ml) at R.T. for 16 hrs. After removing 1,2-dichloroethane, Pt(COD)Cl2 (0.755 g, 2.017 mmol) was added and the reaction mixture was vacuumed and back-filled with nitrogen. 1,2-dichlorobenzene (25 ml) was added and heated at 190° C. for 48 hrs. The solvent was removed and coated on celite and chromatrographed on silica (DCM/Hep=2/1). The product was triturated in MeOH and dried in the vacuum oven (50% yield).
A mixture of 1-(3-bromophenyl)-1H-benzo[d]imidazole (0.8 g, 2.93 mmol), 3-(4-(2,6-diisopropylphenyl)-1H-pyrazol-1-yl)phenol (0.939 g, 2.93 mmol), copper(I) iodide (0.112 g, 0.586 mmol), picolinic acid (0.144 g, 1.172 mmol), and potassium phosphate (1.243 g, 5.86 mmol) was vacuumed and back-filled with nitrogen several times. DMSO (12 ml) was added to the reaction mixture and heated at 140° C. for 16 hrs. The mixture was cooled down and water (20 mL) was added. The resulting solid was collected by filtration and dissolved in DCM and dried with MgSO4. The product was coated on celite and chromatographed on silica (EA/DCM=1/4) (66% yield).
1-(3-(3-(4-(2,6-diisopropylphenyl)-1H-pyrazol-1-yl)phenoxy)phenyl)-1H-benzo[d]imidazole (0.987 g, 1.925 mmol) was dissolved in Ethyl acetate (15 ml) and iodomethane-d3 (0.359 ml, 5.78 mmol) was added and the reaction mixture was heated at 60° C. for 16 hrs. White precipitation appeared and it was collected by filtration and dried in the vacuum oven (75% yield).
A mixture of 1-(3-(3-(4-(2,6-diisopropylphenyl)-1H-pyrazol-1-yl)phenoxy)phenyl)-3-(methyl-d3)-1H-benzo[d]imidazol-3-ium iodide (820 mg, 1.247 mmol) and silver oxide (144 mg, 0.623 mmol) was stirred in 1,2-dichloroethane (8 ml) at R.T. for 16 hrs. After removing 1,2-dichloroethane, Pt(COD)Cl2 (467 mg, 1.247 mmol) was added and the reaction mixture was vacuumed and back-filled with nitrogen. 1,2-dichlorobenzene (8 ml) was added and heated at 80° C. for 16 hrs and 190° C. for 7 days. The solvent was removed and coated on celite and chromatrographed on silica (DCM/Hep=2/1). The product was triturated in MeOH and dried in the vacuum oven (63% yield).
A mixture of 2-bromo-1-(3-bromophenyl)ethan-1-one (3 g, 10.79 mmol) and 2,6-diisopropylaniline (4.02 g, 22.67 mmol) was stirred in Ethanol (15 ml) at R.T. for 2 days. EtOH was removed and triturated in diethyl ether. The white solid (salt) was removed by filtration. The filtrate was concentrated and chromatographed on silica (THF/Hep=1/20). Obtained yellow oil. (74% yield).
A mixture of 1-(3-bromophenyl)-2-((2,6-diisopropylphenyl)amino)ethan-1-one (2.3 g, 6.14 mmol), formaldehyde, 37% in water (0.503 ml, 6.76 mmol), and ammonium acetate (4.74 g, 61.4 mmol) was heated in Acetic Acid (20 ml) at reflux overnight. The mixture was cooled down and partitioned between EA and brine and extracted with EA. The organic extract was basified with Na2CO3(sat) until basic. Coated on celite and chromatographed on silica (EA/Hep=1/3) (20% yield).
A mixture of 4-(3-bromophenyl)-1-(2,6-diisopropylphenyl)-1H-imidazole (0.8 g, 2.087 mmol), copper(I) iodide (0.079 g, 0.417 mmol), picolinic acid (0.103 g, 0.835 mmol), and potassium carbonate (0.886 g, 4.17 mmol) was vacuum and back-filled with nitrogen. 5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-ol (0.633 g, 2.191 mmol) and DMSO (15 ml) was added to the reaction mixture and heated at 140° C. for 16 hrs. The mixture was cooled down and added water (20 mL). The resulting solid was collected by filtration and washed with water and dissolved in DCM. The product was coated on celite and chromatographed on silica (DCM/Hep=3/1 to 5/1) (71% yield).
A mixture of (allyl)PdCl-dimer (0.125 g, 0.342 mmol) and cBRIDP (0.482 g, 1.366 mmol) was vacuumed and back-filled with nitrogen. Toluene (10 ml) was added and refluxed for 3 minutes. The pre-formed catalyst was transferred to a mixture of 1-bromo-2-nitrobenzene (2.3 g, 11.39 mmol), 2,6-diisopropylaniline (2.58 ml, 13.66 mmol), and sodium 2-methylpropan-2-olate (2.74 g, 28.5 mmol) in Toluene (10 ml) and the reaction was refluxed for 2 hrs. The mixture was cooled down and coated on celite and chromatographed on silica (120 g×2, EA/Hep=1/9) (40% yield).
2,6-diisopropyl-N-(2-nitrophenyl)aniline (1.37 g, 4.59 mmol) was dissolved in ethanol (40 ml) and palladium or charcoal on dry basis (0.489 g, 0.459 mmol) was added. The reaction mixture was vacuumed and back-filled with a hydrogen balloon several times and stirred at R.T. for 16 hrs. Filtered through celite and washed with EA and concentrated to give product (93% yield).
A mixture of N1-(2,6-diisopropylphenyl)benzene-1,2-diamine (0.363 g, 1.353 mmol), 4-(3-((5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)oxy)phenyl)-1-(2,6-diisopropylphenyl)-1H-imidazole (0.8 g, 1.353 mmol), (allyl)PdCl-dimer (0.015 g, 0.041 mmol), cBRIDP (0.057 g, 0.162 mmol), and sodium 2-methylpropan-2-olate (0.325 g, 3.38 mmol) was vacuumed and back-filled with nitrogen several times. Toluene (10 ml) was added to the reaction mixture and refluxed for 2 hrs. Coated on celite and chromatographed on silica (DCM/Hep=5/1) (69% yield).
N1-(2,6-diisopropylphenyl)-N2-(5-(3-(1-(2,6-diisopropylphenyl)-1H-imidazol-4-yl)phenoxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)benzene-1,2-diamine (0.76 g, 0.923 mmol) was dissolved in triethoxymethane (7.68 ml, 46.2 mmol) and hydrogen chloride (0.091 ml, 1.108 mmol) was added. The reaction mixture was heated at 80° C. for 16 hrs. Triethyl orthoformate was removed by distillation under vacuum until solid appeared. The solid was washed with diethyl ether and filtered and dried in the vacuum oven (76% yield).
A mixture of 3-(2,6-diisopropylphenyl)-1-(5-(3-(1-(2,6-diisopropylphenyl)-1H-imidazol-4-yl)phenoxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)-1H-benzo[d]imidazol-3-ium chloride (0.6 g, 0.690 mmol) and silver oxide (0.080 g, 0.345 mmol) was stirred in 1,2-dichloroethane (10 ml) at R.T. for 16 hrs. After removing 1,2-dichloroethane, Pt(COD)Cl2 (0.258 g, 0.690 mmol) was added and the reaction mixture was vacuumed and back-filled with nitrogen. 1,2-dichlorobenzene (10 ml) was added and heated at 190° C. for 2 days. The solvent was removed and 1,3-diisopropylbenzene (5 mL) was added and refluxed in a sand bath for 7 days. The solvent was removed and coated on celite and chromatrographed on silica (DCM/Hep=1/1). The product was triturated in MeOH and dried in the vacuum oven (52% yield).
2-bromo-4-(tert-butyl)pyridine (5.75 g, 26.8 mmol), 2-bromo-9H-carbazole (5.08 g, 20.64 mmol), copper(I) iodide (1.572 g, 8.26 mmol), 1-methyl-1H-imidazole (1.637 ml, 20.64 mmol), and lithium 2-methylpropan-2-olate (3.30 g, 41.3 mmol) were added to a two-neck round-bottom flask with a stirbar. The reaction was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (50 ml) was added and the reaction was heated to reflux overnight. The reaction was cooled down and partitioned between EA and water with ˜30 mL 30% NH4OH(aq). The organic layer was separated, and the aqueous layer was extracted with DCM. Chromatographed on silica (DCM). Pure fractions were combined and pumped down to give a tan solid (73% yield).
5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-ol (1.135 g, 3.93 mmol), 2-bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.42 g, 3.74 mmol), copper(I) iodide (0.143 g, 0.749 mmol), picolinic acid (0.184 g, 1.497 mmol), and potassium phosphate, tribasic (1.589 g, 7.49 mmol) were added to a 250 mL round-bottom flask with a stirbar. The flask was cycled onto the line via three vacuum/N2 refill cycles. Dimethyl sulfoxide (25 ml) was added and the reaction was heated to 140° C. overnight. The reaction was cooled to r.t. and water was added to give a white ppt. The solid was then dissolved in DCM and dried with MgSO4, filtered, and coated onto Celite. FC run (4:1 DCM:Hep). Collected pure fractions and pumped down to give a white solid (63% yield).
N1-(2,6-diisopropylphenyl)benzene-1,2-diamine (0.683 g, 2.54 mmol), 9-(4-(tert-butyl)pyridin-2-yl)-2-((5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)oxy)-9H-carbazole (1.358 g, 2.313 mmol), Pd(allyl)Cl (0.025 g, 0.069 mmol), cBRIDP (0.098 g, 0.278 mmol), and sodium 2-methylpropan-2-olate (0.556 g, 5.78 mmol) were added to a 250 mL round-bottom flask with a stirbar. The reaction was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (15 mL) was added and the reaction was heated to reflux for two hours. Reaction was cooled to r.t. and solvent was removed in vacuo. Coated onto Celite and purified by column chromatography (5:1 DCM:Hep→8:1 DCM:Hep) to give a white solid (80% yield).
N1-(5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)-N2-(2,6-diisopropylphenyl)benzene-1,2-diamine (1.3 g, 1.587 mmol) was dissolved in triethoxymethane (13.20 ml, 79 mmol) in a 100 mL round-bottom flask with a stirbar. Hydrogen chloride (0.156 ml, 1.904 mmol) was added to give a color change from dark red to black. The reaction was heated to 80° C. overnight. The reaction was cooled to r.t. and the solvent was removed in vacuo to give a sticky solid (99% yield).
A mixture of 1-(5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)-3-(2,6-diisopropylphenyl)-1H-benzo[d]imidazol-3-ium chloride (1.37 g, 1.583 mmol) and silver oxide (0.183 g, 0.791 mmol) was stirred in 1,2-dichloroethane (10 mL) at r.t. overnight. Removed solvent and added Pt(COD)Cl2 (0.592 g, 1.583 mmol). The reaction mixture was refluxed in 1,2-dichlorobenzene (10 ml) for three nights. Removed solvent and coated on celite. Chromatographed on silica (2:3 DCM:Hep) to give a yellow solid (55% yield).
2-bromo-4-(tert-butyl)pyridine (5.75 g, 26.8 mmol), 2-bromo-9H-carbazole (5.08 g, 20.64 mmol), copper(I) iodide (1.572 g, 8.26 mmol), 1-methyl-1H-imidazole (1.637 ml, 20.64 mmol), and lithium 2-methylpropan-2-olate (3.30 g, 41.3 mmol) were added to a two-neck round-bottom flask with a stirbar. The reaction was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (50 ml) was added and the reaction was heated to reflux overnight. The reaction was cooled down and partitioned between EA and water with ˜30 mL 30% NH4OH(aq). The organic layer was separated, and the aqueous layer was extracted with DCM. Chromatographed on silica (DCM). Pure fractions were combined and pumped down to give a tan solid (73% yield).
5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-ol (1.135 g, 3.93 mmol), 2-bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.42 g, 3.74 mmol), copper(I) iodide (0.143 g, 0.749 mmol), picolinic acid (0.184 g, 1.497 mmol), and potassium phosphate, tribasic (1.589 g, 7.49 mmol) were added to a 250 mL round-bottom flask with a stirbar. The flask was cycled onto the line via three vacuum/N2 refill cycles. Dimethyl sulfoxide (25 ml) was added and the reaction was heated to 140° C. overnight. The reaction was cooled to r.t. and water was added to give a white ppt. The solid was then dissolved in DCM and dried with MgSO4, filtered, and coated onto Celite. FC run (4:1 DCM:Hep). Collected pure fractions and pumped down to give a white solid (63% yield).
9-(4-(tert-butyl)pyridin-2-yl)-2-((5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)oxy)-9H-carbazole (0.928 g, 1.580 mmol), N1-(2,6-diisobutylphenyl)benzene-1,2-diamine (0.515 g, 1.738 mmol), Pd(allyl)Cl (0.017 g, 0.047 mmol), cBRIDP (0.067 g, 0.190 mmol), and sodium 2-methylpropan-2-olate (0.380 g, 3.95 mmol) were added to a 250 mL round-bottom flask with a stirbar. The reaction was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (5 mL) was added and the reaction was heated to reflux. After 2 hr, the reaction was cooled to r.t. and the solvent was removed in vacuo. The reaction was coated onto Celite and purified by column chromatography (5:1 DCM:Hep→8:1 DCM:Hep). Pure fractions were pumped down to give a white foam (49% yield).
N1-(5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)-N2-(2,6-diisobutylphenyl)benzene-1,2-diamine (651 mg, 0.768 mmol) was dissolved in triethoxymethane (6391 μl, 38.4 mmol) in a 100 mL rbf with a stirbar. hydrogen chloride (76 μl, 0.922 mmol) was added to give a color change from dark to lighter red. The reaction was heated to 80° C. overnight. The solvent was removed in vacuo to give a pink solid. Added Et2O and collected solid by filtration (78% yield).
3-(5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)-1-(2,6-diisobutylphenyl)-1H-benzo[d]imidazol-3-ium chloride (534 mg, 0.598 mmol) and monosilver(I) monosilver(III) monoxide (69.2 mg, 0.299 mmol) were dissolved in 1,2-dichloroethane (10 ml) and stirred at r.t. overnight. The solvent was removed in vacuo and Pt(COD)Cl2 (224 mg, 0.598 mmol) was added along with ortho-dichlorobenzene (10.00 ml). The reaction was heated to reflux. After several days the reaction was cooled to r.t. and the solvent was removed in vacuo. The material was coated onto Celite and purified by column chromatography (3:2 Hep:DCM) to give a yellow solid (45% yield).
2-bromo-4-(tert-butyl)pyridine (5.75 g, 26.8 mmol), 2-bromo-9H-carbazole (5.08 g, 20.64 mmol), copper(I) iodide (1.572 g, 8.26 mmol), 1-methyl-1H-imidazole (1.637 ml, 20.64 mmol), and lithium 2-methylpropan-2-olate (3.30 g, 41.3 mmol) were added to a two-neck round-bottom flask with a stirbar. The reaction was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (50 ml) was added and the reaction was heated to reflux overnight. The reaction was cooled down and partitioned between EA and water with ˜30 mL 30% NH4OH(aq). The organic layer was separated, and the aqueous layer was extracted with DCM. Chromatographed on silica (DCM). Pure fractions were combined and pumped down to give a tan solid (73% yield).
5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-ol (1.135 g, 3.93 mmol), 2-bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.42 g, 3.74 mmol), copper(I) iodide (0.143 g, 0.749 mmol), picolinic acid (0.184 g, 1.497 mmol), and potassium phosphate, tribasic (1.589 g, 7.49 mmol) were added to a 250 mL round-bottom flask with a stirbar. The flask was cycled onto the line via three vacuum/N2 refill cycles. Dimethyl sulfoxide (25 ml) was added and the reaction was heated to 140° C. overnight. The reaction was cooled to r.t. and water was added to give a white ppt. The solid was then dissolved in DCM and dried with MgSO4, filtered, and coated onto Celite. FC run (4:1 DCM:Hep). Collected pure fractions and pumped down to give a white solid (63% yield).
N1-(2,6-bis(propan-2-yl-d7)phenyl)benzene-1,2-diamine (0.550 g, 1.948 mmol), 9-(4-(tert-butyl)pyridin-2-yl)-2-((5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)oxy)-9H-carbazole (1.04 g, 1.771 mmol), Pd(allyl)Cl (0.019 g, 0.053 mmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphane (0.075 g, 0.213 mmol), and sodium 2-methylpropan-2-olate (0.426 g, 4.43 mmol) were added to a 250 mL round-bottom flask with a stirbar. The reaction was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (15 mL) was added and the reaction was heated to reflux for two hours. Reaction was cooled to r.t. and solvent was removed in vacuo. Coated onto Celite and purified by column chromatography (5:1 DCM:Hep→8:1 DCM:Hep) to give a white solid (24% yield).
N1-(2,6-bis(propan-2-yl-d7)phenyl)-N2-(5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)benzene-1,2-diamine (0.346 g, 0.415 mmol) was dissolved in triethoxymethane (3.45 ml, 20.76 mmol) in a 100 mL round-bottom flask with a stirbar. Hydrogen chloride (0.041 ml, 0.498 mmol) was added to give a color change from dark red to black. The reaction was heated to 80° C. overnight. The reaction was cooled to r.t. and the solvent was removed in vacuo to give a sticky solid. Et2O was added and the solid was collected by filtration (71% yield).
1-(2,6-bis(propan-2-yl-d7)phenyl)-3-(5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)-1H-benzo[d]imidazol-3-ium chloride (260 mg, 0.296 mmol) and monosilver(I) monosilver(III) monoxide (34.2 mg, 0.148 mmol) were added to a 50 mL round-bottom flask with a stirbar. 1,2-dichloroethane (3 ml) was added and the reaction was allowed to stir at r.t. overnight. The reaction solvent was removed in vacuo and (COD)PtCl2 (111 mg, 0.296 mmol) was added along with ortho-dichlorobenzene (3.00 mL) and the reaction was heated to reflux for two nights. The reaction solvent was removed in vacuo and reaction was coated onto Celite and purified by column chromatography (1:1 DCM:Hep) to give a yellow solid (71% yield).
2-bromo-4-(tert-butyl)pyridine (5.75 g, 26.8 mmol), 2-bromo-9H-carbazole (5.08 g, 20.64 mmol), copper(I) iodide (1.572 g, 8.26 mmol), 1-methyl-1H-imidazole (1.637 ml, 20.64 mmol), and lithium 2-methylpropan-2-olate (3.30 g, 41.3 mmol) were added to a two-neck round-bottom flask with a stirbar. The reaction was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (50 ml) was added and the reaction was heated to reflux overnight. The reaction was cooled down and partitioned between EA and water with ˜30 mL 30% NH4OH(aq). The organic layer was separated, and the aqueous layer was extracted with DCM. Chromatographed on silica (DCM). Pure fractions were combined and pumped down to give a tan solid (73% yield).
5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-ol (1.135 g, 3.93 mmol), 2-bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.42 g, 3.74 mmol), copper(I) iodide (0.143 g, 0.749 mmol), picolinic acid (0.184 g, 1.497 mmol), and potassium phosphate, tribasic (1.589 g, 7.49 mmol) were added to a 250 mL round-bottom flask with a stirbar. The flask was cycled onto the line via three vacuum/N2 refill cycles. Dimethyl sulfoxide (25 ml) was added and the reaction was heated to 140° C. overnight. The reaction was cooled to r.t. and water was added to give a white ppt. The solid was then dissolved in DCM and dried with MgSO4, filtered, and coated onto Celite. FC run (4:1 DCM:Hep). Collected pure fractions and pumped down to give a white solid (63% yield).
N1-(2,6-dimethylphenyl)benzene-1,2-diamine (0.768 g, 3.62 mmol), 9-(4-(tert-butyl)pyridin-2-yl)-2-((5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)oxy)-9H-carbazole (1.93 g, 3.29 mmol), Pd(allyl)Cl (0.036 g, 0.099 mmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphane (0.139 g, 0.394 mmol), and sodium 2-methylpropan-2-olate (0.790 g, 8.22 mmol) were added to a 500 mL round-bottom flask. Anhydrous toluene (30 ml) was added and the reaction was heated to reflux overnight. Solvent was removed in vacuo and the material was coated onto Celite and purified by column chromatography (4:1 DCM:Hep) to give an off-white foam (53% yield).
N1-(5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)-N2-(2,6-dimethylphenyl)benzene-1,2-diamine (1.3 g, 1.704 mmol) was added to a 100 mL round-bottom flask with a stirbar. Triethoxymethane (14.17 ml, 85 mmol) was added followed by hydrogen chloride (0.168 ml, 2.044 mmol). The reaction was heated at 80 deg C. overnight. The reaction was cooled to r.t. and heptanes and Et2O were added to give a white ppt, which was collected by filtration (88% yield).
3-(5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)-1-(2,6-dimethylphenyl)-1H-benzo[d]imidazol-3-ium chloride (834 mg, 1.030 mmol) and monosilver(I) monosilver(III) monoxide (119 mg, 0.515 mmol) were added to a 100 mL round-bottom flask with a stirbar. 1,2-dichloroethane (3 ml) was added and the reaction was stirred at r.t. overnight. The reaction solvent was removed under vacuum and (COD)PtCl2 (385 mg, 1.030 mmol) was added along with ortho-dichlorobenzene (3.00 mL). The reaction was then placed to heat at reflux for four nights. The solvent was removed in vacuo and the reaction was coated onto Celite and purified by column chromatography (1:1 DCM:Hep) to give a yellow solid (69% yield).
2-bromo-4-(tert-butyl)pyridine (5.75 g, 26.8 mmol), 2-bromo-9H-carbazole (5.08 g, 20.64 mmol), copper(I) iodide (1.572 g, 8.26 mmol), 1-methyl-1H-imidazole (1.637 ml, 20.64 mmol), and lithium 2-methylpropan-2-olate (3.30 g, 41.3 mmol) were added to a two-neck round-bottom flask with a stirbar. The reaction was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (50 ml) was added and the reaction was heated to reflux overnight. The reaction was cooled down and partitioned between EA and water with ˜30 mL 30% NH4OH(aq). The organic layer was separated, and the aqueous layer was extracted with DCM. Chromatographed on silica (DCM). Pure fractions were combined and pumped down to give a tan solid (73% yield).
5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-ol (1.135 g, 3.93 mmol), 2-bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.42 g, 3.74 mmol), copper(I) iodide (0.143 g, 0.749 mmol), picolinic acid (0.184 g, 1.497 mmol), and potassium phosphate, tribasic (1.589 g, 7.49 mmol) were added to a 250 mL round-bottom flask with a stirbar. The flask was cycled onto the line via three vacuum/N2 refill cycles. Dimethyl sulfoxide (25 ml) was added and the reaction was heated to 140° C. overnight. The reaction was cooled to r.t. and water was added to give a white ppt. The solid was then dissolved in DCM and dried with MgSO4, filtered, and coated onto Celite. FC run (4:1 DCM:Hep). Collected pure fractions and pumped down to give a white solid (63% yield).
N1-([1,1′:3′,1″-terphenyl]-2′-yl)benzene-1,2-diamine hydrochloride (0.601 g, 1.611 mmol), 9-(4-(tert-butyl)pyridin-2-yl)-2-((5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)oxy)-9H-carbazole (0.946 g, 1.611 mmol), Pd(allyl)Cl (0.018 g, 0.048 mmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphane (0.068 g, 0.193 mmol), and sodium 2-methylpropan-2-olate (0.542 g, 5.64 mmol) were added to a 500 mL round-bottom flask with a stirbar. The reagents were cycled onto the line via three vacuum/N2 refill cycles. After three hours the reaction was pumped down to dryness and the material was coated onto Celite and purified by column chromatography (3:1 DCM:Hep). Pure fractions were combined and pumped down to give an off-white foam (39% yield).
N1-([1,1′:3′,1″-terphenyl]-2′-yl)-N2-(5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)benzene-1,2-diamine (0.55 g, 0.620 mmol) was added to a 250 mL round-bottom flask with a stirbar. Triethoxymethane (5.16 ml, 31.0 mmol) was added followed by hydrogen chloride (0.061 ml, 0.744 mmol). The reaction was placed to heat at 80° C. overnight. The reaction was cooled to r.t. and heptanes was added giving a ppt. This was collected by filtration and dried in a vacuum oven (76% yield).
1-([1,1′:3′,1″-terphenyl]-2′-yl)-3-(5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)-1H-benzo[d]imidazol-3-ium chloride (439 mg, 0.470 mmol) and monosilver(I) monosilver(III) monoxide (54.5 mg, 0.235 mmol) were added to a 100 mL round-bottom flask with a stirbar. 1,2-dichloroethane (3 ml) was added and the reaction was stirred at r.t. overnight. The solvent was removed in vacuo and (COD)PtCl2 (176 mg, 0.470 mmol) was added along with ortho-dichlorobenzene (3.00 mL). The reaction was heated to reflux for three nights. Cooled to r.t. and the solvent was removed using the Kugelrohr. The compound was coated onto Celite and purified by column chromatography (1:1 Hep:DCM) to give a yellow solid that was triturated with MeOH (52% yield).
2-bromo-4-(tert-butyl)pyridine (5.75 g, 26.8 mmol), 2-bromo-9H-carbazole (5.08 g, 20.64 mmol), copper(I) iodide (1.572 g, 8.26 mmol), 1-methyl-1H-imidazole (1.637 ml, 20.64 mmol), and lithium 2-methylpropan-2-olate (3.30 g, 41.3 mmol) were added to a two-neck round-bottom flask with a stirbar. The reaction was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (50 ml) was added and the reaction was heated to reflux overnight. The reaction was cooled down and partitioned between EA and water with ˜30 mL 30% NH4OH(aq). The organic layer was separated, and the aqueous layer was extracted with DCM. Chromatographed on silica (DCM). Pure fractions were combined and pumped down to give a tan solid (73% yield).
5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-ol (1.135 g, 3.93 mmol), 2-bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.42 g, 3.74 mmol), copper(I) iodide (0.143 g, 0.749 mmol), picolinic acid (0.184 g, 1.497 mmol), and potassium phosphate, tribasic (1.589 g, 7.49 mmol) were added to a 250 mL round-bottom flask with a stirbar. The flask was cycled onto the line via three vacuum/N2 refill cycles. Dimethyl sulfoxide (25 ml) was added and the reaction was heated to 140° C. overnight. The reaction was cooled to r.t. and water was added to give a white ppt. The solid was then dissolved in DCM and dried with MgSO4, filtered, and coated onto Celite. FC run (4:1 DCM:Hep). Collected pure fractions and pumped down to give a white solid (63% yield).
N1-(2-(tert-butyl)phenyl)benzene-1,2-diamine (0.336 g, 1.396 mmol), 9-(4-(tert-butyl)pyridin-2-yl)-2-((5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)oxy)-9H-carbazole (0.82 g, 1.396 mmol), Pd(allyl)Cl (0.015 g, 0.042 mmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphane (0.059 g, 0.168 mmol), and sodium 2-methylpropan-2-olate (0.336 g, 3.49 mmol) were added to a 250 mL round-bottom flask with a stirbar. The reaction was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (15 ml) was added and the reaction was placed to heat at reflux overnight. The reaction was cooled to r.t. and the solvent was removed in vacuo. A FC was run (3:1 DCM:Hep). The pure fractions were combined and dried to give a white foam (63% yield).
N1-(2-(tert-butyl)phenyl)-N2-(5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)benzene-1,2-diamine (697 mg, 0.881 mmol) was added to a 100 mL round-bottom flask with a stirbar. Triethoxymethane (7327 μl, 44.1 mmol) was added along with hydrogen chloride (87 μl, 1.057 mmol). The solution was placed to heat at 80° C. overnight. The solvent was removed in vacuo to give a reddish-white solid (99% yield).
1-(2-(tert-butyl)phenyl)-3-(5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)-1H-benzo[d]imidazol-3-ium chloride (950 mg, 1.134 mmol) and monosilver(I) monosilver(III) monoxide (131 mg, 0.567 mmol) were added to a 100 mL round-bottom flask with a stirbar. 1,2-dichloroethane (5 ml) was added and the reaction was stirred at r.t. overnight. The solvent was removed under vacuum and (COD)PtCl2 (424 mg, 1.134 mmol) was added along with ortho-dichlorobenzene (10 ml). The reaction was degassed and heated to reflux for four nights. The reaction was cooled to r.t. and the solvent was removed using the Kugelrohr. The compound was coated onto Celite and purified by column chromatography (1:1 Hep:DCM). The pure fractions were combined and pumped down. The material was dissolved in the minimum amount of DCM and then precipitated using MeOH. The yellow solid was collected on filter paper (62% yield).
2-bromo-4-(tert-butyl)pyridine (5.75 g, 26.8 mmol), 2-bromo-9H-carbazole (5.08 g, 20.64 mmol), copper(I) iodide (1.572 g, 8.26 mmol), 1-methyl-1H-imidazole (1.637 ml, 20.64 mmol), and lithium 2-methylpropan-2-olate (3.30 g, 41.3 mmol) were added to a two-neck round-bottom flask with a stirbar. The reaction was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (50 ml) was added and the reaction was heated to reflux overnight. The reaction was cooled down and partitioned between EA and water with ˜30 mL 30% NH4OH(aq). The organic layer was separated, and the aqueous layer was extracted with DCM. Chromatographed on silica (DCM). Pure fractions were combined and pumped down to give a tan solid (73% yield).
2-bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (5.96 g, 15.71 mmol), picolinic acid (0.774 g, 6.29 mmol), copper(I) iodide (0.599 g, 3.14 mmol), and potassium phosphate, tribasic (6.67 g, 31.4 mmol) were added to a 500 mL round-bottom flask with a stirbar. This was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous DMSO (79 ml) and 3-chlorophenol (1.704 ml, 16.50 mmol) were then added and the reaction was heated to 140° C. overnight. The reaction was cooled to r.t. and water was added to give a precipitate. The solid remaining after filtration was dissolved in DCM and washed with brine. The organic layer was dried over MgSO4, filtered, and coated onto Celite. The product was isolated via column chromatography (4:1 DCM:Hep) to give a white foam (76% yield).
N1-([1,1′:3′,1″-terphenyl]-2′-yl)benzene-1,2-diamine hydrochloride (0.891 g, 2.389 mmol), 9-(4-(tert-butyl)pyridin-2-yl)-2-(3-chlorophenoxy)-9H-carbazole (1.02 g, 2.389 mmol), Pd(allyl)Cl (0.026 g, 0.072 mmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphane (0.101 g, 0.287 mmol), and sodium 2-methylpropan-2-olate (0.804 g, 8.36 mmol) were added to a 250 mL round-bottom flask with a stirbar and cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (15 mL) was added and the reaction was heated to reflux overnight. The solvent was removed in vacuo and the product was isolated via column chromatography (3:1 DCM:Hep) as a white foam (83% yield).
N1-([1,1′:3′,1″-terphenyl]-2′-yl)-N2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine (1.44 g, 1.981 mmol) was added to a 100 mL round-bottom flask with a stirbar. Triethoxymethane (16.47 ml, 99 mmol) and hydrogen chloride (0.195 ml, 2.377 mmol) were added and the reaction was heated to 80° C. overnight. The reaction solvent was removed in vacuo and the compound was isolated as a red-white solid in quantitative yield.
1-([1,1′:3′,1″-terphenyl]-2′-yl)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium chloride (1.532 g, 1.981 mmol) and monosilver(I) monosilver(III) monoxide (0.230 g, 0.990 mmol) were added to a 250 mL round-bottom flask with a stirbar. 1,2-dichloroethane (10 ml) was added and the reaction was stirred at r.t. overnight. The solvent was removed in vacuo and (COD)PtCl2 (0.741 g, 1.981 mmol) and ortho-dichlorobenzene (10 ml) were added and the reaction was heated to reflux for five nights. The solvent was removed using a Kugelrohr apparatus and the compound was isolated via column chromatography (2:1 DCM:Hep) as a yellow solid. It was triturated in MeOH and dried in the vacuum oven (35% yield).
2-bromo-4-(tert-butyl)pyridine (5.75 g, 26.8 mmol), 2-bromo-9H-carbazole (5.08 g, 20.64 mmol), copper(I) iodide (1.572 g, 8.26 mmol), 1-methyl-1H-imidazole (1.637 ml, 20.64 mmol), and lithium 2-methylpropan-2-olate (3.30 g, 41.3 mmol) were added to a two-neck round-bottom flask with a stirbar. The reaction was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (50 ml) was added and the reaction was heated to reflux overnight. The reaction was cooled down and partitioned between EA and water with ˜30 mL 30% NH4OH(aq). The organic layer was separated, and the aqueous layer was extracted with DCM. Chromatographed on silica (DCM). Pure fractions were combined and pumped down to give a tan solid (73% yield).
2-bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (5.96 g, 15.71 mmol), picolinic acid (0.774 g, 6.29 mmol), copper(I) iodide (0.599 g, 3.14 mmol), and potassium phosphate, tribasic (6.67 g, 31.4 mmol) were added to a two-neck round-bottom flask with a stirbar. This was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous dimethyl sulfoxide (79 ml) and 3-chlorophenol (1.704 ml, 16.50 mmol) were then added and the reaction was heated to 140° C. overnight. The reaction was cooled to r.t. and water was added to give a precipitate. The solid was collected via filtration, dissolved in DCM, and washed with brine. The organic layer was dried over MgSO4, filtered, and coated onto Celite. FC run (4:1 DCM:Hep). The pure fractions were collected and pumped down to give a sticky white foam (76% yield).
N1-(2-(tert-butyl)phenyl)benzene-1,2-diamine (0.576 g, 2.396 mmol), 9-(4-(tert-butyl)pyridin-2-yl)-2-(3-chlorophenoxy)-9H-carbazole (1.023 g, 2.396 mmol), Pd(allyl)Cl (0.026 g, 0.072 mmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphane (0.101 g, 0.288 mmol), and sodium 2-methylpropan-2-olate (0.576 g, 5.99 mmol) were added to a two-neck flask with a stirbar. The reagents were cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (15 ml) was added and the reaction was heated to reflux. After 3 hrs, the solvent was removed in vacuo and a FC was run (3:1 DCM:Hep). The material was isolated as an off-white foam (69% yield).
N1-(2-(tert-butyl)phenyl)-N2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine (1.05 g, 1.664 mmol) was added to a 100 mL round-bottom flask with a stirbar. Triethoxymethane (13.84 ml, 83 mmol) was added to give a clear green solution. Addition of conc. hydrogen chloride (0.164 ml, 1.997 mmol) resulted in an immediate color change to orange. The solution was placed to heat at 80° C. overnight. The solvent was removed in vacuo to give a red-white solid (99% yield).
1-(2-(tert-butyl)phenyl)-3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium chloride (1.12 g, 1.654 mmol) and monosilver(I) monosilver(III) monoxide (0.192 g, 0.827 mmol) were added to a 100 mL round-bottom flask with a stirbar. 1,2-dichloroethane (5 ml) was added and the reaction was stirred at r.t. overnight. The solvent was removed in vacuo. (COD)PtCl2 (0.619 g, 1.654 mmol) was added along with ortho-dichlorobenzene (10 ml). The reaction was placed to heat at reflux. After heating for five nights, the reaction was cooled to r.t. and the solvent was removed on the Kugelrohr. Coated onto Celite and FC run (2:1 DCM:Hep). Isolated a yellow solid (59% yield).
2-bromo-4-(tert-butyl)pyridine (5.75 g, 26.8 mmol), 2-bromo-9H-carbazole (5.08 g, 20.64 mmol), copper(I) iodide (1.572 g, 8.26 mmol), 1-methyl-1H-imidazole (1.637 ml, 20.64 mmol), and lithium 2-methylpropan-2-olate (3.30 g, 41.3 mmol) were added to a two-neck round-bottom flask with a stirbar. The reaction was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (50 ml) was added and the reaction was heated to reflux overnight. The reaction was cooled down and partitioned between EA and water with ˜30 mL 30% NH4OH(aq). The organic layer was separated, and the aqueous layer was extracted with DCM. Chromatographed on silica (DCM). Pure fractions were combined and pumped down to give a tan solid (73% yield).
5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-ol (1.135 g, 3.93 mmol), 2-bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.42 g, 3.74 mmol), copper(I) iodide (0.143 g, 0.749 mmol), picolinic acid (0.184 g, 1.497 mmol), and potassium phosphate, tribasic (1.589 g, 7.49 mmol) were added to a 250 mL round-bottom flask with a stirbar. The flask was cycled onto the line via three vacuum/N2 refill cycles. Dimethyl sulfoxide (25 ml) was added and the reaction was heated to 140° C. overnight. The reaction was cooled to r.t. and water was added to give a white ppt. The solid was then dissolved in DCM and dried with MgSO4, filtered, and coated onto Celite. FC run (4:1 DCM:Hep). Collected pure fractions and pumped down to give a white solid (63% yield).
N-(2-(chloro-15-azaneyl)phenyl)-2,6-bis(methyl-d3)aniline (0.807 g, 3.17 mmol), 9-(4-(tert-butyl)pyridin-2-yl)-2-((5-chloro-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)oxy)-9H-carbazole (1.69 g, 2.88 mmol), Pd(allyl)Cl (0.032 g, 0.086 mmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphane (0.122 g, 0.345 mmol), and sodium 2-methylpropan-2-olate (0.968 g, 10.07 mmol) were added to a 250 mL round-bottom flask with a stirbar. Anhydrous toluene (30 ml) was added and the reaction was heated to reflux. After 2 hr, the solvent was removed in vacuo and the compound was isolated via column chromatography (4:1 DCM:Hep) as a white solid (23% yield).
N1-(2,6-bis(methyl-d3)phenyl)-N2-(5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)benzene-1,2-diamine (0.51 g, 0.663 mmol) was added to a 250 mL round-bottom flask with a stirbar. Triethoxymethane (5.52 ml, 33.2 mmol) was then added followed by hydrogen chloride (0.065 ml, 0.796 mmol) and the reaction was heated at 80° C. overnight. The reaction was pumped down to dryness to give a reddish white solid in quantitative yield.
1-(2,6-bis(methyl-d3)phenyl)-3-(5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)-2′,6′-diisopropyl-[1,1′-biphenyl]-3-yl)-1H-benzo[d]imidazol-3-ium chloride (580 mg, 0.711 mmol) and monosilver(I) monosilver(III) monoxide (82 mg, 0.356 mmol) were added to a 250 mL round-bottom flask with a stirbar. 1,2-dichloroethane (10 ml) was added and the reaction was stirred at r.t. overnight. The solvent was removed in vacuo and (COD)PtCl2 (266 mg, 0.711 mmol) and ortho-dichlorobenzene (10.00 ml) were added and the reaction was heated at reflux for five nights. The solvent was then removed in vacuo and the compound was isolated via column chromatography (1:1 Hep:DCM) to give a yellow solid. The solid was triturated with MeOH to give the final complex (43% yield).
A mixture of 1,3-dibromo-5-(tert-butyl)benzene (5.45 g, 18.65 mmol), 9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-ol (2.95 g, 9.32 mmol), copper(I) iodide (0.355 g, 1.865 mmol), picolinic acid (0.459 g, 3.73 mmol), and potassium phosphate (3.96 g, 18.65 mmol) was vacuumed and back-filled with nitrogen several times. DMSO (20 ml) was added to the reaction mixture and heated at 120° C. overnight. Cooled down and added water. The resulting brown solid was collected by filtration and dissolved in DCM, washed with brine, dried over MgSO4, and isolated by column chromatography (2:1 DCM:Hep) to give the final compound (59% yield).
N1-(2-(tert-butyl)phenyl)benzene-1,2-diamine (0.506 g, 2.106 mmol), 2-(3-bromo-5-(tert-butyl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (1.01 g, 1.915 mmol), Pd(allyl)Cl dimer (0.021 g, 0.057 mmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphane (0.081 g, 0.230 mmol), and sodium 2-methylpropan-2-olate (0.460 g, 4.79 mmol) were added to a 250 mL round-bottom flask with a stirbar. The reaction was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (20 ml) was added and the reaction was heated to reflux overnight. The solvent was removed in vacuo and the compound was isolated via column chromatography (4:1 DCM:Hep) to give an off-white foam (82% yield).
N1-(3-(tert-butyl)-5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-N2-(2-(tert-butyl)phenyl)benzene-1,2-diamine (1.08 g, 1.572 mmol) was added to a 100 mL round-bottom flask with a stirbar. Triethoxymethane (13.08 ml, 79 mmol) was added followed by the addition of hydrogen chloride (0.155 ml, 1.887 mmol). The solution was placed to heat at 80° C. overnight. The reaction solvent was removed in vacuo to give the target compound as a reddish-white solid in quantitative yield.
3-(3-(tert-butyl)-5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1-(2-(tert-butyl)phenyl)-1H-benzo[d]imidazol-3-ium chloride (1.1 g, 1.500 mmol) and monosilver(I) monosilver(III) monoxide (0.174 g, 0.750 mmol) were added to a 100 mL round-bottom flask with a stirbar. 1,2-dichloroethane (10 ml) was added and the reaction was stirred at r.t. overnight. The reaction solvent was removed in vacuo. Ortho-dichlorobenzene (10.00 ml) and (COD)PtCl2 (0.561 g, 1.500 mmol) were added and the reaction cycled onto the line via three vacuum/N2 refill cycles. It was placed to heat at reflux for eight days. The reaction was cooled to r.t. and the solvent was removed on the Kugelrohr. The target compound was isolated via column chromatography (1:1 Hep:DCM) as a yellow solid. The yellow solid was triturated in MeOH and dried in the vacuum oven (50% yield).
A mixture of 1,3-dibromo-5-(tert-butyl)benzene (5.45 g, 18.65 mmol), 9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-ol (2.95 g, 9.32 mmol), copper(I) iodide (0.355 g, 1.865 mmol), picolinic acid (0.459 g, 3.73 mmol), and potassium phosphate (3.96 g, 18.65 mmol) was vacuumed and back-filled with nitrogen several times. DMSO (20 ml) was added to the reaction mixture and heated at 120° C. overnight. Cooled down and added water. The resulting brown solid was collected by filtration and dissolved in DCM, washed with brine, dried over MgSO4, and isolated by column chromatography (2:1 DCM:Hep) to give the final compound (59% yield).
N-(2-(chloro-15-azaneyl)phenyl)-[1,1′:3′,1″-terphenyl]-2′-amine (0.762 g, 2.044 mmol), 2-(3-bromo-5-(tert-butyl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (0.98 g, 1.858 mmol), Pd(allyl)Cl dimer (0.020 g, 0.056 mmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphane (0.079 g, 0.223 mmol), and sodium 2-methylpropan-2-olate (0.625 g, 6.50 mmol) were added to a 250 mL round-bottom flask with a stirbar and cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (20 ml) was added and the reaction was heated to reflux overnight. The solvent was then removed in vacuo and the target compound was isolated via column chromatography (4:1 DCM:Hep) as a white foam (82% yield).
N1-([1,1′:3′,1″-terphenyl]-2′-yl)-N2-(3-(tert-butyl)-5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine (1.2 g, 1.533 mmol) was added to a 100 mL round-bottom flask with a stirbar. Triethoxymethane (12.75 ml, 77 mmol) was added followed by hydrogen chloride (0.151 ml, 1.839 mmol) and the reaction was placed to heat at 80° C. overnight. The reaction was cooled to r.t. and heptanes was added to give a sticky solid. The solvent was removed via filtration and the sticky solid was dissolved in DCM and pumped down. Heptanes was added and the material was scraped to give a white powder in (82% yield).
1-([1,1′:3′,1″-terphenyl]-2′-yl)-3-(3-(tert-butyl)-5-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium chloride (1.04 g, 1.254 mmol) and monosilver(I) monosilver(III) monoxide (0.145 g, 0.627 mmol) were added to a 250 mL round-bottom flask with a stirbar. 1,2-dichloroethane (10 ml) was added and the reaction was stirred at r.t. After 4 hrs the reaction was pumped down on the rotovap. (COD)PtCl2 (0.469 g, 1.254 mmol) and ortho-dichlorobenzene (10.00 ml) were added and the reaction was cycled onto the line via three vacuum/N2 refill cycles. The reaction was heated to reflux for seven days. The solvent was removed on the Kugelrohr and the compound was isolated via column chromatography (1:1 Hep:DCM) as a yellow solid that was then triturated in MeOH and dried in the vacuum oven (29% yield).
2-bromo-4-(tert-butyl)pyridine (5.75 g, 26.8 mmol), 2-bromo-9H-carbazole (5.08 g, 20.64 mmol), copper(I) iodide (1.572 g, 8.26 mmol), 1-methyl-1H-imidazole (1.637 ml, 20.64 mmol), and lithium 2-methylpropan-2-olate (3.30 g, 41.3 mmol) were added to a two-neck round-bottom flask with a stirbar. The reaction was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (50 ml) was added and the reaction was heated to reflux overnight. The reaction was cooled down and partitioned between EA and water with ˜30 mL 30% NH4OH(aq). The organic layer was separated, and the aqueous layer was extracted with DCM. Chromatographed on silica (DCM). Pure fractions were combined and pumped down to give a tan solid (73% yield).
2-bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (5.96 g, 15.71 mmol), picolinic acid (0.774 g, 6.29 mmol), copper(I) iodide (0.599 g, 3.14 mmol), and potassium phosphate, tribasic (6.67 g, 31.4 mmol) were added to a 500 mL round-bottom flask with a stirbar. This was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous DMSO (79 ml) and 3-chlorophenol (1.704 ml, 16.50 mmol) were then added and the reaction was heated to 140° C. overnight. The reaction was cooled to r.t. and water was added to give a precipitate. The solid remaining after filtration was dissolved in DCM and washed with brine. The organic layer was dried over MgSO4, filtered, and coated onto Celite. The product was isolated via column chromatography (4:1 DCM:Hep) to give a white foam (76% yield).
3,5-di-tert-butyl-N-(2-(chloro-15-azaneyl)phenyl)aniline (0.873 g, 2.62 mmol), 9-(4-(tert-butyl)pyridin-2-yl)-2-(3-chlorophenoxy)-9H-carbazole (1.018 g, 2.384 mmol), Pd(allyl)Cl (0.026 g, 0.072 mmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphane (0.101 g, 0.286 mmol), and sodium 2-methylpropan-2-olate (0.802 g, 8.35 mmol) were added to a 500 mL round-bottom flask with a stirbar. Anhydrous toluene (23.84 ml) was added and the reaction was heated to reflux overnight. The reaction was cooled to r.t. and the solvent was removed in vacuo. The target compound was isolated via column chromatography (4:1 DCM:Hep) as a white foam (67% yield).
N1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-N2-(3,5-di-tert-butylphenyl)benzene-1,2-diamine (1.1 g, 1.601 mmol) was added to a 100 mL round-bottom flask with a stirbar. Triethoxymethane (13.32 ml, 80 mmol) and hydrogen chloride (0.158 ml, 1.922 mmol) were added and the reaction was heated to 80° C. overnight. The reaction was cooled to r.t and the solvent was removed on the Kugelrohr to give an off-white solid (84% yield).
3-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)-1-(3,5-di-tert-butylphenyl)-1H-benzo[d]imidazol-3-ium chloride (0.99 g, 1.350 mmol) and monosilver(I) monosilver(III) monoxide (0.156 g, 0.675 mmol) were added to a 250 mL round-bottom flask with a stirbar. 1,2-dichloroethane (10 ml) was added and the reaction was stirred at r.t. overnight. The solvent was removed in vacuo and (COD)PtCl2 (0.505 g, 1.350 mmol) and ortho-dichlorobenzene (10.00 ml) were added. The reaction was cycled onto the line via three vacuum/N2 refill cycles. The reaction was heated to reflux for three nights. The reaction was cooled to r.t. and the solvent was removed on the Kugelrohr. The compound was isolated via column chromatography (1:1 DCM:Hep) to give a yellow solid that was triturated in MeOH and dried in the vacuum oven (64% yield).
2-bromo-4-(tert-butyl)pyridine (5.75 g, 26.8 mmol), 2-bromo-9H-carbazole (5.08 g, 20.64 mmol), copper(I) iodide (1.572 g, 8.26 mmol), 1-methyl-1H-imidazole (1.637 ml, 20.64 mmol), and lithium 2-methylpropan-2-olate (3.30 g, 41.3 mmol) were added to a two-neck round-bottom flask with a stirbar. The reaction was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous toluene (50 ml) was added and the reaction was heated to reflux overnight. The reaction was cooled down and partitioned between EA and water with ˜30 mL 30% NH4OH(aq). The organic layer was separated, and the aqueous layer was extracted with DCM. Chromatographed on silica (DCM). Pure fractions were combined and pumped down to give a tan solid (73% yield).
2-bromo-9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazole (5.96 g, 15.71 mmol), picolinic acid (0.774 g, 6.29 mmol), copper(I) iodide (0.599 g, 3.14 mmol), and potassium phosphate, tribasic (6.67 g, 31.4 mmol) were added to a 500 mL round-bottom flask with a stirbar. This was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous DMSO (79 ml) and 3-chlorophenol (1.704 ml, 16.50 mmol) were then added and the reaction was heated to 140° C. overnight. The reaction was cooled to r.t. and water was added to give a precipitate. The solid remaining after filtration was dissolved in DCM and washed with brine. The organic layer was dried over MgSO4, filtered, and coated onto Celite. The product was isolated via column chromatography (4:1 DCM:Hep) to give a white foam (76% yield).
N-(2-(chloro-15-azaneyl)phenyl)-[1,1′: 3′,1″-terphenyl]-2,2″,3,3″,4,4″,5,5″,6,6″-d10-2′-amine (1.717 g, 4.48 mmol), 9-(4-(tert-butyl)pyridin-2-yl)-2-(3-chlorophenoxy)-9H-carbazole (1.74 g, 4.08 mmol), Pd(allyl)Cl (0.045 g, 0.122 mmol), di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphane (0.172 g, 0.489 mmol), and sodium 2-methylpropan-2-olate (1.371 g, 14.26 mmol) were added to a 500 mL round-bottom flask with a stirbar. Anhydrous toluene (30 ml) was added and the reaction was heated to reflux overnight. The reaction was cooled to r.t. and the solvent was removed in vacuo. The target compound was isolated via column chromatography (4:1 DCM:Hep) as a white solid (83% yield).
N1-([1,1′:3′,1″-terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-N2-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine (2.5 g, 3.39 mmol) was added to a 100 mL round-bottom flask with a stirbar. Triethoxymethane (28.2 ml, 170 mmol) and hydrogen chloride (0.334 ml, 4.07 mmol) were added and the solution was heated to 80° C. overnight. The solvent was removed in vacuo and then heptanes was added. The solution was sonicated in heptanes and the white solid was collected via filtration and dried in the vacuum oven (86% yield).
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)-1H-benzo[d]imidazol-3-ium chloride (0.98 g, 1.251 mmol) and monosilver(I) monosilver(III) monoxide (0.145 g, 0.625 mmol) were added to a 250 mL round-bottom flask with a stirbar. 1,2-dichloroethane (10 ml) was added and the reaction was stirred at r.t. The solvent was removed in vacuo and (COD)PtCl2 (0.468 g, 1.251 mmol) and ortho-dichlorobenzene (10.00 ml) were added. The reaction was degassed via three vacuum/N2 refill cycles and heated to reflux for three nights. The reaction was cooled to r.t. and the solvent was removed using the Kugelrohr. The target compound was isolated via column chromatography (1:1 DCM:Hep→2:1 DCM:Hep) as a yellow solid. The compound was triturated in MeOH, collected via filtration, and dried in the vacuum oven overnight (33% yield).
3-(1H-imidazol-1-yl)phenol (0.795 g, 4.96 mmol), 1-(3-bromophenyl)-4-(2,6-diisopropylphenyl)-1H-pyrazole (1.73 g, 4.51 mmol), picolinic acid (0.222 g, 1.805 mmol), copper(I) iodide (0.172 g, 0.903 mmol), and potassium phosphate, tribasic (1.916 g, 9.03 mmol) were added to a 100 mL Schlenk tube with a stirbar. The flask was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous DMSO (45.1 ml) was added and the reaction was heated to 140° C. overnight. The reaction was cooled to r.t. and water was added giving a beige precipitate. The solid was collected via filtration and then dissolved in DCM and partitioned with water. The aq layer was extracted with DCM several times. The organic layers were combined and washed with brine. The organic fraction was then dried with MgSO4, filtered, and coated onto Celite. The compound was isolated via column chromatography (2:1 DCM:Hep) to give a white solid (1.39 g, 67%).
1-(3-(3-(1H-imidazol-1-yl)phenoxy)phenyl)-4-(2,6-diisopropylphenyl)-1H-pyrazole (1.39 g, 3.00 mmol) was dissolved in ethyl acetate (10 mL) in a 100 mL Schlenk tube under N2. iodomethane-d3 (0.935 mL, 15.02 mmol) was added via syringe and the reaction was heated to 60° C. overnight. A white precipitate formed in the reaction. The reaction was cooled to r.t. and heptanes was added. The solid was collected via filtration and dried in the vacuum oven to give an off-white solid (1.63 g, 89%).
1-(3-(3-(4-(2,6-diisopropylphenyl)-1H-pyrazol-1-yl)phenoxy)phenyl)-3-(methyl-d3)-1H-imidazol-3-ium iodide (0.623 g, 1.025 mmol) and monosilver(I) monosilver(III) monoxide (0.119 g, 0.513 mmol) were added to a 250 mL round-bottom flask with a stirbar. 1,2-dichloroethane (10 ml) was added and the reaction was stirred at r.t. overnight. The colorless solution was pumped down to dryness. The compound was dissolved in ortho-dichlorobenzene (10.00 ml) and added to a 100 mL Schlenk tube with a stirbar. (COD)PtCl2 (0.384 g, 1.03 mmol) was added to the reaction and the reaction was cycled onto the line via ten vacuum/N2 refill cycles. The reaction was placed to heat at reflux for several days. The reaction was cooled to r.t. and the solvent was removed in vacuo. The reaction was coated onto Celite and isolated by column chromatography (2:1 DCM:Hep) to give a yellow solid (0.53 g, 76%).
3-(1H-imidazol-1-yl)phenol (0.481 g, 3.00 mmol), 8-bromo-4,4,5,5-tetramethyl-3-phenyl-4,5-dihydropyrazolo[1,5-a]quinoline (1.04 g, 2.73 mmol), picolinic acid (0.134 g, 1.091 mmol), copper(I) iodide (0.104 g, 0.545 mmol), and potassium phosphate, tribasic (1.158 g, 5.45 mmol) were added to a 100 mL Schlenk tube with a stirbar. The flask was cycled onto the line via three vacuum/N2 refill cycles. Anhydrous DMSO (27.3 ml) was added and the reaction was heated to 140° C. overnight. The reaction was cooled to r.t. and water was added to give a beige precipitate. The precipitate was collected via filtration and dissolved in DCM and partitioned between DCM/water. The aq layer was extracted several times with DCM. The organic layers were combined and washed with brine. The organic fraction was dried with MgSO4, filtered, and coated onto Celite. The product was isolated via column chromatography (1:1 DCM:Hep→1:1 DCM:EtOAc) to give a white solid (0.81 g, 65%).
8-(3-(1H-imidazol-1-yl)phenoxy)-4,4,5,5-tetramethyl-3-phenyl-4,5-dihydropyrazolo[1,5-a]quinoline (0.81 g, 1.759 mmol) was added to a 100 mL Schlenk tube with a stirbar. Ethyl acetate (11.72 ml) was added followed by iodomethane-d3 (0.547 ml, 8.79 mmol). The reaction was placed to heat at 60° C. overnight. A white precipitate formed in the reaction. The reaction was cooled to r.t. and heptanes was added. The solid was collected via filtration and dried in the vacuum oven to give an off-white solid (0.89 g, 83%).
3-(methyl-d3)-1-(3-((4,4,5,5-tetramethyl-3-phenyl-4,5-dihydropyrazolo[1,5-a]quinolin-8-yl)oxy)phenyl)-1H-imidazol-3-ium iodide (0.491 g, 0.811 mmol) and monosilver(I) monosilver(III) monoxide (0.094 g, 0.405 mmol) were added to a 250 mL round-bottom flask with a stirbar. ClCH2CH2Cl (10 ml) was added and the reaction was stirred at r.t. overnight. The colorless solution was pumped down to dryness. The compound was dissolved in ortho-dichlorobenzene (10.00 ml) and added to a 100 mL Schlenk tube with a stirbar. (COD)PtCl2 (0.303 g, 0.811 mmol) was added to the reaction and the reaction was cycled onto the line via ten vacuum/N2 refill cycles. The reaction was placed to heat at reflux for several days. The reaction was cooled to r.t. and the solvent was removed in vacuo. The reaction was coated onto Celite and isolated by column chromatography (2:1 Hep:DCM) to give a yellow solid (0.38 g, 70%).
Table 1 shows the emission peak, PLQY, and excited state lifetime for the inventive compounds and Comparative Example. All inventive compounds showed higher PLQYs and shorter excited state lifetime (except for Compound 226820), indicating that they are very efficient emitters, which usually lead to higher device efficiencies. Their emissions in PMMA are in a range of 449-470 nm. Compound 95050 showed a very deep blue emission of 449 nm which is an excellent candidate for generating saturate blue for display application. Experiments have shown that RA and RC play an important role for physical property tuning. For example, when both Ar1 and Ar2=H (Compound 52843111), the complex decomposes before sublimation whereas Compound 20 and 87920 sublime cleanly to allow us to evaluate its device performance. These results suggest the physical properties of this family are very sensitive to the ligand structure. The Comparative Example also shows efficient and blue emission property; however, the device based on it is much less efficient.
OLED Device Fabrication:
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 ultra violet (UV) ozone for 5 minutes.
The devices in Tables 1 were fabricated in high vacuum (<10−6 Torr) by thermal evaporation. The anode electrode was 750 Å of ITO. The device example had organic layers consisting of, sequentially, from the ITO surface, 100 Å thick Compound A (HIL), 250 Å layer of Compound B (HTL), 50 Å of Compound C (EBL), 300 Å of Compound D doped with 10% of Emitter (EML), 50 Å of Compound E (BL), 300 Å of Compound G doped with 35% of Compound F (ETL), 10 Å of Compound G (EIL) followed by 1,000 Å of Al (Cathode). All devices were encapsulated with a glass lid sealed with an epoxy resin in a nitrogen glove box (<1 ppm of H2O and O2,) immediately after fabrication with a moisture getter incorporated inside the package. The doping percentages are in volume percent.
The structures of the compounds used in the experimental devices are shown below:
aa.u. = arbitrary units; all data is normalized relative to Comparative Example.
Table 2 shows device data for the inventive compounds, and Comparative Example. All inventive compounds exhibited lower voltage and higher efficiencies at 1000 nit as compared to those of Comparative Example. Compound 87893, 87894, 95050, 1249492640, 1249492644, 1249509383, and 1249509396 produced a CIE-y of 0.148 which is comparable or better to that of commercial fluorescent blue. Although the Comparative Example exhibited good deep blue color, its CIE-y is worse than most of inventive compounds. The device based on Comparative Example is much less efficient with a higher voltage.
It is understood that the various embodiments described herein are by way of example only, and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without deviating from the spirit of the invention. The present invention as claimed may therefore include variations from the particular examples and preferred embodiments described herein, as will be apparent to one of skill in the art. It is understood that various theories as to why the invention works are not intended to be limiting.
This application is a continuation-in-part of the co-pending U.S. patent application Ser. No. 15/967,732, filed on May 1, 2018, which claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Applications No. 62/524,080, filed Jun. 23, 2017, and No. 62/524,086, filed Jun. 23, 2017, the entire contents of which are incorporated herein by reference.
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| 20190119312 A1 | Apr 2019 | US |
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| 62524086 | Jun 2017 | US |
| Number | Date | Country | |
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| Parent | 15967732 | May 2018 | US |
| Child | 16211332 | US |
