Patent Description:
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 <CIT>,<CIT>, and <CIT>.

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(<NUM>-phenylpyridine) iridium, denoted Ir(ppy)<NUM>, which has the following structure:
<CHM>.

In this, and later figures herein, we depict the dative bond from nitrogen to metal (here, Ir) as a straight line.

As used herein, "solution processible" means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium, either in solution or suspension form.

<CIT> describes an organic electroluminescence device including an anode, an emitting layer, and a cathode, the emitting layer including a delayed-fluorescent first compound and a fluorescent second compound. <CIT> describes agents comprising cationic azacyanine dyes for coloring keratin fibers, such as, for example, wool, silk, furs or hair and, in particular, human hair. <NPL> the synthesis of a series of arylvinylene substituted phenanthroline derivatives and their application as electron transporting materials in organic light emitting diodes (OLEDs). <NPL> the one-step reaction of some amino-substituted heterocycles with diiodomethane to give azacyanines. <CIT> describes an OLED device comprising a light-emitting layer containing a host and a dopant, where the dopant comprises a boron compound complexed by two ring nitrogens of a deprotonated bis(azinyl)amine ligand. <NPL> the synthesis of a family of BODIPY dyes based on the pyridine-pyrimidine hybrid structure. <NPL> the complexation of a boron atom with a series of bidentate heterocyclic ligands to obtain boron(III)-cored dyes. <CIT> describes a one step process for reacting certain aminopyridines and pyrimidines with a methylene halide at reflux for from about overnight to about <NUM> hours to obtain corresponding N,N'-methylene-<NUM>,<NUM>'-azopyridocyanines. <NPL> the synthesis of azapyridocyanines from substituted <NUM>-aminopyridines and dihalomethane. <NPL> boron complexes having a pyridine-pyrimidine hybrid ligand structure.

An optoelectronic device selected from the group consisting of a photovoltaic device, a photodetector device, a photosensitive device, and an OLED, the optoelectronic device including an organic layer that comprises a compound of Formula X.

When a current is applied, the anode injects holes, and the cathode injects electrons into the organic layer(s).

More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in <CIT>. An example of a p-doped hole transport layer is m-MTDATA doped with F<NUM>-TCNQ at a molar ratio of <NUM>:<NUM>, as disclosed in <CIT>. Examples of emissive and host materials are disclosed in <CIT> An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of <NUM>:<NUM>, as disclosed in <CIT>. <CIT> and <CIT> , 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 <CIT> and <CIT>. Examples of injection layers are provided in <CIT>. A description of protective layers may be found in <CIT>.

The simple layered structure illustrated in <FIG> and <FIG> is provided by way of non-limiting example, and it is understood that embodiments of the invention may be used in connection with a wide variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely, based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe various layers as comprising a single material, it is understood that combinations of materials, such as a mixture of host and dopant, or more generally a mixture, may be used. Also, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device <NUM>, hole transport layer <NUM> transports holes and injects holes into emissive layer <NUM>, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to <FIG> and <FIG>.

Structures and materials not specifically described may also be used, such as OLEDs comprised of polymeric materials (PLEDs) such as disclosed in <CIT> By way of further example, OLEDs having a single organic layer may be used. OLEDs may be stacked, for example as described in <CIT> The OLED structure may deviate from the simple layered structure illustrated in <FIG> and <FIG>. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in <CIT>, and/or a pit structure as described in <CIT>.

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 <CIT> and <CIT> organic vapor phase deposition (OVPD), such as described in <CIT>, and deposition by organic vapor jet printing (OVJP), such as described in <CIT>. 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 <CIT> and <CIT>, 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 <NUM> carbons, may be used in small molecules to enhance their ability to undergo solution processing. Substituents having <NUM> carbons or more may be used, and <NUM>-<NUM> carbons is a preferred range. Materials with asymmetric structures may have better solution processibility 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 <CIT>, <CIT> and <CIT>. 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 <NUM>:<NUM> to <NUM>:<NUM>. 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 <NUM> inches diagonal (<NUM> inch = <NUM> centimeters)), <NUM>-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 <NUM> degrees C. to <NUM> degrees C. , and more preferably at room temperature (<NUM>-<NUM> degrees C), but could be used outside this temperature range, for example, from -<NUM> degree C to + <NUM> degree C.

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 -SO<NUM>-Rs radical.

The term "phosphino" refers to a -P(Rs)<NUM> radical, wherein each Rs can be same or different.

The term "silyl" refers to a -Si(Rs)<NUM> 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, <NUM>-methylethyl, butyl, <NUM>-methylpropyl, <NUM>-methylpropyl, pentyl, <NUM>-methylbutyl, <NUM>-methylbutyl, <NUM>-methylbutyl, <NUM>,<NUM>-dimethylpropyl, <NUM>,<NUM>-dimethylpropyl, <NUM>,<NUM>-dimethylpropyl. 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 <NUM> to <NUM> ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, bicyclo[<NUM>. <NUM>]heptyl, spiro[<NUM>]decyl, spiro[<NUM>]undecyl, adamantyl. 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 <NUM> to <NUM> ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino, and cyclic ethers/thioethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene. 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 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 <NUM> or <NUM> 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, <NUM>,<NUM>-azaborine, <NUM>,<NUM>-azaborine, <NUM>,<NUM>-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, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, 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 R<NUM> represents mono-substitution, then one R<NUM> must be other than H (i.e., a substitution). Similarly, when R<NUM> represents di-substitution, then two of R<NUM> must be other than H. Similarly, when R<NUM> represents no substitution, R<NUM>, 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 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, <CIT>, Patent Pub. No. <CIT>, and <CIT> describe the making of deuterium-substituted organometallic complexes. Further reference is made to <NPL> and <NPL> describe the deuteration of the methylene hydrogens in benzyl amines and efficient pathways to replace aromatic ring hydrogens with deuterium, respectively.

It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.

In one embodiment, the compounds of Formula X will have groups RZ and each R<NUM> and R<NUM> are independently hydrogen, or a substituent 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 another embodiment, the groups RZ and each R<NUM> and R<NUM> is independently selected from the group consisting of H, D, F, -CN, -CF<NUM>, alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, aryl, aryloxy, heterocycle, and heteroaryl.

In one embodiment, the compounds of Formula X will have Y as B(R<NUM>)<NUM>. In another embodiment, the compounds of Formula X will have Y as C(R<NUM>)<NUM>.

Of particular interest are compounds of Formula X that have Z as N.

Compounds of Formula X of particular interest will include Z being N, and Y being selected from B(R<NUM>)<NUM> or C(R<NUM>)<NUM>. A more preferred embodiment of such compounds will have R<NUM> being independently selected from the group consisting of H, D, F, -CN, -CF<NUM>, alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, aryl, aryloxy, heterocycle, and heteroaryl.

Compounds of Formula X of particular interest are selected from the group consisting of
<CHM>
wherein
R<NUM>, R<NUM>, and R<NUM> are independently selected from the group consisting of H, D, F, -CN, - CF<NUM>, C<NUM>-C<NUM> alkyl, C<NUM>-C<NUM> alkoxy, C<NUM>-C<NUM> alkenyl, C<NUM>-C<NUM> cycloalkyl, C<NUM>-C<NUM> aryl, C<NUM>-C<NUM> aryloxy, C<NUM>-C<NUM> heterocycle, and C<NUM>-C<NUM> heteroaryl.

The invention is also directed to an optoelectronic device selected from the group consisting of a photovoltaic device, a photodetector device, a photosensitive device, and an OLED, the optoelectronic device including an organic layer that comprises a compound of Formula X
<CHM>
wherein.

As noted above, in one embodiment the optoelectronic device will include an organic layer with the compounds of Formula X that have groups RZ and each R<NUM> and R<NUM> being independently hydrogen or a substituent 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 another embodiment, the groups RZ and each R<NUM> and R<NUM> is independently selected from the group consisting of H, D, F, -CN, -CF<NUM>, alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, aryl, aryloxy, heterocycle, and heteroaryl.

Optoelectronic devices that include compounds of Formula X will tend to emit in the deep blue, blue, and green regions of the visible spectrum.

An optoelectronic device of particular interest is an OLED, wherein the organic layer is disposed between an anode and a cathode. The OLED can be used in such consumer products such as telephones and flat panel displays.

Of particular interest are OLED with an organic layer that further comprises a phosphorescent emissive dopant with a formula of M(LA)x(LB)y(LC), wherein LA, LB and LC are each a ligand; and wherein x is <NUM>, <NUM>, or <NUM>; y is <NUM>, <NUM>, or <NUM>; z is <NUM>, <NUM>, or <NUM>; and x+y+z is the oxidation state of a metal M selected from the group consisting of Os, Ir, Cu, Pt, and Pd;.

In one embodiment, the phosphorescent emissive dopant will have a metal selected from Cu, Pt or Pd, and x is <NUM>, y is <NUM>, and z is <NUM>, wherein ligand LA and ligand LB can be the same or different, and the ligands LA and LB connect to form a tetradentate ligand.

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 <NUM> inch diagonal or <NUM> square inch area. In some embodiments, the OLED is a display panel having at least <NUM> inch diagonal or <NUM> square inch area. In some embodiments, the OLED is a lighting panel. <NUM> inch = <NUM> centimeters.

An emissive region in an OLED (e.g., the organic layer described herein) is disclosed. The emissive region comprises a first compound as described herein. In some embodiments, the first compound in the emissive region is an emissive dopant or a non-emissive dopant. In some embodiments, the emissive dopant further comprises a host, wherein the host comprises at least one selected from the group consisting of metal complex, triphenylene, carbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, azatriphenylene, aza-carbazole, aza-dibenzothiophene, aza-dibenzofuran, and aza-dibenzoselenophene. In some embodiments, the emissive region further comprises a host, wherein the host is selected from the group consisting of:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
and combinations thereof.

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+<NUM>, OCnH2n+<NUM>, OAr<NUM>, N(CnH2n+<NUM>)<NUM>, N(Ar<NUM>)(Ar<NUM>), CH=CH-CnH2n+<NUM>, C≡C-CnH2n+<NUM>, Ar<NUM>, Ar<NUM>-Ar<NUM>, and CnH2n-Ar<NUM>, or the host has no substitutions. In the preceding substituents n can range from <NUM> to <NUM>; and Ar<NUM> and Ar<NUM> 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.

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., <CIT>), triplet-triplet annihilation, or combinations of these processes. In some embodiments, the emissive dopant can be a racemic mixture, or can be enriched in one enantiomer.

In some embodiments, the compound can be used as a fluorescent acceptor in an OLED where one or multiple layers in the OLED contains one or more sensitizer compounds. A sensitizer compound is a compound that can donate energy to an acceptor. The sensitizer may be a phosphorescent compound or emitter, a delayed fluorescent compound or emitter, or an exciplex. The acceptor compound is capable of receiving energy transfer from the sensitizer and then emits the energy as light or further transfers the energy to a final emitter. The compound's concentration may range from <NUM>% to <NUM>% by weight percentage or from <NUM>% to <NUM>% by volume percentage. The compound may be in the same layer as the sensitizer or in one or more different layers. In some embodiments, the emission may arise from any or a combination of the sensitizer, the acceptor, and the final emitter.

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 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.

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: <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, and <CIT>. <CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

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: 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 <NUM>,<NUM>,<NUM>,<NUM>,<NUM>,<NUM>-Hexaazatriphenylenehexacarbonitrile; a metal complex, and a cross-linkable compounds.

Examples of aromatic amine derivatives used in HIL or HTL include the following general structures:
<CHM>
<CHM>.

Each of Ar<NUM> to Ar<NUM> 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 <NUM> to <NUM> 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, Ar<NUM> to Ar<NUM> is independently selected from the group consisting of:
<CHM>
<CHM>
wherein k is an integer from <NUM> to <NUM>; X<NUM> to X<NUM> is C (including CH) or N; Z<NUM> is NAr<NUM>, O, or S; Ar<NUM> has the same group defined above.

Examples of metal complexes used in HIL or HTL include the following general formula:
<CHM>
wherein Met is a metal, which can have an atomic weight greater than <NUM>; (Y<NUM>-Y<NUM>) is a bidentate ligand, Y<NUM> and Y<NUM> are independently selected from C, N, O, P, and S; L<NUM> is an ancillary ligand; k' is an integer value from <NUM> 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, (Y<NUM>-Y<NUM>) is a <NUM>-phenylpyridine derivative. In another aspect, (Y<NUM>-Y<NUM>) 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 <NUM> 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: <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>. <CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
and
<CHM>.

An electron blocking layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a blocking layer in a device may result in substantially higher efficiencies, and/or longer lifetime, as compared to a similar device lacking a blocking layer. Also, a blocking layer may be used to confine emission to a desired region of an OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in EBL contains the same molecule or the same functional groups used as one of the hosts described below.

The light emitting layer of the organic EL device of the present 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:
<CHM>
wherein Met is a metal; (Y<NUM>-Y<NUM>) is a bidentate ligand, Y<NUM> and Y<NUM> are independently selected from C, N, O, P, and S; L<NUM> is an another ligand; k' is an integer value from <NUM> 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:
<CHM>
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, (Y<NUM>-Y<NUM>) is a carbene ligand.

Examples of other organic compounds used as host are 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 <NUM> to <NUM> 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:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
and
<CHM>
wherein R<NUM> 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 <NUM> to <NUM> or <NUM> to <NUM>. X<NUM> to X<NUM> are independently selected from C (including CH) or N. Z<NUM> and Z<NUM> are independently selected from NR<NUM>, 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: <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>,
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

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 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: <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>. <CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
and
<CHM>.

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:
<CHM>
wherein k is an integer from <NUM> to <NUM>; L<NUM> is another ligand, k' is an integer from <NUM> to <NUM>.

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:
<CHM>
<CHM>
wherein R<NUM> 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. Ar<NUM> to Ar<NUM> has the similar definition as Ar's mentioned above. k is an integer from <NUM> to <NUM>. X<NUM> to X<NUM> is selected from C (including CH) or N.

In another aspect, the metal complexes used in ETL contains the following general formula:
<CHM>
wherein (O-N) or (N-N) is a bidentate ligand, having metal coordinated to atoms O, N or N, N; L<NUM> is another ligand; k' is an integer value from <NUM> 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: <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>, <CIT>,
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

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 methyl, phenyl, pyridyl, etc. may be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof.

<NUM> Torr = <NUM> Pa (not within the scope of the claims).

<NUM>,<NUM>-bis(<NUM>-(pyridin-<NUM>-yl)phenyl)-<NUM>-phenanthro[<NUM>,<NUM>-d]imidazole (I6) : A mixture of phenanthrene-<NUM>,<NUM>-dione (<NUM>, <NUM> mmol), <NUM>-(pyridin-<NUM>-yl)aniline (<NUM> <NUM> mmol), <NUM>-(pyridin-<NUM>-yl)benzaldehyde (<NUM>, <NUM> mmol) and ammonium acetate (<NUM>, <NUM> mmol) in glacial acetic acid (<NUM>) was refluxed for <NUM>. The precipitate was filtered and washed with aqueous NaOH deionized water. The residue is dried and sublimed at <NUM> and <NUM> ×<NUM>-<NUM> torr to give pure product. White solid (<NUM>, <NUM> mmol, <NUM>%).

Synthesis of aD: (a) <NUM>,<NUM>'-dipyridylamine (aD ligand): A reported procedure was followed (cite); bis(<NUM>-diphenylphosphinophenyl) ether(<NUM>, <NUM>. 51µmol), <NUM>-bromopyridine(<NUM>, <NUM>. 16mmol), <NUM>-aminopyridine (<NUM>, <NUM>. 16mmol) and t-BuONa (<NUM>, <NUM>. 43mmol) were purged with nitrogen gas in a re-sealable schlenk flask where a degassed dry toluene is cannula transferred. Pd(OAc)<NUM> catalyst was added to the air free flask and refluxed in a <NUM> oil bath for <NUM> hours. The reaction mixture is cooled to room temperature and diluted with THF and ethyl ether. The solid precipitate was filtered, concentrated, and purified via silica gel column chromatography (<NUM>%MeOH/CH<NUM>Cl<NUM>). An alternative route is to purchase the commercially available <NUM>,<NUM>'-dipyridylamine.

(b) aza-DIPYR (aD) (not part of the claimed invention): All reagents were purchased from Sigma Aldrich and used without purification. Anhydrous <NUM>,<NUM> dichloroethane was purchased from EMD Millipore. A solution of the <NUM>,<NUM>'-dipyridylamine ligand (<NUM>, <NUM>. 75mmol) in dry <NUM>,<NUM>-dichloroethane was prepared in an N2-purged schlenk flask equipped with a magnetic stir bar and fitted with a reflux condenser. The flask was submerged in a preheated oil bath and brought to reflux, at which time <NUM> eq. boron trifluoride diethyl etherate (<NUM>, <NUM>. 50mmol) were added dropwise. The solution was stirred for <NUM> hours at reflux, then cooled to room temperature and treated with <NUM> eq. N,N diisopropylethylamine (<NUM>, <NUM>. The solution was washed with water and the aqueous layer was separated and extracted three times with DCM. The total organic extractions were filtered, and reduced concentrated by rotary evaporation. The products were purified by silica gel flash chromatography with the eluent <NUM>% dichloromethane in hexanes.

(a) <NUM>,<NUM>'-diquinolylamine (α-aD ligand): A reported procedure was followed (cite); bis(<NUM>-diphenylphosphinophenyl) ether(<NUM>, <NUM>. 48µmol), <NUM>-bromoquinoline(<NUM>, <NUM>. 34mmol), <NUM>-aminoquinoline (<NUM>, <NUM>. 25mmol) and t-BuONa (<NUM>, <NUM>. 67mmol) were purged with nitrogen gas in a re-sealable schlenk flask where degassed dry toluene is cannula transferred. Pd(OAc)<NUM> (<NUM>, <NUM>. 48µmol) catalyst was added to the air free flask and refluxed in a <NUM> oil bath for <NUM> hours. The reaction mixture is cooled to room temperature and diluted with THF and ethyl ether. The solid precipitate was filtered, concentrated, and purified via silica gel column chromatography (<NUM>%MeOH/CH<NUM>Cl<NUM>). A white solid is isolated upon purification (<NUM>-<NUM>% yield).

(b) α-azaDIPYR (α-aD) (not part of the claimed invention): All reagents were purchased from Sigma Aldrich and used without purification. Anhydrous <NUM>,<NUM> dichloroethane was purchased from EMD Millipore. A <NUM> solution of <NUM>,<NUM>'-diquinolylamine in dry <NUM>,<NUM>-dichloroethane was prepared in an N<NUM>-purged schlenk flask equipped with a magnetic stir bar and fitted with a reflux condenser. The flask was submerged in a preheated oil bath and brought to reflux, at which time <NUM> eq. boron trifluoride diethyl etherate were added dropwise. The solution was stirred for <NUM> hours at reflux, then cooled to room temperature and treated with <NUM> eq. N,N diisopropylethylamine, causing the precipitate to dissolve. The solution was washed with water and the aqueous layer was separated and extracted three times with dichloromethane. The organic layers were combined, dried over sodium sulfate, filtered, and reduced concentrated by rotary evaporation. The products were purified by silica gel flash chromatography with the eluent <NUM>% <NUM>%MeOH/CH<NUM>Cl<NUM> solvent mixture in hexanes. For further purification, the material was sublimed.

<NUM>-isopropylquinoline (1a). <NUM>-isopropylaniline (<NUM>, <NUM>. 147mole), nitrobenzene (<NUM>, <NUM> mole), Glycerol (<NUM>, <NUM> mole), and FeSO<NUM>. <NUM><NUM>O (<NUM>, <NUM> mole) were added to a three-neck round bottom flask. While the flask was kept in an ice bath, H<NUM>SO<NUM> (<NUM>, <NUM> mole) was added slowly to the reaction mixture. After the addition was completed, the ice bath was removed followed by refluxing the mixture for <NUM> under inert conditions. After cooling to room temperature, the pH of the solution was adjusted to pH <NUM> with <NUM> % NaOH aq. Then, solution was extracted with diethyl ether. After the extraction, MgSO<NUM> was used as a drying agent. Filtration followed by evaporation to give a brown liquid. The product was isolated by reduced pressure distillation to yield the desired light-yellow liquid (yield <NUM> %).

<NUM>-isopropylquinoline-<NUM>-oxide (2a). Compound (1a) (<NUM>, <NUM> mole) was dissolved in one-neck round bottom flask with CH<NUM>Cl<NUM> (<NUM>). M-chloroperoxybenzoic acid (m-CPBA) (<NUM>, <NUM> mole) was added slowly the stirred solution at room temperature. The reaction was stirred overnight. Next, saturated NaHCO<NUM> aq solution was added to stirring solution until no CO<NUM> gas bubbles were observed anymore. Then, pH was adjusted to <NUM> with NaOH aq solution and extracted with CH<NUM>Cl<NUM> <NUM> three times. The solution was dried over MgSO<NUM>. The solvent was removed under reduced pressure. The crude product was then purified by silica gel column chromatography (<NUM> % Methanol/ CH<NUM>Cl<NUM>). White pale-yellow solid was afforded at <NUM> % yield.

<NUM>-isopropylquinoline-<NUM>-amine (3a). To a round bottom flask, compound (2a) (<NUM>, <NUM> mole) and <NUM> of trifluorotoluene (<NUM>, <NUM> mole) were mixed in <NUM> of chloroform. After compound (2a) was dissolved, the mixture was cooled to <NUM> with an ice bath. T-butylamine (<NUM>, <NUM> mole) was added slowly followed by Ts<NUM>O (<NUM>, <NUM> mole). The reaction was left to stir for two hours. If the reaction were not completed, portions of t-butylamine (<NUM> equiv. to <NUM> equiv. ) and Ts<NUM>O (<NUM> equiv. to <NUM> equiv. ) would be added until the reaction is completed. The reaction was then treated with <NUM> TFA at <NUM> <NUM>C for overnight under inert atmosphere. After that, most of the solvents were removed under reduced pressure and them the concentrated oil residue was diluted with CH<NUM>Cl<NUM> and quenched with <NUM> % of aq solution of NaOH to pH <NUM>. The solution was extracted with CH<NUM>Cl<NUM> three times, dried over MgSO<NUM>, and removed under reduced pressure. The crude product was then purified using a silica gel column chromatography (<NUM>% Methanol/CH<NUM>Cl<NUM>). The desired white solid was obtained at <NUM> %.

<NUM>-bromo-<NUM>-isopropylquinoline (4a). To a round bottom flask cooled to <NUM> with an ice bath, benzoyl chloride (<NUM>, <NUM> mol) was added slowly to the vigorously stirred mixture of compound (2a) (<NUM>, <NUM> mol), sodium hydroxide (<NUM>, <NUM> mol) in water (<NUM>) and CH<NUM>Cl<NUM> (<NUM>). After the addition is complete, the reaction mixture was left to stir for few hours. Then, the mixture was extracted from CH<NUM>Cl<NUM>. The combined organic layer was dried over MgSO<NUM>. Solvent was removed under reduced pressure to obtain a white solid product. After that, the solid was mixed with POBr<NUM> (<NUM>, <NUM> mol) in dry toluene (<NUM>) under inert atmosphere, heated to reflux overnight. After cooling to room temperature, the mixture was poured on ice, washed with saturated NaHCO<NUM> and extracted with CH<NUM>Cl<NUM> several times. The solvent was removed under reduced pressure. The crude product was then purified using a silica gel column chromatography (<NUM> % Hexane/CH<NUM>Cl<NUM>). The desired white solid was obtained at <NUM> %.

Bis(<NUM>-isopropylquinoline-<NUM>-yl)amine (5a). Compound (3a) (<NUM>, <NUM> mol) and compound (4a) (<NUM>, <NUM> mol) were mixed with bis(<NUM>-diphenylphosphinophenyl)ether (<NUM>, <NUM>% mmol), t-BuONa (<NUM>, <NUM> mol), and Pd(OAc)<NUM> (<NUM>, <NUM> % mmol) in a three-neck round bottom flask. The flask was subjected to three cycles of evacuation-backfilling with N<NUM>. Dry toluene purged with N<NUM> was transferred to the reaction mixture using a cannula. The reaction was refluxed for <NUM> at <NUM> under inert atmosphere. After that, the mixture was cooled to room temperature, extracted from CH<NUM>Cl<NUM>, dried over MgSO<NUM>, and solvent removed under reduced pressure. The crude product was then purified using a silica gel column chromatography (<NUM>% Methanol/CH<NUM>Cl<NUM>). The desired white solid was obtained at <NUM> %.

(α-aID) (not part of the claimed invention). Compound (5a) (<NUM>, <NUM> mol) was dissolved in dry toluene under N<NUM> in a three-neck round bottom flask. DIEA (<NUM>, <NUM>. 008mol) was slowly injected to the solution. After <NUM> stirring, BF<NUM>OEt<NUM> (<NUM>, <NUM> mol) was slowly added dropwise to the solution. The reaction was then left to reflux overnight. After cooling to room temperature, saturated solution of NaHCO<NUM> aq was added to the reaction mixture, followed by extraction from CH<NUM>Cl<NUM>. The combined organic layers were dried over MgSO<NUM>, and solvent removed under reduced pressure. The crude product was purified by silica gel chromatography (<NUM> % Hexane/ Ethyl acetate) to afford a yellow solid. The desired product was further sublimed at <NUM> under <NUM> × <NUM>-<NUM> torr.

<NUM>,<NUM>'-di-<NUM>-methoxyquinolylamine (α-5OD ligand): bis(<NUM>-diphenylphosphinophenyl) ether (<NUM>, <NUM>µmol), <NUM>-bromo-<NUM>-methoxyquinoline (<NUM>, <NUM> mmol), <NUM>-amino-<NUM>-methoxyquinoline (<NUM>, <NUM> mmol) and t-BuONa (<NUM>, <NUM> mmol), and Pd(OAc)<NUM> (<NUM>, <NUM>µmol) catalyst were added to a three-neck round bottom flask. The air free flask and refluxed in a <NUM> oil bath for <NUM> hours. The flask was subjected to three cycles of evacuation-backfilling with N<NUM>. Dry toluene purged with N<NUM> was transferred to the reaction mixture using a cannula. The reaction was refluxed for <NUM> at <NUM> under inert atmosphere. After that, the mixture was cooled to room temperature, extracted from CH<NUM>Cl<NUM>, dried over MgSO<NUM>, and solvent removed under reduced pressure. The crude product was then purified using a silica gel column chromatography (<NUM>% Methanol/CH<NUM>Cl<NUM>).

(α-5OD) (not part of the claimed invention). In a three-neck round bottom flask, the ligand, <NUM>,<NUM>'-di-<NUM>-methoxyquinolylamine (α-5OD ligand) (<NUM>, <NUM> mmol) was dissolved in dry toluene under N<NUM>. DIEA (<NUM>, <NUM> mmol) was slowly injected to the solution. After <NUM> of stirring, BF<NUM>OEt<NUM> (<NUM>, <NUM> mmol) was slowly added dropwise to the solution. The reaction was then left to reflux overnight. After cooling to room temperature, saturated solution of NaHCO<NUM> aq was added to the reaction mixture, followed by extraction from CH<NUM>Cl<NUM>. The combined organic layers were dried over MgSO<NUM>, and solvent removed under reduced pressure. The crude product was purified by silica gel chromatography (<NUM>% Methanol/CH<NUM>Cl<NUM>) to afford a yellow solid. The desired product was further sublimed at <NUM> under <NUM> × <NUM>-<NUM> torr.

<NUM>-methoxy-N-(quinolin-<NUM>-yl)quinolin-<NUM>-amine (αα-OD ligand): bis(<NUM>-diphenylphosphinophenyl) ether (<NUM>, <NUM>µmol), <NUM>-bromo-<NUM>-methoxyquinoline (<NUM>, <NUM> mmol), <NUM>-aminoquinoline (<NUM>, <NUM> mmol) and t-BuONa (<NUM>, <NUM> mmol), and Pd(OAc)<NUM> (<NUM>, <NUM>µmol) catalyst were added to a three-neck round bottom flask. The air free flask and refluxed in a <NUM> oil bath for <NUM> hours. The flask was subjected to three cycles of evacuation-backfilling with N<NUM>. Dry toluene purged with N<NUM> was transferred to the reaction mixture using a cannula. The reaction was refluxed for <NUM> at <NUM> under inert atmosphere. After that, the mixture was cooled to room temperature, extracted from CH<NUM>Cl<NUM>, dried over MgSO<NUM>, and solvent removed under reduced pressure. The crude product was then purified using a silica gel column chromatography (<NUM>% Methanol/CH<NUM>Cl<NUM>).

In a three-neck round bottom flask, the ligand, <NUM>-methoxy-N-(quinolin-<NUM>-yl)quinolin-<NUM>-amine (α-5OD ligand) (<NUM>, <NUM> mmol) was dissolved in dry toluene under N<NUM>. DIEA (<NUM>, <NUM> mmol) was slowly injected to the solution. After <NUM> of stirring, BF<NUM>OEt<NUM> (<NUM>, <NUM> mmol) was slowly added dropwise to the solution. The reaction was then left to reflux overnight. After cooling to room temperature, saturated solution of NaHCO<NUM> aq was added to the reaction mixture, followed by extraction from CH<NUM>Cl<NUM>. The combined organic layers were dried over MgSO<NUM>, and solvent removed under reduced pressure. The crude product was purified by silica gel chromatography (<NUM>% Methanol/CH<NUM>Cl<NUM>) to afford a yellow solid. The desired product was further sublimed at <NUM> under <NUM> × <NUM>-<NUM> torr.

N-(isoquinolin-<NUM>-yl)-<NUM>-methoxyquinolin-<NUM>-amine (α□-OD ligand): bis(<NUM>-diphenylphosphinophenyl) ether (<NUM>, <NUM>µmol), <NUM>-amino-<NUM>-methoxyquinoline (<NUM>, <NUM> mmol), <NUM>-chloroisoquinoline (<NUM>, <NUM> mmol) and t-BuONa (<NUM>, <NUM> mmol), and Pd(OAc)<NUM> (<NUM>, <NUM>µmol) catalyst were added to a three-neck round bottom flask. The air free flask and refluxed in a <NUM> oil bath for <NUM> hours. The flask was subjected to three cycles of evacuation-backfilling with N<NUM>. Dry toluene purged with N<NUM> was transferred to the reaction mixture using a cannula. The reaction was refluxed for <NUM> at <NUM> under inert atmosphere. After that, the mixture was cooled to room temperature, extracted from CH<NUM>Cl<NUM>, dried over MgSO<NUM>, and solvent removed under reduced pressure. The crude product was then purified using a silica gel column chromatography (<NUM>% Methanol/CH<NUM>Cl<NUM>).

Claim 1:
A compound of Formula X
<CHM>
wherein
ring A is absent, or present and selected from a <NUM>-membered or <NUM>-membered, carbocyclic or heterocyclic ring, which is optionally substituted;
ring B is absent, or present and selected from a <NUM>-membered or <NUM>-membered, carbocyclic or heterocyclic ring, which is optionally substituted;
wherein at least one of ring A or ring B is present, and the hash line represents ring A fused to ring N-W<NUM>-W<NUM> and ring B fused to ring N-W<NUM>-W<NUM>;
W<NUM>, W<NUM>, W<NUM>, W<NUM>, W<NUM>, and W<NUM> are independently selected from CR<NUM> or N;
Z is selected from CRZ or N;
Y is selected from a group consisting of C(R<NUM>)<NUM>, B(R<NUM>)<NUM>, Al(R<NUM>)<NUM>, Si(R<NUM>)<NUM>, and Ge(R<NUM>)<NUM>; wherein
RZ and each R<NUM> and R<NUM> are independently 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; or optionally, two R<NUM> join to form a cycloalkyl or heterocyclic ring;
wherein optionally, R<NUM> can join with RZ to form a five-membered or six-membered, carbocyclic or heterocyclic ring, which is optionally substituted; and
wherein one of W<NUM>, W<NUM>, or W<NUM> is N, and one of W<NUM>, W<NUM>, or W<NUM> is N.