ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES

Provided are organometallic compounds. Also provided are formulations comprising these organometallic compounds. Further provided are OLEDs and related consumer products that utilize these organometallic compounds.

FIELD

The present disclosure generally relates to organometallic compounds and formulations and their various uses including as emitters in devices such as organic light emitting diodes and related electronic devices.

BACKGROUND

Opto-electronic devices that make use of organic materials are becoming increasingly desirable for various reasons. Many of the materials used to make such devices are relatively inexpensive, so organic opto-electronic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications such as fabrication on a flexible substrate. Examples of organic opto-electronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, the organic materials may have performance advantages over conventional materials.

OLEDs make use of thin organic films that emit light when voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, illumination, and backlighting.

SUMMARY

In one aspect, the present disclosure provides a compound comprising a ligand LAof

wherein one of Z1and Z2is C and the other is N; each of K1and K2is independently a direct bond, S, or O; ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; RArepresents zero, mono, or up to the maximum allowed number of substitutions to its associated ring; each of X1-X7is independently N or CR; at least one of R and RAhas a structure of

wherein: each of X8-X15is independently N or CR′, the particular one of X8-X15that is bonded to one of X1-X7or ring A of Formula I is C; the maximum number of N atoms that can connect to each other within a ring is two; each of the remaining R and RAis independently a hydrogen, Formula II, Formula III, or a substituent selected from the group consisting of the general substituents defined herein; each of R′ and RBis independently a hydrogen, or a substituent selected from the group consisting of the general substituents defined herein; the ligand LAis coordinated to a metal M by the indicated dash lines; the ligand LAcan be linked with other ligands to form a tridentate or tetradentate ligand; M is Pd or Pt, and can be coordinated to additional ligands; and any two adjacent R, R′, or RAcan be joined or fused together to form a ring.

In another aspect, the present disclosure provides a formulation of a compound comprising a ligand LAof Formula I as described herein.

In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a compound comprising a ligand LAof Formula I as described herein.

In yet another aspect, the present disclosure provides a consumer product comprising an OLED with an organic layer comprising a compound comprising a ligand LAof Formula I as described herein.

DETAILED DESCRIPTION

The term “ester” refers to a substituted oxycarbonyl (—O—C(O)—R5or —C(O)—O—R5) radical.

The term “ether” refers to an —OR5radical.

The term “sulfinyl” refers to a —S(O)—R5radical.

The term “sulfonyl” refers to a —SO2—R5radical.

The term “phosphino” refers to a —P(R5)3radical, wherein each R5can be same or different.

The term “silyl” refers to a —Si(R5)3radical, wherein each R5can be same or different.

The term “boryl” refers to a —B(R5)2radical or its Lewis adduct —B(R5)3radical, wherein R5can be same or different.

The term “alkenyl” refers to and includes both straight and branched chain alkene radicals. Alkenyl groups are essentially alkyl groups that include at least one carbon-carbon double bond in the alkyl chain Cycloalkenyl groups are essentially cycloalkyl groups that include at least one carbon-carbon double bond in the cycloalkyl ring. The term “heteroalkenyl” as used herein refers to an alkenyl radical having at least one carbon atom replaced by a heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Preferred alkenyl, cycloalkenyl, or heteroalkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl, cycloalkenyl, or heteroalkenyl group may be optionally substituted.

The term “alkynyl” refers to and includes both straight and branched chain alkyne radicals. Alkynyl groups are essentially alkyl groups that include at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted.

The terms “aralkyl” or “arylalkyl” are used interchangeably and refer to an alkyl group that is substituted with an aryl group. Additionally, the aralkyl group may be optionally substituted.

The term “heterocyclic group” refers to and includes aromatic and non-aromatic cyclic radicals containing at least one heteroatom. Optionally the at least one heteroatom is selected from O, S, N, P, B, Si, and Se, preferably, O, S, or N. Hetero-aromatic cyclic radicals may be used interchangeably with heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino, and the like, and cyclic ethers/thio-ethers, such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. Additionally, the heterocyclic group may be optionally substituted.

In some instances, the preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, boryl, aryl, heteroaryl, sulfanyl, and combinations thereof.

In yet other instances, the more preferred general substituents are selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

The terms “substituted” and “substitution” refer to a substituent other than H that is bonded to the relevant position, e.g., a carbon or nitrogen. For example, when R1represents mono-substitution, then one R1must be other than H (i.e., a substitution). Similarly, when R1represents di-substitution, then two of R1must be other than H. Similarly, when R1represents zero or no substitution, R1, for example, can be a hydrogen for available valencies of ring atoms, as in carbon atoms for benzene and the nitrogen atom in pyrrole, or simply represents nothing for ring atoms with fully filled valencies, e.g., the nitrogen atom in pyridine. The maximum number of substitutions possible in a ring structure will depend on the total number of available valencies in the ring atoms.

In some instance, a pair of adjacent substituents can be optionally joined or fused into a ring. The preferred ring is a five, six, or seven-membered carbocyclic or heterocyclic ring, includes both instances where the portion of the ring formed by the pair of substituents is saturated and where the portion of the ring formed by the pair of substituents is unsaturated. As used herein, “adjacent” means that the two substituents involved can be on the same ring next to each other, or on two neighboring rings having the two closest available substitutable positions, such as 2, 2′ positions in a biphenyl, or 1, 8 position in a naphthalene, as long as they can form a stable fused ring system.

B. The Compounds of the Present Disclosure

In one aspect, the present disclosure provides a compound comprising a ligand LAof

wherein:
one of Z1and Z2is C and the other is N;
each of K1and K2is independently a direct bond, S, or O;
ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring;
RArepresents zero, mono, or up to the maximum allowed number of substitutions to its associated ring;
each of X1-X7is independently N or CR;
at least one of R and RAhas a structure of

wherein: each squiggly line represents a bond to the relevant part of Formula I;
each of X8-X15is independently N or CR′, the particular one of X8-X15that is bonded to one of X1-X7or ring A of Formula I is C;
the maximum number of N atoms that can connect to each other within a ring is two;
each of the remaining R and RAis independently a hydrogen, Formula II, Formula III, or a substituent selected from the group consisting of then general substituents defined herein;
each of R1and RBis independently a hydrogen or a substituent selected from the group consisting of the general substituents defined herein;
the ligand LAis coordinated to a metal M by the indicated dash lines;
the ligand LAcan be linked with other ligands to form a tridentate or tetradentate ligand;
M is Pd or Pt, and can be coordinated to additional ligands; and
any two adjacent R, R′, or RAcan be joined or fused together to form a ring.

In some embodiments, one R can have a structure of Formula II or Formula III. In some embodiments, one RAcan have a structure of Formula II or Formula III.

In some embodiments, in addition to at least one of R and RAhaving a structure of Formula II or Formula III, each of the remaining R and RAcan be independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof.

In some embodiments, K1and K2can be each a direct bond. In some embodiments, one of K1or K2can be 0.

In some embodiments, X1-X7can each be independently CR, and X8-X15can each be independently C or CR′. In some embodiments, one of X1-X15can be N, and the remainder can each be independently CR for X1-X7and independently C or CR1for X8-X15. In some embodiments, one of X1-X4can be N, and the remainder of X1-X15can each be independently CR for X1-X7and independently C or CR1for X8-X15. In some embodiments, one of X5-X7can be N, and the remainder of X1-X15can each be independently CR for X1-X7and independently C or CR1for X8-X15. In some embodiments, one of X8-X15can be N, and the remainder of X1-X15can each be independently CR for X1-X7and independently C or CR1for X8-X15. In some embodiments, one of X12-X15can be N, and the remainder of X1-X15can each be independently CR for X1-X7and independently C or CR1for X8-X15. In some embodiments, two of X1-X15can be N, and the remainder of X1-X15can each be independently CR for X1-X7and independently C or CR1for X8-X15. In some embodiments, two of X1-X7can be N, and the remainder of X1-X15can each be independently CR for X1-X7and independently C or CR1for X8-X15. In some embodiments, two of X8-X15can be N, and the remainder of X1-X15can each be independently CR for X1-X7and independently C or CR1for X8-X15. In some embodiments, one of X1-X7can be N, one of X8-X15can be N, and the remainder of X1-X15can each be independently CR for X1-X7and independently C or CR1for X8-X15.

In some embodiments, Z1can be N, and Z2can be C. In some embodiments, Z1can be C, and Z2can be N.

In some embodiments, ring A can be a 5-membered or 6-membered aromatic ring. In some embodiments, ring A can be selected from the group consisting of pyrimidine, pyridine, pyridazine, pyrazine, triazine, benzene, imidazole, triazole, pyrazole, isothiazole, oxazole, and thiazole. In some embodiments, ring A can be selected from the group consisting of pyridine, pyrimidine, benzene, and imidazole.

In some embodiments, the compound can comprise a ligand LAof

wherein X1-X15, Z1, Z2, R, RA, RBand ring A are all same as defined above for Formula I.

In the above embodiments, RAcan be an alkyl, a cycloalkyl, an aryl, a heteroaryl, or a combination thereof. In some embodiments, RAcan be an alkyl, or a cycloalkyl.

In some embodiments, the ligand LAcan be a tetradentate ligand.

In some embodiments, the compound can have a structure of

wherein:
each of X1-X6is independently N or CR;
at least one of R and RAhas a structure of

wherein: each squiggly line represents a bond to the relevant part of Formula VI;
each of X8-X15is independently N or CR′, the particular one of X8-X15that is bonded to one of X1-X6or ring A of Formula I is C; rings C and D are each independently a 5-membered or 6-membered cathocyclic or heterocyclic ring;
each of K1, K2, K3or K4is independently a direct bond, S, or O, with at least two of them being direct bonds; Z3, Z4, Z5, and Z6are each independently C or N;
L, L1, and L2are each independently selected from the group consisting of a direct bond, being absent, O, S, CR″R′″ SiR″R′″, BR″, and NR″, wherein at least one of L1and L2is present;
RCand RDeach independently represent zero, mono, or up to the maximum allowed number of substitutions to its associated ring;
each of R″, R′″, RC, and RDis independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof;

M is Pd or Pt;

any two adjacent R, R′, R″, R′″, RA, RB, RC, or RDcan be joined or fused together to form a ring where chemically feasible; and X1-X6, X8-X15, Z1, Z2, RA, RBand ring A are all defined the same as above.

In some of the above embodiments, ring C can be a 5-membered or 6-membered heteroaromatic ring. In some embodiments, ring C and ring D can both be 6-membered aromatic rings. In some embodiments, ring C and ring D can both be independently pyrimidine, pyridine, pyridazine, pyrazine, triazine, or benzene. In some embodiments, ring D can be a 5-membered heteroaromatic ring. In some embodiments, ring D can be imidazole, triazole, pyrazole, isothiazole, oxazole, or thiazole ring.

In some of the above embodiments, two RDsubstituents can be joined to form a fused ring. In some embodiments, two RCsubstituents can be joined to form a fused ring system. In some embodiments, the fused ring can be a 6-membered aromatic ring.

In some embodiments, each of K1, K2, K3or K4can be independently a direct bond. In some embodiments, one of K1, K2, K3or K4can be O. In some embodiments, one of K1or K2can be O. In some embodiments, one of K3or K4can be O.

In some of the above embodiments, Z3can be N and Z6can be C. In some embodiments, Z3can be C and Z6can be N. In some embodiments, both Z3and Z6can be C. In some embodiments, both Z4and Z5can be C. In some embodiments, Z4can be N and Z5can be C.

In some of the above embodiments, L can be a direct bond. In some embodiments, L can be NR″. In some embodiments, L1can be absent. In some embodiments, L2can be O, NR″, or CR″R′″. In some embodiments, L2can be O. In some embodiments, L can be a direct bond, L1can be absent, and L2can be 0.

In some embodiments, M can be Pd. In some embodiments, M can be Pt.

In some embodiments, the compound can be selected from the group consisting of:

wherein: each of X1-X6is independently N or CR; and at least one R or RAhas a structure of

wherein: each squiggly line represents a bond to the relevant part of the base compound structure;
each of X8-X15is independently N or CR′, the particular one of X8-X15that is bonded to one of X1-X6is C; Rxand Ryare each independently selected from the group consisting of alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, and combinations thereof;
REfor each occurrence is independently a hydrogen or a substituent selected from the group consisting of deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, boryl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, sulfanyl, and combinations thereof; and
X1-X6, X8-X15, Z1, Z2, RA, RB, RC, R1, L1and L2are all same as defined above for Formula I and Formula VI.

In the above embodiments, L1can be absent. In the above embodiments, L2can be O, NR″, or CR″R′″.

In some embodiments, the compound can be selected from the group consisting of the structures listed in LIST 1 below:

In some embodiments, the compound can be selected from the group consisting of Compound (l)-I-(A′i)(Bj)(Bk) to Compound (l)-XIV-(A′i)(Bj)(Bk), wherein 1, i, j, and k are as defined below, and each Compound having the formula of Pt(LA)(LB) with the following structure:

wherein LAhas the structure shown above and is selected from the group consisting of I-(A′i)(Bj)(Bk) to XIV-(A′i)(Bj)(Bk), wherein i is an integer from 1 to 7 and k is an integer from 1 to 47, and when i=1 to 3, j is an integer from 1 to 41, and when i=4 to 7, j is an integer from 1 to 47;

wherein LBhas the structure shown above and is selected from the group consisting of Ll, wherein l is an integer from 1 to 230107;

wherein rings C and D are as defined above for Formula VI; or

the compound can be selected from the group consisting of Compound [I-(A′i)(Bj)(Bk)][I-(A′m)(Bn)(Bo)] to Compound [XIV-(A′i)(Bj)(Bk)][XIV-(A′m)(Bn)(Bo)], each Compound having the formula of Pt(LA)(LC) with the
following structure:

wherein LAis as defined above;
wherein LChas the structure shown above and is selected from the group consisting of I-(A′m)(Bn)(Bo) to XIV-(A′m)(Bn)(Bo);

wherein Ll for each occurrence independently has the structure defined in the following LIST 2 below, wherein each squiggly line in each structure is independently for linking to the relevant part of LA:

and
wherein R1 to R330 have the following structures:

wherein LAand LCindependently have the structures defined in the following LIST 3:

wherein B1 to B47 have the following structures:

In some embodiments, Ai for each occurrence can be independently selected from the group consisting of A1, A2, A3, A7, A10, A11, A12, A13, A19, A20, A21, A23, and A29.

In some embodiments, the compound can be selected from the group consisting of LIST 4 below:

C. The OLEDs and the Devices of the Present Disclosure

In another aspect, the present disclosure also provides an OLED device comprising an organic layer that contains a compound as disclosed in the above compounds section of the present disclosure.

In some embodiments, the organic layer may comprise a compound comprising a ligand LAof

wherein one of Z1and Z2is C and the other is N; each of K1and K2is independently a direct bond, S, or O; ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; RArepresents zero, mono, or up to the maximum allowed number of substitutions to its associated ring; each of X1-X7is independently N or CR; at least one of R and RAhas a structure of

wherein: each of X8-X15is independently N or CR′, the particular one of X8-X15that is bonded to one of X1-X7or ring A of Formula I is C; the maximum number of N atoms that can connect to each other within a ring is two; each of remaining R and RAis independently a hydrogen, Formula II, Formula III, or a substituent selected from the group consisting of the general substituents defined herein; each of R1and RBis independently a hydrogen, or a substituent selected from the group consisting of the general substituents defined herein; the ligand LAis coordinated to a metal M by the indicated dash lines; the ligand LAcan be linked with other ligands to form a tridentate or tetradentate ligand; M is Pd or Pt, and can be coordinated to additional ligands; and any two adjacent R, R′, or RAcan be joined or fused together to form a ring.

In some embodiments, the organic layer may be an emissive layer and the compound as described herein may be an emissive dopant or a non-emissive dopant.

In some embodiments, the organic layer may further comprise a host, wherein the host comprises a triphenylene containing benzo-fused thiophene or benzo-fused furan, wherein any substituent in the host is an unfused substituent independently selected from the group consisting of CnF2n+1, OCnH2n+1, OAr1, N(CnH2n+1)2, N(Ar1)(Ar2), CH═CH—CnH2n+1, C≡CCnH2n+1, Ar1, Ar1-Ar2, CnH2n-Ar1, or no substitution, wherein n is from 1 to 10;

and wherein Ar1and Ar2are independently selected from the group consisting of benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.

In some embodiments, the organic layer may further comprise a host, wherein host comprises at least one chemical moiety selected from the group consisting of triphenylene, carbazole, indolocarbazole, dibenzothiphene, dibenzofuran, dibenzoselenophene, 5,9-dioxa-13b-boranaphtho[3,2,1-de]anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza-(5,9-dioxa-13b-bomnaphtho[3,2,1-de]anthracene).

In some embodiments, the host may be selected from the group consisting of:

and combinations thereof.

In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.

In some embodiments, the compound as described herein may be a sensitizer; wherein the device may further comprise an acceptor; and wherein the acceptor may be selected from the group consisting of fluorescent emitter, delayed fluorescence emitter, and combination thereof.

In yet another aspect, the OLED of the present disclosure may also comprise an emissive region containing a compound as disclosed in the above compounds section of the present disclosure.

In some embodiments, the emissive region may comprise a compound comprising a ligand LAof

wherein one of Z1and Z2is C and the other is N; each of K1and K2is independently a direct bond, S, or O; ring A is a 5-membered or 6-membered carbocyclic or heterocyclic ring; RArepresents zero, mono, or up to the maximum allowed number of substitutions to its associated ring; each of X1-X7is independently N or CR; at least one of R and RAhas a structure of

wherein: each of X8-X15is independently N or CR′, the particular one of X8-X15that is bonded to one of X1-X7or ring A of Formula I is C; the maximum number of N atoms that can connect to each other within a ring is two; each of remaining R and RAis independently a hydrogen, Formula II, Formula III, or a substituent selected from the group consisting of the general substituents defined herein; each of R′ and RBis independently a hydrogen, or a substituent selected from the group consisting of the general substituents defined herein; the ligand LAis coordinated to a metal M by the indicated dash lines; the ligand LAcan be linked with other ligands to form a tridentate or tetradentate ligand; M is Pd or Pt, and can be coordinated to additional ligands; and any two adjacent R, R′, or RAcan be joined or fused together to form a ring.

In yet another aspect, the present disclosure also provides a consumer product comprising an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as disclosed in the above compounds section of the present disclosure.

In some embodiments, the consumer product comprises an organic light-emitting device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound comprising a ligand LAof Formula I as described herein.

In some embodiments, the consumer product can be one of a flat panel display, a computer monitor, a medical monitor, a television, a billboard, a light for interior or exterior illumination and/or signaling, a heads-up display, a fully or partially transparent display, a flexible display, a laser printer, a telephone, a cell phone, tablet, a phablet, a personal digital assistant (PDA), a wearable device, a laptop computer, a digital camera, a camcorder, a viewfinder, a micro-display that is less than 2 inches diagonal, a 3-D display, a virtual reality or augmented reality display, a vehicle, a video wall comprising multiple displays tiled together, a theater or stadium screen, a light therapy device, and a sign.

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.

FIG. 1shows an organic light emitting device 100. The figures are not necessarily drawn to scale. Device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a barrier layer 170. Cathode 160 is a compound cathode having a first conductive layer 162 and a second conductive layer 164. Device 100 may be fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which are incorporated by reference.

FIG. 2shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. Device 200 may be fabricated by depositing the layers described, in order. Because the most common OLED configuration has a cathode disposed over the anode, and device 200 has cathode 215 disposed under anode 230, device 200 may be referred to as an “inverted” OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200.FIG. 2provides one example of how some layers may be omitted from the structure of device 100.

In some embodiments, the compound can be an emissive dopant. In some embodiments, the compound can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence, i.e., TADF (also referred to as E-type delayed fluorescence; see, e.g., U.S. application Ser. No. 15/700,352, which is hereby incorporated by reference in its entirety), triplet-triplet annihilation, or combinations of these processes. In some embodiments, the emissive dopant can be a racemic mixture, or can be enriched in one enantiomer. In some embodiments, the compound can be homoleptic (each ligand is the same). In some embodiments, the compound can be heteroleptic (at least one ligand is different from others). When there are more than one ligand coordinated to a metal, the ligands can all be the same in some embodiments. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, every ligand can be different from each other. This is also true in embodiments where a ligand being coordinated to a metal can be linked with other ligands being coordinated to that metal to form a tridentate, tetradentate, pentadentate, or hexadentate ligands Thus, where the coordinating ligands are being linked together, all of the ligands can be the same in some embodiments, and at least one of the ligands being linked can be different from the other ligand(s) in some other embodiments.

In some embodiments, the compound can be used as a phosphorescent sensitizer in an OLED where one or multiple layers in the OLED contains an acceptor in the form of one or more fluorescent and/or delayed fluorescence emitters. In some embodiments, the compound can be used as one component of an exciplex to be used as a sensitizer. As a phosphorescent sensitizer, the compound must be capable of energy transfer to the acceptor and the acceptor will emit the energy or further transfer energy to a final emitter. The acceptor concentrations can range from 0.001% to 100%. The acceptor could be in either the same layer as the phosphorescent sensitizer or in one or more different layers. In some embodiments, the acceptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission can arise from any or all of the sensitizer, acceptor, and final emitter

According to another aspect, a formulation comprising the compound described herein is also disclosed.

In yet another aspect of the present disclosure, a formulation that comprises the novel compound disclosed herein is described. The formulation can include one or more components selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, electron blocking material, hole blocking material, and an electron transport material, disclosed herein.

The present disclosure encompasses any chemical structure comprising the novel compound of the present disclosure, or a monovalent or polyvalent variant thereof. In other words, the inventive compound, or a monovalent or polyvalent variant thereof, can be a part of a larger chemical structure. Such chemical structure can be selected from the group consisting of a monomer, a polymer, a macromolecule, and a supramolecule (also known as supermolecule). As used herein, a “monovalent variant of a compound” refers to a moiety that is identical to the compound except that one hydrogen has been removed and replaced with a bond to the rest of the chemical structure. As used herein, a “polyvalent variant of a compound” refers to a moiety that is identical to the compound except that more than one hydrogen has been removed and replaced with a bond or bonds to the rest of the chemical structure. In the instance of a supramolecule, the inventive compound can also be incorporated into the supramolecule complex without covalent bonds.

D. Combination of the Compounds of the Present Disclosure with Other Materials

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. Fe/Fc couple less than about 0.6 V.

In one aspect, the metal complexes are:

wherein k is an integer from 1 to 20; L101is another ligand, k′ is an integer from 1 to 3.

E. Experimental Section

Synthesis of (L79253)-III-(A′3)(B1)(B3)

Synthesis of 2-(3-Bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazole

A suspension of 9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-ol (50 g, 143 mmol, 1 equiv), potassium phosphate tribasic (60.5 g, 285 mmol, 2 equiv), copper(I) iodide (4.07 g, 21.4 mmol, 0.15 equiv), 1,3-dibromobenzene (88 ml, 713 mmol, 5 equiv) and 2-picolinic acid (5.26 g, 42.8 mmol, 0.3 equiv) in dimethyl sulfoxide (713 ml) was sparged with nitrogen for 50 minutes. The reaction temperature was raised to 120° C. and the reaction was stirred for 18 hours. The reaction mixture was cooled to room temperature and poured into water (3.6 L). The mixture was extracted with ethyl acetate (4×2 L). The combined organic layers were washed with saturated aqueous ammonium chloride (3 L), dried over anhydrous sodium sulfate (150 g) and concentrated under reduced pressure. The crude product was purified by column chromatography on silica eluting with a gradient of 5 to 40% ethyl acetate in hexanes as a gray solid (95% yield).

Synthesis of 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)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine

A mixture of 2-(3-Bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazole (29.4 g, 58.1 mmol, 1 equiv), N1-([1,1′:3′,1″-terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)benzene-1,2-diamine (20.1 g, 58.1 mmol, 1 equiv) and sodium tert-butoxide (8.94 g, 93 mmol, 1.6 equiv) in anhydrous toluene (232 ml) was sparged with nitrogen for 40 minutes. BINAP (2.90 g, 4.65 mmol, 0.08 equiv) and tris(dibenzylideneacetone)dipalladium(0) (2.13 g, 2.33 mmol, 0.04 equiv) were added. The reaction mixture was sparged with nitrogen for 15 minutes and then heated at 100° C. for 12 hours. The reaction mixture was cooled to room temperature and diluted with dichloromethane (300 mL). The resulting mixture was filtered through a pad of Celite, rinsing with dichloromethane (750 mL). The filtrate was concentrated under reduced pressure and the residue was purified by column chromatography on silica eluting with a gradient of 60 to 100% dichloromethane in hexanes to give product as a light brown solid (75% yield).

Synthesis of 3-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium chloride

35 wt. % solution of deuterium chloride solution in D2O (8.81 ml, 106 mmol, 1.6 equiv) was added dropwise to a solution of 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)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine (51 g, 66.1 mmol, 1 equiv) in triethyl orthoformate (330 ml). The reaction temperature was raised to 90° C. and the reaction was stirred for 1 hour. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. Toluene (50 mL) was added and the resulting slurry was concentrated under reduced pressure. The residue was triturated with a 1:2 diethyl ether-hexane mixture (450 mL) to give product as an off-white solid (99% yield).

Synthesis of 7-(3-(3-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-1H-3λ4-benzo[d]imidazol-1-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-3-chloro-9H-carbazole-platinum(II)

A mixture of 3-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium chloride (25.5 g, 32.6 mmol, 1 equiv), a platinum precursor (1.1 equiv) and a base (3.3 equiv) in an organic solvent (652 ml) was sparged with nitrogen for 40 minutes. The mixture was refluxed for 14.5 hours, cooled to room temperature, and filtered. The filter cake was washed with methanol (100 mL) and dried on the filter to give crude product (30 g). The crude product was purified by column chromatography on silica eluting with 80% dichloromethane in hexanes to yield product as a yellow solid (70% yield).

Synthesis of (L79253)-III-(A′3)(B1)(B3)

A mixture of allylpalladium chloride dimer (28.2 mg, 0.08 mmol, 0.15 equiv) and cBRIDP (54.3 mg, 0.15 mmol, 0.3 equiv) was stirred in anhydrous THF (0.5 mL) under nitrogen for 5 minutes. 7-(3-(3-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-1H-3λ4-benzo[d]imidazol-1-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-3-chloro-9H-carbazole-platinum(II) (500 mg, 0.51 mmol, 1.0 equiv) was added followed by anhydrous xylene (2.5 mL) (Vial A). In another vial (Vial B), 1,8-dimethyl-9H-carbazole (601 mg, 3.08 mmol, 6 equiv) was dissolved in anhydrous THF (0.5 mL) and cooled to 0° C. A 3 M solution of methylmagnesium chloride in THF (1.03 mL, 3.08 mmol, 6 equiv) was added under nitrogen. The mixture was stirred at 0° C. for 5 minutes. The Vial A solution was added via syringe to Vial B under nitrogen. Vial A was rinsed with xylenes (2.5 mL) and added to Vial B. The reaction mixture (Vial B) was heated at 120° C. for 20 hours. After cooling to room temperature, the mixture was diluted with dichloromethane (5 mL) and filtered through a pad of celite. The celite pad was rinsed with additional dichloromethane (3×20 mL). The filtrate was purified by column chromatography eluting with a gradient of 10%-40% dichloromethane (containing 5% ethyl acetate) in hexanes to give product as a light yellow solid (41% yield).

Synthesis of (L79253)-III-(A′4)(B34)(B3)

Synthesis of 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)-9-phenyl-9H,9′H-[1,3′-bicarbazol]-7′-yl)oxy)phenyl)benzene-1,2-diamine

A mixture of 7′-(3-bromophenoxy)-9′-(4-(tert-butyl)pyridin-2-yl)-9-phenyl-9H,9′H-1,3′-bicarbazole (400 mg, 0.56 mmol, 1 equiv), N1-([1,1′:31,1″-terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)benzene-1,2-diamine (233 mg, 0.67 mmol, 1.1 equiv) and sodium tert-butoxide (162 mg, 1.7 mmol, 3 equiv) in toluene (4 mL) was sparged with nitrogen for 15 minutes. A mixture of allylpalladium chloride dimer (24 mg, 0.06 mmol, 0.1 equiv) and cBRIDP (40 mg, 0.11 mmol, 0.2 equiv) in toluene (2 mL) was sparged with nitrogen for 15 minutes and transferred by syringe to the first mixture. After refluxing for 18 hours, the reaction mixture was cooled to room temperature and filtered through a pad of Celite, which was washed with dichloromethane (0.5 L). The filtrate was concentrated under reduced pressure to give crude product (99% yield).

Synthesis of (3-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-1-(3-((9′-(4-(tert-butyl)pyridin-2-yl)-9-phenyl-9H,9′H-[1,3′-bicarbazol]-7′-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium) chloride

A mixture of crude 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)-9-phenyl-9H,9′H-[1,3′-bicarbazol]-7′-yl)oxy)phenyl)benzene-1,2-diamine (549 mg, 1.1 mmol) and 35% deuterium chloride in deuterium oxide (0.8 mL, 9 mmol, 8 equiv) in triethyl orthoformate (15 mL) was refluxed for 18 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The crude material was absorbed onto Celite and purified by column chromatography, eluting with a gradient of 80 to 100% dichloromethane in hexanes followed by 0 to 10% methanol in dichloromethane to give product (78% yield)

Synthesis of (L79253)-III-(A′4)(B34)(B3)

An organic solvent (18 mL) was sparged with nitrogen for 30 minutes and was transferred to a round bottom flask containing (3-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-1-(3-((9′-(4-(tert-butyl)pyridin-2-yl)-9-phenyl-9H,9′H-[1,3′-bicarbazol]-7′-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium) chloride (380 mg, 0.37 mmol, 1 equiv) and a base (3 equiv). The mixture was sparged with nitrogen for 15 minutes. A platinum precursor (1 equiv) was added and sparging was continued for 5 minutes. The reaction mixture was heated at 60° C. for one hour and at 190° C. for four days. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The crude material was absorbed onto Celite and purified by column chromatography, eluting with a gradient of 0 to 70% dichloromethane in hexanes to give product (30% yield).

Synthesis of (L79253)-III-(A′6)(B34)(B3)

Synthesis of 2-(3-Bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazole

A suspension of 9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-ol (50 g, 143 mmol, 1 equiv), potassium phosphate tribasic (60.5 g, 285 mmol, 2 equiv), copper(I) iodide (4.07 g, 21.4 mmol, 0.15 equiv), 1,3-dibromobenzene (88 ml, 713 mmol, 5 equiv) and 2-picolinic acid (5.26 g, 42.8 mmol, 0.3 equiv) in dimethyl sulfoxide (713 ml) was sparged with nitrogen for 50 minutes. The reaction temperature was raised to 120° C. and the reaction was stirred for 18 hours. The reaction mixture was cooled to room temperature and poured into water (3.6 L). The mixture was extracted with ethyl acetate (4×2 L). The combined organic layers were washed with saturated aqueous ammonium chloride (3 L), dried over anhydrous sodium sulfate (150 g) and concentrated under reduced pressure. The residue was absorbed onto Celite and purified by column chromatography system eluting with a gradient of 5 to 40% ethyl acetate in hexanes to give product as a gray solid (95% yield).

Synthesis of 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)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine

A mixture of 2-(3-Bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazole (29.4 g, 58.1 mmol, 1 equiv), N1-([1,1′:3′,1″-terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)benzene-1,2-diamine (20.1 g, 58.1 mmol, 1 equiv) and sodium tert-butoxide (8.94 g, 93 mmol, 1.6 equiv) in anhydrous toluene (232 ml) was sparged with nitrogen for 40 minutes. BINAP (2.90 g, 4.65 mmol, 0.08 equiv) and tris(dibenzylideneacetone)dipalladium(0) (2.13 g, 2.33 mmol, 0.04 equiv) were added. The reaction mixture was sparged with nitrogen for 15 minutes and then heated at 100° C. for 12 hours. The reaction mixture was cooled to room temperature and diluted with dichloromethane (300 mL). The resulting mixture was filtered through a pad of Celite, rinsing with dichloromethane (750 mL). The filtrate was concentrated under reduced pressure and the residue was absorbed onto Celite (150 g). The crude product was purified by column chromatography, eluting with a gradient of 60 to 100% dichloromethane in hexanes to give product as a light brown solid (75% yield).

Synthesis of 3-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium chloride

A 35 wt. % solution of deuterium chloride solution in D2O (8.81 ml, 106 mmol, 1.6 equiv) was added dropwise to a solution of 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)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)benzene-1,2-diamine (51 g, 66.1 mmol, 1 equiv) in triethyl orthoformate (330 ml). The reaction temperature was raised to 90° C. and the reaction was stirred for 1 hour. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The residue was triturated with a 1:2 diethyl ether-hexane mixture (450 mL) to give product as an off-white solid (99% yield).

Synthesis of 7-(3-(3-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-1H-3λ4-benzo[d]imidazol-1-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-3-chloro-9H-carbazole-platinum(11)

A mixture of 3-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-6-chloro-9H-carbazol-2-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium chloride (25.5 g, 32.6 mmol, 1 equiv), a platinum precurser (1.1 equiv) and a base (3.3 equiv) in a solvent (652 ml) was sparged with nitrogen for 40 minutes. The mixture was refluxed for 14.5 hours, cooled to room temperature, and filtered. The crude product was absorbed onto Celite and purified by column chromatography, eluting with 80% dichloromethane in hexanes to yield as a yellow solid (70% yield).

Synthesis of (L79253)-III-(A′6)(B34)(B3)

A solution of 7-(3-(3-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-1H-3λ4-benzo[d]imidazol-1-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-3-chloro-9H-carbazole-platinum(II) (800 mg, 0.82 mmol, 1.0 equiv), potassium phosphate tribasic monohydrate (756 mg, 3.28 mmol, 4.0 equiv), (9-phenyl-9H-carbazol-3-yl)boronic acid (943 mg, 3.28 mmol, 4.0 equiv), and SPhos-Pd-G2 (59.2 mg, 0.08 mmol, 0.1 equiv) in a 10 to 1 mixture of dioxane and water (8.8 mL) was sparged with nitrogen for 15 minutes. The reaction mixture was heated at 100° C. for 18 h. The crude mixture was cooled to room temperature and filtered over a pad of celite. The crude material was absorbed onto celite and purified by column chromatography, eluting with 30% dichloromethane in hexanes to give product as a light yellow solid (41% yield).

Synthesis of (L79253)-III-(A′1)(B41)(B3)

Synthesis of 9-(4-(tert-Butyl)pyridin-2-yl)-7-methoxy-9H-3,9′-bicarbazole

A solution of tris(dibenzylideneacetone)dipalladium(0) (3.1 g, 3.4 mmol, 0.09 equiv) and tri-tert-butylphosphonium tetrafluoroborate (1.97 g, 6.79 mmol, 17.2 equiv) in toluene (400 mL) was sparged with nitrogen for 20 minutes followed by the addition of 9H-carbazole (7.0 g, 42 mmol, 1.1 equiv), 9-(4-(tert-Butyl)pyridin-2-yl)-6-chloro-2-methoxy-9H-carbazole (15.8 g, 39.4 mmol, 1.00 equiv), and additional toluene (450 mL). The mixture was sparged with nitrogen for an additional 10 minutes and then treated with sodium tert-butoxide (11.9 g, 124 mmol, 3.14 equiv) added in portions over one minute. The reaction mixture was heated at 111° C. for 17 hours, and then cooled to room temperature. The mixture was filtered through Celite and the filter pad was washed with toluene (1 L). The filtrate was washed with water (2×500 mL), saturated brine (500 mL), dried over sodium sulfate (30 g). The crude product was absorbed onto celite and purified by column chromatography, eluting with a gradient of 0 to 10% ethyl acetate in heptanes to give product as a light tan foam (69% yield).

Synthesis of 9-(4-(tert-Butyl)pyridin-2-yl)-9H-[3,9′-bicarbazol]-7-ol

A mixture of 9-(4-(tert-Butyl)pyridin-2-yl)-7-methoxy-9H-3,9′-bicarbazole (14.4 g, 29.0 mmol, 1.00 equiv) in 48% HBr (440 mL, 656 g, 8.11 mol, 280 equiv) was heated at reflux for 16 hours. The mixture was cooled to room temperature, neutralized with solid sodium bicarbonate (450 g), partitioned between water (200 mL) and ethyl acetate (500 mL), and the layers were separated. The aqueous layer was extracted with ethyl acetate (400 mL). The combined organic layers were washed with saturated sodium chloride (300 mL), dried over sodium sulfate (50 g) and the residue was adsorbed onto Celite and purified by column chromatography, eluting with a gradient of 0 to 25% ethyl acetate in heptanes to give product as an off-white solid (76% yield).

Synthesis of 7-(3-Bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-3,9′-bicarbazole

Synthesis of 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-[3,9′-bicarbazol]-7-yl)oxy)phenyl)benzene-1,2-diamine

A mixture of allyl palladium chloride dimer (386 mg, 1.05 mmol, 0.060 equiv) and di-tert-butyl(1-methyl-2,2-diphenylcyclopropyl)phosphane (cBRIDP, 753 mg, 2.14 mmol, 1.22 equiv) in toluene (50 mL) was sparged with nitrogen for 25 minutes while heating to 80° C. to give a yellow solution. Separately, a mixture of N1-([1,1′:3′,1″-terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)benzene-1,2-diamine (6.06 g, 17.5 mmol, 1.00 equiv), 7-(3-Bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-3,9′-bicarbazole (11.7 g, 18.4 mmol, 1.05 equiv), and sodium tert-butoxide (5.28 g, 54.9 mmol, 3.14 equiv) in toluene (300 mL) was sparged with nitrogen for 15 minutes while heating to 85° C. The catalyst solution was transferred to the reagent mixture at 85° C. The combined mixture was sparged with nitrogen for five minutes at 85° C. then heated at 111° C. for eight hours. The mixture was cooled to room temperature and diluted with water (200 mL). The biphasic mixture was filtered through celite. The filter pad was washed with ethyl acetate (500 mL), and the layers of the filtrate were separated. The organic layer was washed with water (500 mL) and saturated brine (400 mL), dried over sodium sulfate (80 g) and concentrated under reduced pressure to a black foam (18.9 g). The residue was absorbed onto celite and purified by column chromatography, eluting with a gradient of 0 to 25% ethyl acetate in heptanes to give product as a brown solid (75% yield).

Synthesis of 3-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9′-bicarbazol]-7-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium chloride

A solution of 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-[3,9′-bicarbazol]-7-yl)oxy)phenyl)benzene-1,2-diamine (12.5 g, 13.9 mmol, 1.00 equiv) in triethylorthoformate (75 mL) was treated with concentrated hydrochloric acid (2.0 mL, 24 mmol, 1.7 equiv) at room temperature. The mixture was stirred at room temperature for one hour, then at 80° C. for six hours. The reaction mixture was cooled to room temperature, concentrated under reduced pressure, then concentrated from ethanol (75 mL) to give a red/brown residue (18.7 g), which was absorbed onto silica gel. The residue was purified by column chromatography, eluting with a gradient of 0 to 10% methanol in dichloromethane to give product as a light tan foam (70% yield).

Synthesis of (L79253)-III-(A′1)(B41)(B3)

A solution of 3-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-1-(3-((9-(4-(tert-butyl)pyridin-2-yl)-9H-[3,9′-bicarbazol]-7-yl)oxy)phenyl)-1H-benzo[d]imidazol-3-ium chloride (9.18 g, 9.68 mmol, 1.0 equiv) in an organic solvent (200 mL) was sparged with nitrogen for ten minutes in the absence of light at room temperature. The solution was treated with a base (3.33 equiv) and sparged with nitrogen for 15 minutes at room temperature. The reaction was treated with a platinum precursor (1.01 equiv), sparged with nitrogen for five minutes, then heated at 110° C. for 32 hours. The reaction was cooled to room temperature and concentrated under reduced pressure. The residue was absorbed onto celite and purified by column chromatography, eluting with 55% dichloromethane in hexanes. The product was triturated in methanol (230 mL) at 26° C. for 70 minutes, filtered and washed with methanol (100 mL) to give product as a yellow solid (41% yield).

Synthesis of (L79221)-III-(A′6)(B34)(B3)

Synthesis of (L79221)-III-(A′6)(B34)(B3)

A solution of 7′-(3-(1H-benzo[d]imidazol-1-yl)phenoxy)-9′-(4-(tert-butyl)pyridin-2-yl)-9-phenyl-9H,91H-1,3′-bicarbazole (3.00 g, 3.35 mmol, 1.00 equiv) and silver(I) oxide (390 mg, 1.7 mmol, 0.50 equiv) in 1,2-dichloroethane (120 mL) was sparged with nitrogen for 20 minutes then stirred at room temperature for 3 days in the absence of light. The mixture was concentrated under reduced pressure. 1,2-Dichlorobenzene (120 mL) and dichloro(1,5-cyclooctadiene) platinum(II) (1.25 g, 3.35 mmol, 1.00 equiv) were added and the suspension was sparged with nitrogen for 20 minutes. The mixture was stirred at reflux for 26 hours in the absence of light. After cooling to room temperature, the solvent was removed under reduced pressure. The residue was absorbed onto Celite and purified by column chromatography, eluting with 50% dichloromethane in hexanes. Product fractions were triturated in methanol (80 mL) at room temperature for 3 hours, then filtered to give product as a yellow solid (57% yield).

Synthesis of (L79221)-III-(A′1)(B41)(B3)

Synthesis of (L79221)-III-(A′1)(B41)(B3)

7-(3-(1H-benzo[d]imidazol-1-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-3,9′-bicarbazole (2.5 g, 3.05 mmol, 1.0 equiv) was stirred in 1,2-dichloroethane (120 mL) at room temperature until completely dissolved. Silver(I) oxide (0.352 g, 1.52 mmol, 0.5 equiv) was added and the mixture was stirred in the dark overnight. The mixture was concentrated under reduced pressure and the residue was dissolved in 1,2-dichlorobenzene (120 mL). The solution was sparged with nitrogen for 5 minutes and dichloro(1,5-cyclooctadiene)platinum(II) (1.14 g, 3.05 mmol, 1.0 equiv) was added. The mixture was heated at vigorous reflux overnight at which point LC/MS analysis indicated that the reaction was complete. The mixture was cooled to room temperature and concentrated under reduced pressure. The crude material was dry loaded on Celite and purified by column chromatography, eluting with 60% dichloromethane in hexanes to give a yellow solid. The purified compound was triturated with methanol (100 mL) and dried under vacuum at 50° C. for 18 hours to give product as a yellow solid (37% yield).

Synthesis of 3-Bromo-2-methoxy-9H-carbazole

A solution of 2-methoxy-9H-carbazole (20.1 g, 102 mmol, 1.00 equiv) and N-bromosuccinimide (18.1 g, 102 mmol, 1.00 equiv) in dichloromethane (1 L) was stirred at room temperature for 18 h. The reaction mixture was washed with saturated aqueous ammonium chloride solution (2×800 mL) and saturated brine (800 mL), dried over sodium sulfate and concentrated under reduced pressure. The crude product was absorbed onto Celite and purified by column chromatography, eluting with a gradient from 0 to 50% ethyl acetate in heptanes to give product as a white solid (88% yield).

Synthesis of 3-Bromo-9-(4-tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole

A mixture of 3-Bromo-2-methoxy-9H-carbazole (25.1 g, 91.0 mmol, 1.00 equiv) and 2-bromo-4-(tert-butyl)pyridine (20.4 g, 95.3 mmol, 1.05 equiv) in toluene (500 mL) was sparged with nitrogen for five minutes. 1-Methyl-N-imidazole (7.25 mL, 7.46 g, 91.0 mmol, 1.00 equiv), lithium tert-butoxide (15.3 g, 191 mmol, 2.1 equiv), and copper(I) iodide (6.97 g, 37.0 mmol, 0.40 equiv) were added and the mixture was sparged with nitrogen for five minutes, then heated at reflux for 18 hours. The reaction mixture was cooled to room temperature, partitioned between ethyl acetate (300 mL) and 28-30% aqueous ammonium hydroxide (200 mL), and the layers were separated. The organic layer was washed with 28-30% aqueous ammonium hydroxide (3×200 mL). The aqueous layer was extracted with ethyl acetate (700 mL). The combined organic layers were washed with saturated brine (500 mL), dried over sodium sulfate, and concentrated under reduced pressure. The residue was absorbed onto celite and purified by column chromatography, eluting with a gradient from 0 to 10% ethyl acetate in heptanes to give a 2:1 mixture of 3-Bromo-9-(4-tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole and 3-Iodo-9-(4-tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole as a yellow and white heterogeneous solid (75% yield).

Synthesis of N-(9-(4-(tert-Butyl)pyridin-2-yl)-2-methoxy-9H-carbazol-3-yl)acetamide

A mixture of 3-Bromo-9-(4-tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole and 3-Iodo-9-(4-tert-butyl)pyridin-2-yl)-2-methoxy-9H-carbazole (31.5 g, 72.8 mmol, 1.00 equiv) in toluene (750 mL) was sparged with nitrogen for 30 minutes while acetamide (22.8 g, 386 mmol, 5.02 equiv), potassium carbonate (22.6 g, 164 mmol, 2.25 equiv), 1,2-diaminocyclohexane (9.25 mL, 8.80 g, 77.0 mmol, 1.06 equiv), and copper(I) iodide (3.60 g, 18.9 mmol, 0.26 equiv) were added. The mixture was sparged with nitrogen for five minutes and heated to 111° C. for four days. The reaction mixture was cooled to room temperature, treated with water (500 mL), then filtered through celite (160 g) rinsing with ethyl acetate (1.5 L) and water (500 mL). The layers of the biphasic filtrate were separated and the aqueous layer was extracted with ethyl acetate (500 mL). The combined organic layers were washed with 10% aqueous ammonium hydroxide (2×300 mL), water (500 mL), and saturated brine (500 mL), dried over sodium sulfate and concentrated under reduced pressure. The crude product was absorbed onto Celite and purified by column chromatography, eluting with a gradient from 20 to 100% ethyl acetate in heptanes to give product as an off-white solid (83% yield).

Synthesis of 9-(4-(tert-Butyl)pyridin-2-yl)-2-methoxy-9H-carbazol-3-amine

A solution of N-(9-(4-(tert-Butyl)pyridin-2-yl)-2-methoxy-9H-carbazol-3-yl)acetamide (25.6 g, 66.1 mmol, 1.00 equiv) in 2-propanol (600 mL) was treated with a solution of potassium hydroxide (157 g, 2.80 mol, 42 equiv) in water (75 mL) at 80° C. for 22 hours. The mixture was cooled to room temperature and the layers were separated. The organic layer was concentrated to a minimum volume under reduced pressure. The aqueous layer was extracted with ethyl acetate (500 mL). The combined organics were washed with saturated brine (400 mL), dried over sodium sulfate, and concentrated under reduced pressure to give a black foam (23.5 g). The residue was absorbed onto Celite and purified by column chromatography, eluting with a gradient from 10 to 25% ethyl acetate in heptanes to give product as a brown solid (83% yield).

Synthesis of 9-(4-(tert-Butyl)pyridin-2-yl)-2-methoxy-9H-carbazol-3-amine

A mixture of 9-(4-(tert-Butyl)pyridin-2-yl)-2-methoxy-9H-carbazol-3-amine (20.0 g, 57.9 mmol, 1.00 equiv) and 2,2′-dibromo-1,1′-biphenyl (19.9 g, 63.8, 1.10 equiv) in xylenes (1.1 L) was sparged with nitrogen for 20 minutes at room temperature. The mixture was treated with sodium tert-butoxide (11.8 g, 123 mmol, 2.10 equiv) and sparged with nitrogen for another 20 minutes while heating to 90° C. Separately, a mixture of tris(dibenzylideneacetone)dipalladium(0) (3.18 g, 3.47 mmol, 0.06 equiv) and dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2-yl)phosphane (SPhos, 2.87 g, 6.99 mmol, 0.12 equiv) in xylenes (100 mL) was sparged with nitrogen for 30 minutes while heating to 90° C. The catalyst mixture (at 90° C.) was poured directly into the reagent mixture (at 90° C.), which was sparged with nitrogen for another 10 minutes, then heated at 111° C. for 18 hours. The mixture was cooled to room temperature and diluted with water (1 L) with vigorous stirring. The biphasic mixture was filtered through celite (100 g) washing with ethyl acetate (1 L). The layers of the filtrate were separated. The organic layer was washed with saturated brine (1 L), dried over sodium sulfate, and concentrated under reduced pressure to give a brown oil. The residue was absorbed onto Celite and purified by column chromatography, eluting with a gradient of 0 to 25% ethyl acetate in heptanes to give product as a red oil (92% yield).

Synthesis of 9-(4-(tert-Butyl)pyridin-2-yl)-9H-[3,9′-bicarbazol]-2-ol

A solution of 9-(4-(tert-Butyl)pyridin-2-yl)-2-methoxy-9H-carbazol-3-amine (27 g, 55 mmol, 1.00 equiv) and sodium ethanethiolate (13.8 g, 163 mmol, 3.0 equiv) in N-methyl-2-pyrrolidinone (400 mL) was heated at 130° C. for 18 hours. The reaction mixture was cooled to room temperature and diluted with saturated aqueous ammonium chloride (400 mL) and ethyl acetate (250 mL). The layers were separated and the aqueous layer was extracted with ethyl acetate (250 mL). The combined organic layers were washed with saturated aqueous sodium bicarbonate (2×250 mL) and saturated brine (500 mL), dried over sodium sulfate and concentrated under reduced pressure. The crude product was absorbed onto Celite and purified by column chromatography, eluting with a gradient of 0 to 20% ethyl acetate in heptanes to give product as a light brown solid (92% yield).

Synthesis of 2-(3-Bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-3,9′-bicarbazole

A mixture of 9-(4-(tert-Butyl)pyridin-2-yl)-9H-[3,9′-bicarbazol]-2-ol (24.9 g, 51.7 mmol, 1.00 equiv) and 1,3-dibromobenzene (24.0 g, 102 mmol, 1.97 equiv) in dimethyl sulfoxide (300 mL) was sparged with nitrogen for 30 minutes while picolinic acid (0.75 g, 6.1 mmol, 0.12 equiv), tribasic potassium phosphate (22.7 g, 107 mmol, 2.07 equiv), and copper(I) iodide (0.58 g, 3.1 mmol, 0.06 equiv) were added. The mixture was heated at 120° C. for 47 hours. The reaction mixture was cooled to room temperature and diluted with methyl tert-butyl ether (250 mL) and 10% aqueous ammonium hydroxide (250 mL). The layers were separated and the organic layer was washed with 10% aqueous ammonium hydroxide (2×250 mL). The combined aqueous layers were extracted with methyl tert-butyl ether (250 mL). The combined organic layers were washed with saturated brine (500 mL), dried over sodium sulfate, and concentrated under reduced pressure to give a black oil. The residue was absorbed onto Celite and purified by column chromatography system, eluting with a gradient from 5 to 50% dichloromethane in heptanes to give product as a dull yellow solid (49% yield).

A mixture of N1-([1,1′:3′,1″-terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)benzene-1,2-diamine (0.286 g, 0.825 mmol, 1.05 equiv), 2-(3-Bromophenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-3,9′-bicarbazole (0.5 g, 0.785 mmol, 1.0 equiv) and sodium tert-butoxide (0.266 g, 2.356 mmol, 3 equiv) in toluene (8 mL) was sparged with nitrogen for 15 minutes. A mixture of tris(dibenzylideneacetone)dipalladium(0) (29 mg, 0.031 mmol, 0.04 equiv) and BINAP (39 mg, 0.063 mmol, 0.08 equiv) in toluene (1 mL) was sparged with nitrogen for 15 minutes and transferred by syringe to the first mixture. After refluxing for 18 hours, the reaction mixture was cooled to room temperature and concentrated under reduced pressure. The crude material was absorbed onto Celite and purified by column, eluting with a gradient of 10 to 30% ethyl acetate in hexanes to give product as a white solid (71% yield).

Synthesis of 2-(3-(1-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-1H-3λ4-Benzo[d]imidazol-3-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-3,9′-bicarbazole

A mixture of 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-[3,9′-bicarbazol]-2-yl)oxy)phenyl)benzene-1,2-diamine (5.0 g, 5.54 mmol, 1 equiv) and 35% deuterium chloride in deuterium oxide (0.9 mL, 22.17 mmol, 4 equiv) in triethylorthoformate (37 mL) was refluxed for 18 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The crude material was absorbed onto Celite and purified by column chromatography, eluting with a gradient of 0 to 10% methanol in dichloromethane to give product (65% yield).

Synthesis of (L79253)-VI-(A′1)B41)(B3)

A suspension of 2-(3-(1-([1,1′:3′,1″-Terphenyl]-2′-yl-2,2″,3,3″,4,4″,5,5″,6,6″-d10)-1H-3λ4-Benzo[d]imidazol-3-yl)phenoxy)-9-(4-(tert-butyl)pyridin-2-yl)-9H-3,9′-bicarbazole (0.1 g, 0.11 mmol, 1.0 equiv) and a platinum precursor (59 mg, 0.142 mmol, 1.3 equiv) in an organic solvent (3 mL) in a pressure tube was sparged with nitrogen for 15 minutes. A base (47 mg, 0.438 mmol, 4.0 equiv) was added to the reaction mixture in one portion. The reaction mixture was heated at 130° C. for 16 hours. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The residue was dissolved in dichloromethane (20 mL), absorbed onto Celite and purified by column chromatography, eluting with 50% dichloromethane in hexanes. Product was concentrated under reduced pressure and dried in a vacuum oven at 50° C. for 18 hours as a pale yellow solid (40% yield).

Formula I and Formula II of the present disclosure are believed to result in narrow blue emission, and can be used in OLED devices for narrow and deep blue color. Table 1 below shows some of the photoluminescent properties of some representative compounds of the present disclosure. It can be seen that these compounds have a peak wavelength of less than 460 nm and a full width half maximum (FWHM) of less than 21 nm. Emission spectrum were acquired using a Hamamatsu Quantaurus-QY Plus UV-NIR absolute PL quantum yield spectrometer with an excitation wavelength of 340 nm on films of the Compound in polymethyl methacrylate (PMMA). Films were made by creating solutions of less than 1% emitter with PMMA in toluene which were prepared, filtered, and dropcast onto Quartz substrates.

OLEDs were made with several representative compounds and were found to be narrow with FWHMs under 30 nm. Further, the OLED devices reached deep blue color with 1931 CIE y less than 0.160. In general, the FWHM for a conversional phosphorescent emitter complex is above 60 nm. It has been a long-sought goal to achieve the small FWHM. The smaller FWHM, the better color purity for the display application. As a background information, the ideal line shape is a single wavelength (single line). As can be seen here, the current inventive compounds can cut more than half of the FWHM number from the conversional phosphorescent emitters. In the past of the OLED research, narrowing emission lineshape has been achieved nanometer by nanometer, the large decrease of the FWHM obtained from these inventive compounds is a remarkably unexpected result.

The OLEDs were grown on a glass substrate pre-coated with an indium-tin-oxide (ITO) layer having a sheet resistance of 15-52/sq. Prior to any organic layer deposition or coating, the substrate was degreased with solvents and then treated with an oxygen plasma for 1.5 minutes with 50 W at 100 mTorr and with UV ozone for 5 minutes.

The devices in Tables 2 were fabricated in high vacuum (<10-6 Torr) by thermal evaporation. The anode electrode was 750 Å of indium tin oxide (ITO). The device example had organic layers consisting of, sequentially, from the ITO surface, 100 Å of Compound 1 (HIL), 250 Å of Compound 2 (HTL), 50 Å of Compound 3 (EBL), 300 Å of Compound 4 doped with 20% of Compound 4 and 5% of Compound 3 and 10% of Emitter 1 (EML), 50 Å of Compound 5 (BL), 300 Å of Compound 6 doped with 35% of Compound 7 (ETL), 10 Å of Compound 6 (EIL) followed by 1,000 Å of A1 (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. Doping percentages are in volume percent.