CN112079873B

CN112079873B - Organic electroluminescent material and device

Info

Publication number: CN112079873B
Application number: CN202010544003.7A
Authority: CN
Inventors: 蔡瑞益; 亚力克西·鲍里索维奇·迪亚特金; T·费利塔姆; J·费尔德曼; 沃尔特·耶格尔; 皮埃尔-吕克·T·布德罗; 伯特·阿莱恩
Original assignee: Universal Display Corp
Current assignee: Universal Display Corp
Priority date: 2019-06-14
Filing date: 2020-06-15
Publication date: 2023-08-25
Anticipated expiration: 2040-06-15
Also published as: CN117186158A; CN112079873A

Abstract

The present application relates to organic electroluminescent materials and devices. Organometallic Compounds of formula IFormulations comprising these organometallic compounds are also provided. Further provided are OLEDs and related consumer products utilizing these organometallic compounds.

Description

Organic electroluminescent material and device

Cross reference to related applications

The present application claims priority from U.S. c. ≡119 (e) to U.S. provisional application No. 62/861,537 filed on 6-month 14 of 2019, the entire contents of which are incorporated herein by reference.

Technical Field

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

Background

Optoelectronic devices utilizing organic materials are becoming increasingly popular for a variety of reasons. Many of the materials used to fabricate the devices are relatively inexpensive, so organic photovoltaic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials (e.g., their flexibility) may make them more suitable for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can have performance advantages over conventional materials.

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

One application of phosphorescent emissive molecules is in full color displays. Industry standards for such displays require pixels adapted to emit a particular color (referred to as a "saturated" color). In particular, these standards require saturated red, green and blue pixels. Alternatively, the OLED may be designed to emit white light. In conventional liquid crystal displays, the emission from a white backlight is filtered using an absorbing filter to produce red, green and blue emissions. The same technique can also be used for OLEDs. The white OLED may be a single emissive layer (EML) device or a stacked structure. The colors may be measured using CIE coordinates well known in the art.

Disclosure of Invention

In one aspect, the present disclosure provides a compound of formula IWherein M is Pd or Pt; A. b and C are each independently a 5-or 6-membered carbocyclic or heterocyclic ring; part Z alone or with L ⁴ Together when present as a linking group is a fused ring structure comprising four or more fused heterocyclic or carbocyclic rings each of which is a 5-membered ring or a 6-membered ring; l (L) ¹ 、L ² 、L ³ And L ⁴ Each independently selected from the group consisting of: direct bond, BR, BRR', NR, PR, O, S, se, C = O, S = O, SO ₂ CRR ', siRR ', geRR ', alkyl, cycloalkyl andcombining; x is X ¹ -X ⁶ Each independently is C or N; y is Y ¹ 、Y ² 、Y ³ And Y ⁴ Each independently selected from the group consisting of: direct bond, O and S; y is Y ¹ 、Y ² 、Y ³ And Y ⁴ At least two of which are direct bonds; z is Z ¹ -Z ⁴ Each independently is C or N; m1, m2, m3, m4 are each independently integers of 0 or 1; r is R ^A 、R ^B 、R ^C And R is ^Z Each independently represents zero substitution, mono substitution or up to the maximum allowable substitution of its associated ring; r, R', R ^A 、R ^B 、R ^C And R is ^Z Each independently is hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and any two substituents may be joined or fused together to form a ring.

In another aspect, the present disclosure provides a formulation of a compound of formula I as described herein.

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

In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a compound of formula I as described herein.

Drawings

Fig. 1 shows an organic light emitting device.

Fig. 2 shows an inverted organic light emitting device without a separate electron transport layer.

Detailed Description

A. Terminology

Unless otherwise specified, the following terms used herein are defined as follows:

as used herein, the term "organic" includes polymeric materials and small molecule organic materials that can be used to fabricate organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and may be substantial in nature. In some cases, the small molecule may include a repeating unit. For example, the use of long chain alkyl groups as substituents does not remove a molecule from the "small molecule" class. Small molecules may also be incorporated into the polymer, for example as pendant groups on the polymer backbone or as part of the backbone. Small molecules can also act as the core of a dendrimer, which consists of a series of chemical shells built on the core. The core moiety of the dendrimer may be a fluorescent or phosphorescent small molecule emitter. Dendrimers may be "small molecules" and all dendrimers currently used in the OLED field are considered small molecules.

As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. Where a first layer is described as being "disposed" over "a second layer, the first layer is disposed farther from the substrate. Unless a first layer is "in contact with" a second layer, other layers may be present between the first and second layers. For example, a cathode may be described as "disposed over" an anode even though various organic layers are present between the cathode and the anode.

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

A ligand may be referred to as "photosensitive" when it is believed that the ligand contributes directly to the photosensitive properties of the emissive material. When the ligand is considered not to contribute to the photosensitive properties of the emissive material, the ligand may be referred to as "ancillary", but the ancillary ligand may alter the properties of the photosensitive ligand.

As used herein, and as will be generally understood by those of skill in the art, if the first energy level is closer to the vacuum energy level, then the first "highest occupied molecular orbital" (Highest Occupied Molecular Orbital, HOMO) or "lowest unoccupied molecular orbital" (Lowest Unoccupied Molecular Orbital, LUMO) energy level is "greater than" or "higher than" the second HOMO or LUMO energy level. Since Ionization Potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO level corresponds to an IP with a smaller absolute value (less negative). Similarly, a higher LUMO energy level corresponds to an Electron Affinity (EA) with a smaller absolute value (less negative EA). On a conventional energy level diagram with vacuum energy level on top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. The "higher" HOMO or LUMO energy level appears closer to the top of this figure than the "lower" HOMO or LUMO energy level.

As used herein, and as will be generally understood by those of skill in the art, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Since work function is typically measured as a negative number relative to the vacuum level, this means that the "higher" work function is more negative (more negative). On a conventional energy level diagram with the vacuum energy level on top, a "higher" work function is illustrated as being farther from the vacuum energy level in a downward direction. Thus, the definition of HOMO and LUMO energy levels follows a different rule than work function.

The terms "halo", "halogen" and "halo" are used interchangeably and refer to fluoro, chloro, bromo and iodo. The term "acyl" refers to a substituted carbonyl (C (O) -R _s ). The term "ester" refers to a substituted oxycarbonyl (-O-C (O) -R) _s or-C (O) -O-R _s ) A group. The term "ether" means-OR _s A group. The terms "thio" or "thioether" are used interchangeably and refer to-SR _s A group. The term "sulfinyl" refers to-S (O) -R _s A group. The term "sulfonyl" refers to-SO ₂ -R _s A group. The term "phosphino" refers to-P (R _s ) ₃ A group wherein each R _s May be the same or different. The term "silane group" means-Si (R _s ) ₃ A group wherein each R _s May be the same or different. The term "oxyboronyl" means-B (R _s ) ₂ A group or Lewis addition product-B (R) _s ) ₃ A group, wherein R is _s May be the same or different.

In each of the above, R _s May be hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. Preferred R _s Selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.

The term "alkyl" refers to and includes straight and branched chain alkyl groups. Preferred alkyl groups are those containing from one to fifteen carbon atoms and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, and the like. In addition, alkyl groups may be optionally substituted.

The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyl groups. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo [3.1.1] heptyl, spiro [4.5] decyl, spiro [5.5] undecyl, adamantyl, and the like. In addition, cycloalkyl groups may be optionally substituted.

The term "heteroalkyl" or "heterocycloalkyl" refers to an alkyl or cycloalkyl group, respectively, having at least one carbon atom replaced with a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, si and Se, preferably O, S or N. In addition, heteroalkyl or heterocycloalkyl groups may be optionally substituted. The term "alkenyl" refers to and includes both straight and branched alkenyl groups. Alkenyl is essentially an alkyl group comprising at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl is essentially cycloalkyl including at least one carbon-carbon double bond in the cycloalkyl ring. The term "heteroalkenyl" as used herein refers to an alkenyl group having at least one carbon atom replaced with 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 from two to fifteen carbon atoms. In addition, alkenyl, cycloalkenyl, or heteroalkenyl groups may be optionally substituted.

The term "alkynyl" refers to and includes both straight and branched chain alkynyl groups. Alkynyl is essentially an alkyl group that includes at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing from two to fifteen carbon atoms. In addition, alkynyl groups may be optionally substituted. The term "aralkyl" or "arylalkyl" is used interchangeably and refers to an alkyl group substituted with an aryl group. In addition, aralkyl groups may be optionally substituted.

The term "heterocyclyl" refers to and includes aromatic and non-aromatic cyclic groups 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. Aromatic heterocyclic groups may be used interchangeably with heteroaryl. Preferred non-aromatic heterocyclic groups are heterocyclic groups containing 3 to 7 ring atoms including at least one heteroatom and include cyclic amines such as morpholinyl, piperidinyl, pyrrolidinyl, and the like, and cyclic ethers/sulfides such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. In addition, the heterocyclic group may be optionally substituted.

The term "aryl" refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. The polycyclic ring may have two or more rings in common in which two carbons are two adjoining rings (the rings being "fused"), wherein at least one of the rings is an aromatic hydrocarbon group, e.g., the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl. Preferred aryl groups are those containing from six to thirty carbon atoms, preferably from six to twenty carbon atoms, more preferably from six to twelve carbon atoms. Particularly preferred are aryl groups having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, triphenylene, fluorene and naphthalene. In addition, aryl groups may be optionally substituted.

The term "heteroaryl" refers to and includes monocyclic aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. Heteroatoms include, but are not limited to O, S, N, P, B, si and Se. In many cases O, S or N are preferred heteroatoms. The monocyclic heteroaromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring may have one to six heteroatoms. The heteropolycyclic ring system may have two or more rings in which two atoms are common to two adjoining rings (the rings being "fused"), wherein at least one of the rings is heteroaryl, e.g., the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl. The heteropolycyclic aromatic ring system may have one to six heteroatoms in each ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing from three to thirty carbon atoms, preferably from three to twenty carbon atoms, more preferably from 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, diazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene (xanthene), acridine, phenazine, phenothiazine, phenoxazine, benzofurandipyridine, benzothiophene pyridine, thienodipyridine, benzoselenophene dipyridine, dibenzofuran, dibenzoselenium, carbazole, indolocarbazole, benzimidazole, triazine, 1, 2-borazine, 1-boron-nitrogen, 1-nitrogen, 4-boron-nitrogen, boron-nitrogen-like compounds, and the like. In addition, heteroaryl groups may be optionally substituted.

Of the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and their respective corresponding aza analogues, are of particular interest.

The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclyl, aryl, and heteroaryl as used herein are independently unsubstituted or independently substituted with one or more common substituents.

In many cases, the typical substituents are selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In some cases, preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

In some cases, preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, oxyboroyl, aryl, heteroaryl, thio, and combinations thereof.

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

The terms "substituted" and "substituted" refer to substituents other than H bonded to the relevant position, such as carbon or nitrogen. For example, when R ¹ When single substitution is represented, then one R ¹ It must not be H (i.e., substitution). Similarly, when R ¹ When two are substituted, two R ¹ It must not be H. Similarly, when R ¹ R represents zero or no substitution ¹ For example, it may be hydrogen of available valence of the ring atoms, such as carbon atoms of benzene and nitrogen atoms in pyrrole, or for ring atoms having a fully saturated valence, it may simply represent none, such as nitrogen atoms in pyridine. In the ring structure is possibleThe maximum number of substitutions of (a) will depend on the total number of available valences in the ring atoms.

As used herein, "combination thereof" means 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 contemplate from the applicable list. For example, alkyl and deuterium can combine to form a partially or fully deuterated alkyl group; halogen and alkyl may combine to form a haloalkyl substituent; and halogen, alkyl and aryl may combine to form a haloaralkyl. In one example, the term substitution includes a combination of two to four of the listed groups. In another example, the term substitution includes a combination of two to three groups. In yet another example, the term substitution includes a combination of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms other than hydrogen or deuterium, or combinations comprising up to forty atoms other than hydrogen or deuterium, or combinations comprising up to thirty atoms other than hydrogen or deuterium. In many cases, a preferred combination of substituents will include up to twenty atoms that are not hydrogen or deuterium.

The term "aza" in the fragments described herein, i.e., aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the C-H groups in the corresponding aromatic ring may be replaced with a nitrogen atom, for example and without limitation, aza-triphenylene encompasses dibenzo [ f, H ] quinoxaline and dibenzo [ f, H ] quinoline. Other nitrogen analogs of the aza-derivatives described above can be readily envisioned by those of ordinary skill in the art, and all such analogs are intended to be encompassed by the terms as set forth herein.

As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. patent No. 8,557,400, patent publication No. WO 2006/095951, and U.S. patent application publication No. US 2011/0037057 (which are incorporated herein by reference in their entirety) describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Yan Ming (Ming Yan) et al, tetrahedron 2015,71,1425-30 and Azrote (Atzrodt) et al, germany application chemistry (Angew. Chem. Int. Ed.) (reviewed) 2007,46,7744-65, which is incorporated by reference in its entirety, describes the deuteration of methylene hydrogen in benzylamine and the efficient pathway of replacement of aromatic ring hydrogen with deuterium, respectively.

It will be appreciated that when a fragment of a molecule is described as a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or linking fragments are considered equivalent.

In some cases, a pair of adjacent substituents may optionally be joined or fused into a ring. Preferred rings are five-, six-, or seven-membered carbocycles or heterocycles, including both cases where a portion of the ring formed by the pair of substituents is saturated and a portion of the ring formed by the pair of substituents is unsaturated. As used herein, "adjacent" means that the two substituents involved can be next to each other on the same ring, or on two adjacent rings having two nearest available substitutable positions (e.g., the 2, 2' positions in biphenyl or the 1, 8 positions in naphthalene) so long as they can form a stable fused ring system.

B. Compounds of the present disclosure

In one aspect, the present disclosure provides a compound of formula IWherein:

m is Pd or Pt;

A. b and C are each independently a 5-or 6-membered carbocyclic or heterocyclic ring;

Part Z alone or with L ⁴ Together when present as a linking group is a fused ring structure comprising four or more fused heterocyclic or carbocyclic rings each of which is a 5-membered ring or a 6-membered ring;

L ¹ 、L ² 、L ³ and L ⁴ Each independently selected from the group consisting of: direct bond, BR, BRR', NR, PR, O, S, se, C = O, S = O, SO ₂ CRR ', siRR ', geRR ', alkyl, cycloAlkyl groups and combinations thereof;

X ¹ -X ⁶ each independently is C or N;

Y ¹ 、Y ² 、Y ³ and Y ⁴ Each independently selected from the group consisting of: direct bond, O and S;

Y ¹ 、Y ² 、Y ³ and Y ⁴ At least two of which are direct bonds;

Z ¹ -Z ⁴ each independently is C or N;

m1, m2, m3, m4 are each independently integers of 0 or 1;

R ^A 、R ^B 、R ^C and R is ^Z Each independently represents zero substitution, mono substitution or substitution up to maximum allowed for its associated ring;

R、R'、R ^A 、R ^B 、R ^C and R is ^Z Each independently is hydrogen or a substituent selected from the group consisting of the general substituents as described herein; and is also provided with

Any two substituents may be joined or fused together to form a ring.

In some embodiments, R, R', R ^A 、R ^B 、R ^C And R is ^Z Each may independently be hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein.

In some embodiments, m1 and m3 may each be 0, and m2 and m4 may each be 1. In these embodiments, ring B and ring C may be linked to form a bidentate ligand, and ring a and ring Z may also be linked to form a bidentate ligand. In some embodiments, only one of m1, m2, m3, and m4 may be 0, and the remainder may each independently be 1. In some embodiments, m1 may be 0, and m2, m3, and m4 may each independently be 1. In some embodiments, m3 may be 0, and m1, m2, and m4 may each independently be 1. In these embodiments, rings A, B, C and Z can be linked to form a tetradentate ligand. In some embodiments, each of m1, m2, m3, and m4 may independently be 1. In these embodiments, rings A, B, C and Z can be linked to form a closed tetradentate ligand.

In some embodiments, moiety Z alone may be a fused ring structure comprising four or more fused heterocycles or carbocycles, wherein each of the fused heterocycles or carbocycles is independently a 5-membered ring or a 6-membered ring. In some embodiments, moiety Z is attached to linking group L ⁴ May be linked to form a fused ring structure comprising four or more fused heterocycles or carbocycles, wherein each of the fused heterocycles or carbocycles is independently a 5-membered ring or a 6-membered ring. In some embodiments, the linking group L ⁴ May be BR, BRR ', NR, PR, CRR ', and SiRR ', where R is joined with a moiety Z to form a fused ring structure comprising four or more fused heterocycles or carbocycles, where each of the fused heterocycles or carbocycles is independently a 5-membered ring or a 6-membered ring. In some embodiments, the linking group L ⁴ May be NR or CRR' where R is joined with a moiety Z to form a fused ring structure comprising four or more fused heterocycles or carbocycles, where each of the fused heterocycles or carbocycles is independently a 5-membered ring or a 6-membered ring. In some embodiments, the linking group L ⁴ May be NR, wherein R is joined with a moiety Z to form a fused ring structure comprising four or more fused heterocycles or carbocycles, wherein each of the fused heterocycles or carbocycles is independently a 5-membered ring or a 6-membered ring.

In some embodiments, Y ¹ 、Y ² 、Y ³ And Y ⁴ Is a direct bond. In some embodiments, Y ¹ 、Y ² 、Y ³ And Y ⁴ Is a direct bond. In some embodiments, Y ¹ And Y ⁴ Is a direct bond. In some embodiments, Y ¹ 、Y ² 、Y ³ And Y ⁴ One of them is O or S, and Y ¹ 、Y ² 、Y ³ And Y ⁴ The remainder of which are direct bonds. In some embodiments, Y ⁴ Is O or S, and Y ¹ 、Y ² And Y ³ Is a direct bond. In some embodiments, Y ¹ And Y ³ One of them is O or S, and Y ¹ 、Y ² 、Y ³ And Y ⁴ The remainder of which are direct bonds.

In some embodiments of the compounds of formula I, the compounds may have the structure of formula IIWherein at least two of m1, m2 and m3 are each independently 1; and the remaining variables are the same as previously defined.

With respect to formula II, in some embodiments, R ^A 、R ^B 、R ^C And R is ^Z Each may independently be hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein.

With respect to formula II, in some embodiments, m1 and m3 may each be 0, and m2 may be 1. In these embodiments, ring B and ring C may be linked to form a bidentate ligand. In some embodiments, only one of m1, m2, and m3 may be 0, and the remainder may each independently be 1. In some embodiments, m1 may be 0, and m2 and m3 may each be independently 1. In some embodiments, m3 may be 0, and m1 and m2 may each be independently 1. In these embodiments, rings A, B, C and Z can be linked to form a tetradentate ligand. In some embodiments, each of m1, m2, and m3 may independently be 1. In these embodiments, rings A, B, C and Z can be linked to form a closed tetradentate ligand.

With respect to formula II, in some embodiments, rings A, B and C can each independently be a 6 membered aromatic ring. In some embodiments, at least one of rings a and B may be a 5 membered aromatic ring. In some embodiments, if one or more 5-membered rings are present in Z, at least one may be a furan ring. In some embodiments, m1 may be 0. In some embodiments, m2 may be 1, and L ² May be a direct bond. In some embodiments, m2 may be 1, and L ² May be NR. In some embodiments, m3 may be 1, and L ³ May be O or CRR'. In some embodiments, Y ¹ And Y ² May be a direct bond. In some embodiments, Y ¹ And Y ² One of them isO，Y ¹ And Y ² The other of which is a direct bond. In some embodiments, Z ¹ And Z ² May be N. In some embodiments, X ¹ To X ³ Each may be C. In some embodiments, m2+m3 may be 2.

With respect to formula II, in some embodiments, R ^A And R is ^B Each independently can be hydrogen or a substituent selected from the group consisting of deuterium, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, and combinations thereof. In some embodiments, two R ^A Substituents may be joined together to form a fused 6-membered aromatic ring. In some embodiments, two R ^B Substituents may be joined together to form a fused 6-membered aromatic ring. In some embodiments, Z may comprise four fused rings. In some embodiments, Z may comprise five fused rings. In some embodiments, Z may comprise six fused rings. In some embodiments, Z may comprise seven fused rings. In some embodiments, Z may comprise a 5 membered ring. In some embodiments, Z may comprise two 5 membered rings. In some embodiments, Z may comprise three 6 membered rings. In some embodiments, Z may comprise four 6 membered rings. In some embodiments, ring a may be selected from the group consisting of pyridine, imidazole, and imidazole-derived carbenes.

With respect to formula II, in some embodiments, Z may comprise a structure selected from the group consisting of:

wherein the dotted line labeled with a # -, represents a direct bond to ring A; wherein the dotted line marked with an asterisk indicates a direct bond to M; and is also provided with

Wherein the sign of the sign is%&) Is indicated by the dotted line of L ³ Is a direct bond to (c).

With respect to formula II, in some embodiments, the compound may comprise a structure selected from the group consisting of:

and is also provided with

Wherein R is ^F And R is ^G Each independently represents zero substitution, mono substitution or substitution up to maximum allowed for its associated ring;

R ^F 、R ^G And R is ^X Each independently is hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and is also provided with

Any two substituents may be joined or fused together to form a ring.

In some embodiments, the compound may be selected from the group consisting of compound k-Si-j; wherein k is an integer of 1 to 3, i is an integer of 1 to 114, and j is an integer of 1 to 44, and for each Si, the compound has a structure defined in the following list 1, wherein X in the structure is O when k=1, and X in the structure is CMe when k=2 ₂ The method comprises the steps of carrying out a first treatment on the surface of the And when k=3, X in the structure is NPh:

/>

wherein for each j R ¹ To R ⁵ The definition is as follows:

/>

in some embodiments, the compound may have the structure of formula III

Wherein:

rings Z1, Z2, Z3, Z4 and Z5 are each independently a 5-or 6-membered carbocycle or heterocycle, wherein the carbocycle or heterocycle are each continuously fused to each other;

R ^Z1 、R ^Z2 、R ^Z3 、R ^Z4 And R is ^Z5 Each independently is hydrogen or a general substituent as described herein;

the remaining variables are the same as previously defined, and

any two substituents may be joined or fused to form a ring.

With respect to formula III, in some embodiments, R ^Z1 、R ^Z2 、R ^Z3 、R ^Z4 、R ^Z5 、R ^A 、R ^B And R is ^C Each may independently be hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein.

With respect to formula III, in some embodiments, L ³ May be selected from the group consisting of O, S, CRR' and NR. In some embodiments, L ² May be a single bond or NR. In some embodiments, R and one R ^C Substituents may join to form fused ring moieties. In some embodiments, ring a may be a 5-membered ring. In some embodiments, ring a may be selected from the group consisting of N-heterocyclic carbenes, imidazoles, and pyrazoles. In some embodiments, ring a may be a 6 membered ring. In some embodiments, ring a may be a pyridine ring. In some embodiments, ring B may be a 5-membered ring. In some embodiments, ring B may be selected from the group consisting of N-heterocyclic carbenes, imidazoles, and pyrazoles. In some embodiments, ring B may be a 6 membered ring. In some embodiments, ring B may be a pyridine ring. In some embodiments, ring C may be a 6 membered ring.

With respect to formula III, in some embodiments, ring Z1 may be a 6 membered ring. In some embodiments, rings Z2 and Z4 may be 5 membered rings. In some embodiments, rings Z3 and Z5 may be 6 membered rings. In some embodiments, rings Z2 and Z3 may be 6 membered rings. In some embodiments, ring Z4 may be a 5-membered ring, and ring Z5 is a 6-membered ring. In some embodiments, rings Z1, Z2, Z3, Z4, and Z5 may each independently be aromatic. In the above embodiments, rings Z1, Z2, Z3, Z4, and Z5 may be fused in any chemically feasible manner, even though formula III illustrates linear fusion as a non-limiting example only. More specifically, rings Z1, Z2, Z3, Z4 and Z5 may be fused linearly or nonlinearly. In some embodiments, Z ¹ And Z ² May be N, and Z ³ And Z ⁴ May be C. In some embodiments, Z ¹ May be C, Z ² Is N, and Z ³ And Z ⁴ May be C. In some embodiments, X ⁴ And X ⁵ May be C. In some embodiments, X ⁵ May be N, and X ⁴ May be C.

With respect to formula III, in some embodiments, two adjacent R' s ^A Substituents may be joined to form a fused ring structure. In some embodiments, two adjacent R ^B Substituents may be joined to form a fused ring structure. In some embodiments, two adjacent R ^C Substituents may be joined to form a fused ring structure. In some embodiments, R ^Z1 、R ^Z2 、R ^Z3 、R ^Z4 、R ^Z5 、R ^A 、R ^B And R is ^C Each independently can be deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some embodiments, M may be Pt.

With respect to formula III, in some embodiments, the compound may be selected from the group consisting of:

wherein the variables R, R ^A 、R ^B 、R ^C 、R ^Z1 、R ^Z3 、R ^Z5 、L ² And L ³ As previously defined.

In some of the above embodiments, L ² And L ³ Each independently can be O, S, BR, NR, CRR ' or SiRR ', where R and R ' are as defined previously.

/>

wherein the variables R, R ^A 、R ^B 、R ^C And L ³ As previously defined.

In some of the above embodiments, L is present at each occurrence ³ Can be O, S, BR, NR, CRR 'or SiRR' independently, whichR and R' are as defined previously.

In some embodiments, the compound may be selected from the group consisting of list 2:

/>

in some embodiments, the compound may have a structure according to a formula selected from the group consisting of:

IVa/>

IVb

IVc

IVd/>

IVeFormula IVf->And IVg +>Wherein:

Rings Z1', Z3', Z4', Z5', Z6', and Z7' are each independently a 5-or 6-membered carbocyclic or heterocyclic ring, wherein rings Z1 'to Z7' are continuously fused to each other;

R ^Z1 '、R ^Z3 '、R ^Z4 '、R ^Z5 '、R ^Z6 ' and R ^Z7 ' each independently is hydrogen or a general substituent as described herein;

the remaining variables are the same as previously defined, and

any two substituents may be joined or fused together to form a ring.

With respect to the above formula, in some embodiments, R ^Z1 '、R ^Z3 '、R ^Z4 '、R ^Z5 '、R ^Z6 '、R ^Z7 '、R ^A 、R ^B And R is ^C Each independently can be hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.

With respect to the above formula, in some embodiments, L ³ May be selected from the group consisting of O, S, CRR' and NR. In some embodiments, L ³ May be O or NR. In some embodiments, ring a may be a 6 membered aromatic ring. In some embodiments, ring B may be a 6 membered aromatic ring. In some embodiments, ring C may be a 6 membered aromatic ring. In some embodiments, Z ¹ And Z ² Each may independently be N. In some embodiments, Z ³ And Z ⁴ May each independently be C. In some embodiments, X ² 、X ³ 、X ⁴ And X ⁹ May each independently be C. In some embodiments, ring Z1' may be a 6 membered aromatic ring. In some embodiments, ring Z3' may be a 6 membered aromatic ring. In some embodiments, ring Z4' may be a 5 membered aromatic ring. In some embodiments, ring Z4' may be a furan ring. In some embodiments, rings Z5', Z6', and Z7' may each independently be a 6 membered aromatic ring. In the above embodiments, the rings Z1', Z2', Z3', Z4', Z5', Z6' and Z7' may be fused in any chemically feasible manner, i.e. linear or non-linear.

Regarding the above formula, in some embodiments, two adjacent R' s ^A Substituents may be joined to form a fused ring structure. In some embodiments, two adjacent R ^B Substituents may be joined to form a fused ring structure. In some embodiments, two adjacent R ^C Substituents may be joined to form a fused ring structure. In some embodiments, R ^Z1 '、R ^Z3 '、R ^Z4 '、R ^Z5 '、R ^Z6 '、R ^Z7 '、R ^A 、R ^B And R is ^C Each independently can be deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some embodiments, M may be Pt.

With respect to the above formula, the compound may be selected from the group consisting of:

/>

wherein each R is ^C ' is hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, oxyboronyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and is also provided with

Any two substituents may be joined or fused together to form a ring.

In some of the above embodiments, L is present at each occurrence ³ May be O, S, BR, NR, CRR ' or SiRR ', where R and R ' are as defined previously.

With respect to formulas IVa, IVb, IVc, IVd, IVe, IVf and IVg above, in some embodiments, the compound may be selected from the group consisting of the structures in list 3 below:

/>

wherein the variables R, R ^A 、R ^B 、R ^C 、R ^Z1 '、R ^Z3 '、R ^Z4 '、R ^Z5 '、R ^Z6 '、R ^Z7 ' and L ³ As previously defined.

In some of the above embodiments, L is present at each occurrence ³ May independently be O, S, BR, NR, CRR ' or SiRR ', where R and R ' are as defined previously.

In some embodiments, the compound may be selected from the group consisting of compounds Ti-j, wherein i is an integer from 1 to 72 and j is an integer from 1 to 20, and for each Ti, the compound has the structure defined in the following list 4:

/>

wherein for each j R ¹¹ To R ¹⁵ The definition is as follows:

/>

C. OLED and device of the present disclosure

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

In some embodiments, the organic layer may comprise a compound of formula I Wherein:

m is Pd or Pt;

L ¹ 、L ² 、L ³ and L ⁴ Each independently selected from the group consisting of: direct bond, BR, BRR', NR, PR, O, S, se, C = O, S = O, SO ₂ CRR ', siRR ', geRR ', alkyl, cycloalkyl, and combinations thereof;

X ¹ -X ⁶ each independently is C or N;

Y ¹ 、Y ² 、Y ³ and Y ⁴ At least two of which are direct bonds;

Z ¹ -Z ⁴ each independently is C or N;

m1, m2, m3, m4 are each independently integers of 0 or 1;

R、R'、R ^A 、R ^B 、R ^C and R is ^Z Each independently is hydrogen or a substituent selected from the group consisting of the general substituents as described herein; and any two substituents may 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 comprising a benzofused thiophene or benzofused furan, wherein any substituent in the host is a non-fused substituent independently selected from the group consisting of: c (C) _n H _2n+1 、OC _n H _2n+1 、OAr ₁ 、N(C _n H _2n+1 ) ₂ 、N(Ar ₁ )(Ar ₂ )、CH＝CH-C _n H _2n+1 、C≡CC _n H _2n+1 、Ar ₁ 、Ar ₁ -Ar ₂ 、C _n H _2n -Ar ₁ Or no substituent, wherein n is 1 to 10; and wherein Ar is ₁ With Ar ₂ 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 the host comprises at least one chemical moiety selected from the group consisting of: triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5, 9-dioxa-13 b-boronaphtho [3,2,1-de ] anthracene, aza-triphenylene, aza-carbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, and aza- (5, 9-dioxa-13 b-boronaphtho [3,2,1-de ] anthracene).

In some embodiments, the subject 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, a compound as described herein may be a sensitizer; wherein the device may further comprise a recipient; and wherein the receptor may be selected from the group consisting of: fluorescent emitters, delayed fluorescent emitters, and combinations thereof.

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

In some embodiments, the emissive region may comprise a compound of formula IWherein:

m is Pd or Pt;

X ¹ -X ⁶ each independently is C or N;

Y ¹ 、Y ² 、Y ³ and Y ⁴ At least two of which are direct bonds;

Z ¹ -Z ⁴ Each independently is C or N;

m1, m2, m3, m4 are each independently integers of 0 or 1;

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 compound section of the disclosure.

In some embodiments, the consumer product comprises an organic light emitting deviceAn Organic Light Emitting Device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound of formula IWherein:

m is Pd or Pt;

X ¹ -X ⁶ each independently is C or N;

Y ¹ 、Y ² 、Y ³ and Y ⁴ At least two of which are direct bonds;

Z ¹ -Z ⁴ each independently is C or N;

m1, m2, m3, m4 are each independently integers of 0 or 1;

In some embodiments, the consumer product may be one of the following products: flat panel 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, laser printers, telephones, cellular telephones, tablet computers, tablet handsets, personal Digital Assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, micro-displays with a diagonal of less than 2 inches, 3-D displays, virtual or augmented reality displays, vehicles, video walls comprising a plurality of displays tiled together, theatre or gym screens, phototherapy devices, and billboards.

In general, an OLED includes at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer. The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and a hole are localized on the same molecule, an "exciton" is formed, which is a localized electron-hole pair having an excited energy state. Light is emitted when the exciton relaxes through a light emission mechanism. In some cases, excitons may be localized on an excimer or exciplex. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.

Several OLED materials and configurations are described in U.S. patent nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.

Initial OLEDs used emissive molecules that emitted light ("fluorescence") from a singlet state, as disclosed, for example, in U.S. patent No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission typically occurs in time frames less than 10 nanoseconds.

Recently, OLEDs have been demonstrated that have emissive materials that emit light from a triplet state ("phosphorescence"). Baldo et al, "efficient phosphorescent emission from organic electroluminescent devices (Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices)", nature, vol.395, 151-154,1998 ("Baldo-I"); and Bardo et al, "Very efficient green organic light emitting device based on electrophosphorescence (Very high-efficiency green organic light-emitting devices based on electrophosphorescence)", applied physical fast report (appl. Phys. Lett.), vol.75, stages 3,4-6 (1999) ("Bardo-II"), incorporated by reference in its entirety. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704, columns 5-6, which is incorporated by reference.

Fig. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. The 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 blocking layer 170. Cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. The device 100 may be fabricated by depositing the layers in sequence. The nature and function of these various layers and example materials are described in more detail in U.S. Pat. No. 7,279,704 at columns 6-10, which is incorporated by reference.

Further examples of each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is doped with F in a 50:1 molar ratio ₄ m-MTDATA of TCNQ, as disclosed in U.S. patent application publication No. 2003/0239980, which is incorporated by reference in its entirety. Examples of luminescent and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al, which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a molar ratio of 1:1, as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of cathodes are disclosed in U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, that include composite cathodes having a thin layer of metal (e.g., mg: ag) containing an overlying transparent, electrically conductive, sputter-deposited ITO layer. Theory of barrier layer And uses are described in more detail in U.S. patent No. 6,097,147 and U.S. patent application publication No. 2003/0230980, which are incorporated by reference in their entirety. Examples of implanted layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.

Fig. 2 shows 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. The device 200 may be fabricated by depositing the layers in sequence. Because the most common OLED configuration has a cathode disposed above an anode, and the device 200 has a cathode 215 disposed below an anode 230, the 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. 2 provides one example of how some layers may be omitted from the structure of the apparatus 100.

The simple layered structure illustrated in fig. 1 and 2 is provided by way of non-limiting example, and it should be understood that embodiments of the present disclosure may be used in conjunction with a 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 obtained by combining the various layers described in different ways, or the 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 the various layers as comprising a single material, it should be understood that combinations of materials may be used, such as mixtures of host and dopant, or more generally, mixtures. Further, 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 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, 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. 1 and 2.

Structures and materials not specifically described, such as OLEDs (PLEDs) comprising polymeric materials, such as disclosed in frank (Friend) et al, U.S. patent No. 5,247,190, which is incorporated by reference in its entirety, may also be used. By way of another example, an OLED with a single organic layer may be used. The OLEDs can be stacked, for example, as described in U.S. patent No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in fig. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Furster et al, and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Boolean et al, which are incorporated by reference in their entirety.

Any of the layers of the various embodiments may be deposited by any suitable method unless otherwise specified. Preferred methods for the organic layer include thermal evaporation, ink jet (as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, incorporated by reference in their entirety), organic vapor deposition (OVPD) (as described in U.S. Pat. No. 6,337,102, incorporated by reference in its entirety), and deposition by Organic Vapor Jet Printing (OVJP) (as described in U.S. Pat. No. 7,431,968, incorporated by reference in its entirety). Other suitable deposition methods include spin-coating and other solution-based processes. The solution-based process is preferably carried out under nitrogen or an inert atmosphere. For other layers, the preferred method includes thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding (as described in U.S. patent nos. 6,294,398 and 6,468,819, incorporated by reference in their entirety), and patterning associated with some of the deposition methods such as inkjet and Organic Vapor Jet Printing (OVJP). Other methods may also be used. The material to be deposited may be modified to suit the particular deposition method. For example, substituents such as alkyl and aryl groups that are branched or unbranched and preferably contain at least 3 carbons can be used in small molecules to enhance their ability to withstand solution processing. Substituents having 20 carbons or more may be used, and 3 to 20 carbons are a preferred range. A material with an asymmetric structure may have better solution processibility than a material with a symmetric structure because an asymmetric material 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 according to embodiments of the present disclosure may further optionally include a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from harmful substances exposed to the environment including moisture, vapors and/or gases, etc. The barrier layer may be deposited on the substrate, electrode, under or beside the substrate, electrode, or on any other portion of the device, including the 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 a composition having a single phase and a composition having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic compounds or organic compounds or both. Preferred barrier layers comprise a mixture of polymeric and non-polymeric materials, as described in U.S. patent No. 7,968,146, PCT patent application No. PCT/US2007/023098, and PCT/US2009/042829, which are incorporated herein by reference in their entirety. To be considered as a "mixture", the aforementioned polymeric and non-polymeric materials that make up the barrier layer should be deposited under the same reaction conditions and/or simultaneously. The weight ratio of polymeric material to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be produced from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.

Devices manufactured in accordance with embodiments of the present disclosure may be incorporated into a wide variety of electronic component modules (or units), which may be incorporated into a wide variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices (e.g., discrete light source devices or lighting panels), etc., that may be utilized by end user product manufacturers. The electronics assembly module may optionally include drive electronics and/or a power source. Devices manufactured in accordance with embodiments of the present disclosure may be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. Disclosed is a consumer product comprising an OLED comprising a compound of the present disclosure in an organic layer in the OLED. The consumer product should include any kind of product that contains one or more light sources and/or one or more of some type of visual display. 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, cellular telephones, tablet computers, tablet phones, personal Digital Assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, micro-displays (displays with a diagonal of less than 2 inches), 3-D displays, virtual or augmented reality displays, vehicles, video walls including a plurality of tiled displays, theatre or gym screens, phototherapy devices, and signs. Various control mechanisms may be used to control devices manufactured in accordance with the present disclosure, including passive matrices and active matrices. Many of the devices are intended to be used in a temperature range that is comfortable for humans, such as 18 ℃ to 30 ℃, and more preferably at room temperature (20-25 ℃), but can be used outside this temperature range (e.g., -40 ℃ to +80 ℃).

Further details regarding OLEDs and the definitions described above can be found in U.S. patent No. 7,279,704, which is incorporated herein by reference in its entirety.

The materials and structures described herein may be applied in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices such as organic transistors may employ the materials and structures.

In some embodiments, the OLED has one or more features selected from the group consisting of: flexible, crimpable, collapsible, stretchable and bendable. In some embodiments, the OLED is transparent or translucent. 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 includes an RGB pixel arrangement or a white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel having a diagonal of less than 10 inches or an area of less than 50 square inches. In some embodiments, the OLED is a display panel having a diagonal of at least 10 inches or an area of at least 50 square inches. In some embodiments, the OLED is an illumination panel.

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

In some embodiments, the compounds may be used as a phosphor-photosensitizing agent in an OLED, where one or more layers in the OLED contain receptors in the form of one or more fluorescent and/or delayed fluorescent emitters. In some embodiments, the compound may be used as a component of an exciplex to be used as a sensitizer. As a phosphorus photosensitizer, the compound must be able to transfer energy to the acceptor and the acceptor will emit energy or further transfer energy to the final emitter. The receptor concentration may be in the range of 0.001% to 100%. The acceptor may be in the same layer as the phosphorus photosensitizer or in one or more different layers. In some embodiments, the receptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission may be produced by any or all of the sensitizer, acceptor, and final emitter.

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

The OLEDs disclosed herein can be incorporated into one or more of consumer products, electronics assembly modules, and lighting panels. The organic layer may be an emissive layer, and the compound may be an emissive dopant in some embodiments, and the compound may be a non-emissive dopant in other embodiments.

In yet another aspect of the invention, a formulation comprising the novel compounds disclosed herein is described. The formulation may comprise one or more components disclosed herein selected from the group consisting of: a solvent, a host, a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, and an electron transport material.

The present disclosure encompasses any chemical structure comprising the novel compounds of the present disclosure or monovalent or multivalent variants thereof. In other words, the compounds of the invention or monovalent or multivalent variants thereof may be part of a larger chemical structure. Such chemical structures may be selected from the group consisting of: monomers, polymers, macromolecules and supramolecules (also known as supramolecules). As used herein, "monovalent variant of a compound" refers to the same moiety as the compound but with one hydrogen removed and replaced with a bond to the rest of the chemical structure. As used herein, "multivalent variant of a compound" refers to a moiety that is identical to the compound but where more than one hydrogen has been removed and replaced with one or more bonds to the rest of the chemical structure. In the case of supramolecules, the compounds of the present invention may also be incorporated into supramolecular complexes without covalent bonds.

D. Combinations of compounds of the present disclosure with other materials

Materials described herein as suitable for use in particular layers in an organic light emitting device may be used in combination with a variety of other materials present in the device. For example, the emissive dopants disclosed herein can be used in combination with a wide variety of hosts, transport layers, barrier layers, implant layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one of ordinary skill in the art may readily review the literature to identify other materials that may be used in combination.

a) Conductive dopants:

the charge transport layer may be doped with a conductive dopant to substantially change its charge carrier density, which in turn will change its conductivity. Conductivity is increased by the generation of charge carriers in the host material and, depending on the type of dopant, a change in Fermi level (Fermi level) of the semiconductor can also be achieved. The hole transport layer may be doped with a p-type conductivity dopant, and an n-type conductivity dopant is used in the electron transport layer.

Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references disclosing those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047 and US2012146012.

b)HIL/HTL：

The hole injection/transport material used in the present disclosure is not particularly limited, and any compound may be used as long as the compound is generally used as a hole injection/transport material. Examples of materials include (but are not limited to): phthalocyanines or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; a fluorocarbon-containing polymer; a polymer having a conductive dopant; conductive polymers such as PEDOT/PSS; self-assembled monomers derived from compounds such as phosphonic acids and silane derivatives; metal oxide derivatives, e.g. MoO _x The method comprises the steps of carrying out a first treatment on the surface of the p-type semiconducting organic compounds such as 1,4,5,8,9, 12-hexaazatriphenylene hexacarbonitrile; a metal complex; a crosslinkable compound.

Examples of aromatic amine derivatives for the HIL or HTL include, but are not limited to, the following general structures:

Ar ¹ to Ar ⁹ Is selected from: a group consisting of, for example, the following aromatic hydrocarbon cyclic compounds: benzene, biphenyl, triphenylene, naphthalene, anthracene, benzene, phenanthrene, fluorene, pyrene, and the like,Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindol, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxazole Triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazole, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furandipyridine, benzothiophenopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units which are the same type or different types of groups selected from an aromatic hydrocarbon ring group and an aromatic heterocyclic group and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group. Each Ar may be unsubstituted or may be substituted with a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, ar ¹ To Ar ⁹ Independently selected from the group consisting of:

wherein k is an integer from 1 to 20; x is X ¹⁰¹ To X ¹⁰⁸ Is C (including CH) or N; z is Z ¹⁰¹ Is NAr ¹ O or S; ar (Ar) ¹ Having the same groups as defined above.

Examples of metal complexes used in the HIL or HTL include, but are not limited to, the following general formula:

wherein Met is a metal that may have an atomic weight greater than 40; (Y) ¹⁰¹ -Y ¹⁰² ) Is a bidentate ligand, Y ¹⁰¹ And Y ¹⁰² Independently selected from C, N, O, P and S; l (L) ¹⁰¹ Is an auxiliary ligand; k' is an integer value of 1 to the maximum number of ligands that can be attached to the metal; and k' +k "is the maximum number of ligands that can be attached to the metal.

In one aspect, (Y) ¹⁰¹ -Y ¹⁰² ) Is a 2-phenylpyridine derivative. In another aspect, (Y) ¹⁰¹ -Y ¹⁰² ) Is a carbene ligand. In another aspect, met is selected from Ir, pt, os, and Zn. In another aspect, the metal complex has a chemical structure as compared to an Fc ⁺ The minimum oxidation potential in solution of less than about 0.6V for Fc coupling.

Non-limiting examples of HIL and HTL materials that can be used in an OLED in combination with the materials disclosed herein are exemplified with references disclosing those materials as follows: CN, DE, EP EP, JP07-, JP EP, EP JP07-, JP US, US US, WO US, US WO, WO.

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c)EBL：

An Electron Blocking Layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a barrier layer in a device may result in substantially higher efficiency and/or longer lifetime than a similar device lacking such a barrier layer. Furthermore, a blocking layer may be used to limit the emission to a desired area of the 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 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 the EBL contains the same molecule or the same functional group as used in one of the hosts described below.

d) A main body:

the light-emitting layer of the organic EL device of the present disclosure preferably contains at least a metal complex as a 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 complex or organic compound may be used as long as the triplet energy of the host is greater than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria are met.

Examples of metal complexes used as hosts preferably have the general formula:

wherein Met is a metal; (Y) ¹⁰³ -Y ¹⁰⁴ ) Is a bidentate ligand, Y ¹⁰³ And Y ¹⁰⁴ Independently selected from C, N, O, P and S; l (L) ¹⁰¹ Is another ligand; k' is an integer value of 1 to the maximum number of ligands that can be attached to the metal; and k' +k "is the maximum number of ligands that can be attached to the metal.

In one aspect, the metal complex is:

wherein (O-N) is a bidentate ligand having a metal coordinated to the O and N atoms.

In another aspect, met is selected from Ir and Pt. In another aspect, (Y) ¹⁰³ -Y ¹⁰⁴ ) Is a carbene ligand.

In one aspect, the host compound contains at least one selected from the group consisting of: a group consisting of, for example, the following aromatic hydrocarbon cyclic compounds: benzene, biphenyl, triphenylene, tetramethylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as: dibenzothiophene, dibenzofuran and dibenzoselenopheneFuran, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazole, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furodipyridine, benzothiophene pyridine, thiophenodipyridine, benzoselenophenopyridine and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units which are the same type or different types of groups selected from an aromatic hydrocarbon ring group and an aromatic heterocyclic group and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group. Each option in each group may be unsubstituted or may be substituted with a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.

In one aspect, the host compound contains in the molecule at least one of the following groups:

wherein R is ¹⁰¹ Selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl,Aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof, and when it is aryl or heteroaryl, it has a similar definition as Ar as mentioned above. k is an integer from 0 to 20 or from 1 to 20. X is X ¹⁰¹ To X ¹⁰⁸ Independently selected from C (including CH) or N. Z is Z ¹⁰¹ And Z ¹⁰² Independently selected from NR ¹⁰¹ O or S.

Non-limiting examples of host materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references disclosing those materials: US, WO WO, WO-based US, WO WO, US, US and US,

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e) Other emitters:

one or more other emitter dopants may be used in combination with the compounds of the present invention. Examples of other emitter dopants are not particularly limited, and any compound may be used as long as the compound is generally used as an emitter material. Examples of suitable emitter materials include, but are not limited to, compounds that can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also known as E-delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.

Non-limiting examples of emitter materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references disclosing those materials: CN, EB, EP1239526, EP, JP, KR TW, US20010019782, US TW, US20010019782, US US, US US, WO US, US US, WO.

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f)HBL：

A Hole Blocking Layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a barrier layer in a device may result in substantially higher efficiency and/or longer lifetime than a similar device lacking the barrier layer. Furthermore, a blocking layer may be used to limit the emission to a desired area of the OLED. In some embodiments, the HBL material has a lower HOMO (farther 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 (farther from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.

In one aspect, the compound used in the HBL contains the same molecules or the same functional groups as used in the host described above.

In another aspect, the compound used in the HBL contains in the molecule at least one of the following groups:

wherein k is an integer from 1 to 20; l (L) ¹⁰¹ Is another ligand, and k' is an integer from 1 to 3.

g)ETL：

An Electron Transport Layer (ETL) may include a material capable of transporting electrons. The 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 complex or organic compound may be used as long as it is generally used to transport electrons.

In one aspect, the compounds used in ETL contain in the molecule at least one of the following groups:

wherein R is ¹⁰¹ Selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof, when aryl or heteroaryl, have similar definitions as for Ar described above. Ar (Ar) ¹ To Ar ³ Has a similar definition to Ar mentioned above. k is an integer of 1 to 20. X is X ¹⁰¹ To X ¹⁰⁸ Selected from C (including CH) or N.

In another aspect, the metal complex used in ETL contains (but is not limited to) the following formula:

wherein (O-N) or (N-N) is a bidentate ligand having a metal coordinated to atom O, N or N, N; l (L) ¹⁰¹ Is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal.

Non-limiting examples of ETL materials that can be used in an OLED in combination with the materials disclosed herein are exemplified below along with references disclosing those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,

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h) Charge Generation Layer (CGL)

In tandem or stacked OLEDs, CGL plays a fundamental role in performance, consisting of n-doped and p-doped layers for injecting electrons and holes, respectively. Electrons and holes are supplied by the CGL and the electrode. Electrons and holes consumed in the CGL are refilled with electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials include n and p conductivity dopants used in the transport layer.

In any of the above mentioned compounds used in each layer of the OLED device, the hydrogen atoms may be partially or fully deuterated. Thus, any of the specifically listed substituents, such as (but not limited to) methyl, phenyl, pyridyl, and the like, can be in their non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (e.g., without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc.) can also be in their non-deuterated, partially deuterated, and fully deuterated forms.

It should be understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. For example, many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the invention. The invention as claimed may thus include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that the various theories as to why the present invention works are not intended to be limiting.

Experiment

Synthesis of examples of the invention

Examples of the invention

Process flow

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Examples of the invention

Step 1: synthesis of 1- (4-methoxy-2-nitrophenoxy) naphthalene: naphthalene-1-ol (21.06 g,146 mmol) was dissolved in anhydrous dimethylsulfoxide (500 mL) under an inert atmosphere in a 2L 3-necked round bottom flask equipped with an air condenser at the top. Potassium carbonate (40.4 g,292 mmol) and 1-fluoro-4-methoxy-2-nitrobenzene (25.0 g,146 mmol) were then both added in one portion and the reaction mixture stirred at 100℃for 2 hours. The reaction mixture was cooled to room temperature and poured into an ice/water mixture. A brown solid precipitated out, which was subsequently filtered off and rinsed with water. The resulting brown solid was wet milled with diethyl ether until the color changed from brown to yellow. Finally the solid was dried under vacuum to give (42 g,141mmol, 96%).

Step 2: synthesis of 8-methoxy-10-nitronaphtho [1,2-b ] benzofuran: 1- (4-methoxy-2-nitrophenoxy) naphthalene (21 g,71.1 mmol), potassium carbonate (3.94 g,28.4 mmol) and palladium (II) acetate (3.2 g,14.2 mmol) were suspended in pivalic acid (80 mL) in a 250mL round bottom flask and stirred under an open air atmosphere at 120℃for 72 hours. The mixture was cooled to room temperature, transferred to a 3L round bottom flask, and dissolved in DCM (1L). 2M sodium hydroxide (1L) was then added with stirring and the resulting suspension was filtered off through the celite route. The organic phase was separated, washed with brine, dried over magnesium sulfate and the solvent was removed. The resulting crude mixture was purified by chromatography using a mixture of isohexane/dichloromethane to give a yellow solid (8.5 g,28.7mmol, 40.3%).

Step 3: synthesis of 8-methoxynaphtho [1,2-b ] benzofuran-10-amine: 8-methoxy-10-nitronaphtho [1,2-b ] benzofuran (25.0 g,85 mmol) was dissolved in a round bottom flask with an air condenser on top and then dissolved in hot anhydrous 1, 4-dioxane (240 mL) until a clear solution was obtained. Water (60 mL), iron powder (36.7 g, 560 mmol) and ammonium chloride (30.5 g,571 mmol) were then added and the mixture stirred at 100deg.C for 18 hours. The reaction mixture was cooled to room temperature and filtered through a celite route. The solvent was removed in vacuo and the resulting crude mixture was partitioned between 2-methyltetrahydrofuran (200 mL) and water (200 mL). The organics were separated, dried over magnesium sulfate, and the solvent was removed to give a brown solid. Finally wet trituration with methanol gave a yellow solid (14 g,53.2mmol, 63%).

Step 4: synthesis of 10-bromo-8-methoxynaphtho [1,2-b ] benzofuran: copper (II) bromide (1.272 g,5.70 mmol) was added to a stirred solution of hydrated 4-methylbenzenesulfonic acid (13.00 g,68.4 mmol), t-butyl nitrite (7.05 g,68.4 mmol), 8-methoxynaphtho [1,2-b ] benzofuran-10-amine (15 g,57.0 mmol) and tetrabutylammonium bromide (22.04 g,68.4 mmol) in anhydrous acetonitrile (500 mL) in a 3-neck round bottom flask under an inert atmosphere. The mixture was stirred at room temperature for 1 hour. The solvent was then removed in vacuo and the resulting mixture was partitioned between 2-methyltetrahydrofuran (200 mL) and water (200 mL). The organics were separated, dried over magnesium sulfate, and the solvent was removed to give a brown oil. The crude mixture was purified by chromatography using a mixture of isohexane/tetrahydrofuran to give a brown solid which was then wet-triturated with methanol to give a white solid (11 g,33.6mmol, 57%).

Step 5: synthesis of 2- (8-methoxynaphtho [1, 2-b)]Benzofuran-10-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan: potassium acetate (13.5 g,138 mmol), 10-bromo-8-methoxynaphtho [1,2-b ] was placed in a 1L three-necked round bottom flask equipped with a reflux condenser on top]Benzofuran (15 g,45.8 mmol), 1' -bis (diphenylphosphino) ferrocene-palladium (II) dichloride dichloromethane complex (3.73 g,4.58 mmol) and bis(pinacol) diboron (23.28 g,92 mmol) was dissolved in anhydrous dioxane (300 mL). N for mixtures ₂ Bubbling was carried out for 30 minutes, and the reaction was stirred at 100℃for 4 hours. The crude reaction product was then partitioned between ethyl acetate (300 mL) and water (300 mL), the organics separated, washed with brine (2 x 200 mL), dried over magnesium sulfate and the solvent removed. The crude product was purified by chromatography using a mixture of isohexane/ethyl acetate to give a yellow solid (12 g,45.8mmol, 70%).

Step 6: synthesis of 4- (tert-butyl) -2- (8-methoxynaphtho [1, 2-b)]Benzofuran-10-yl) pyridine: sodium carbonate (8.5 g,80 mmol), 2- (8-methoxynaphtho [1, 2-b) was placed in a 500mL round bottom flask equipped with an air condenser on top]Benzofuran-10-yl) -4, 5-tetramethyl-1, 3, 2-dioxaborolan (12 g,32.1 mmol) and 4- (tert-butyl) -2-chloropyridine (10.88 g,64.1 mmol) were dissolved in a 1, 4-dioxane:water (250 mL) mixture (4:1). N for mixtures ₂ Bubbling for 15 min followed by addition of tetrakis (triphenylphosphine) palladium (0) (3.71 g,3.21 mmol) and the mixture was purified with N ₂ Bubbling was performed for another 15 minutes. The reaction was stirred at 100℃for 18 hours. The reaction crude product was partitioned between ethyl acetate (300 mL) and brine (300 mL), the organics separated, washed with brine (2 x 300 mL), dried over magnesium sulfate and the solvent removed. The crude mixture was purified by chromatography using a mixture of isohexane/ethyl acetate to give a white solid (7.5 g,19.66mmol, 61.3%).

Step 7: synthesis of 10- (4- (tert-butyl) pyridin-2-yl) naphtho [1,2-b ] benzofuran-8-ol: 4- (tert-butyl) -2- (8-methoxynaphtho [1,2-b ] benzofuran-10-yl) pyridine (7.5 g,19.66 mmol) and pyridine hydrochloride (11.36 g,98 mmol) were mixed in a 250mL round bottom flask equipped with an air condenser at the top. The mixture was stirred at 190 ℃ under an air atmosphere for 3 hours. It was allowed to cool to room temperature and the pH was adjusted to 7 using 2M sodium hydroxide solution. Partitioned between ethyl acetate (100 mL) and water (100 mL). The organics were separated, dried over magnesium sulfate, and the solvent was removed to give a black solid. The crude mixture was purified by chromatography using a mixture of isohexane/acetone to give a yellow solid (2.1 g,6mmol, 29%).

Step 8: synthesis of 9- (4- (tert-butyl) pyridin-2-yl) -2- ((10- (4- (tert-butyl) pyridin-2-yl) naphtho [1,2-b ] benzofuran-8-yl) oxy) -9H-carbazole: copper (I) iodide (0.038 g,0.197mmol,0.06 eq.) was added to a mixture of 10- (4- (tert-butyl) pyridin-2-yl) -naphtho [1,2-b ] benzofuran-8-ol (1.448 g,3.94mmol,1.2 eq.), 9- (4- (tert-butyl) -pyridin-2-yl) -2-iodo-9H-carbazole (1.4 g,3.28mmol,1.0 eq.), picolinic acid (0.049 g, 0.390 mmol,0.12 eq.) and tripotassium phosphate monohydrate (1.460 g,6.90mmol,2.1 eq.) in dimethyl sulfoxide (10 mL). The reaction mixture was heated at 120 ℃ for 2 hours. LCMS analysis indicated 96.4% conversion to the desired product. The reaction mixture was cooled to room temperature and diluted with water (5 mL). The resulting solid was filtered and washed with methanol (5×5 mL) to give 9- (4- (tert-butyl) pyridin-2-yl) -2- ((10- (4- (tert-butyl) pyridin-2-yl) naphtho [1,2-b ] benzofuran-8-yl) oxy) -9H-carbazole (1.9 g,87% yield, 98.5% lc purity) as an off-white solid.

Step 9: the embodiment of the invention is synthesized: a mixture of 9- (4- (tert-butyl) pyridin-2-yl) -2- ((10- (4- (tert-butyl) pyridin-2-yl) naphtho [1,2-b ] benzofuran-8-yl) oxy) -9H-carbazole (1.8 g,2.70mmol,1.0 eq.) and platinum (II) acetylacetonate (1.06 g,2.70mmol,1.0 eq.) in acetic acid (10 mL) was bubbled with nitrogen for 10 min, followed by heating to reflux. After 40 hours, the reaction mixture was cooled to room temperature and diluted with water (10 mL). The resulting solid was filtered and washed with water (2X 2 mL) and methanol (5 mL) to give a brown solid. The crude product was purified on an intel automated chromatography system (80 g silica gel stub) eluting with a gradient of 0 to 50% dichloromethane/heptane. The product was wet-milled with methanol (about 10 mL) containing about 10% dichloromethane to give 9- (4- (tert-butyl) pyridin-2-yl) -2- ((10- (4- (tert-butyl) pyridin-2-yl) naphtho [1,2-b ] benzofuran-8-yl) oxy) -9H-carbazole (1.7 g,73.2% yield, 99.7% uplc purity) as an orange solid.

Comparative examples were synthesized

Process flow

Comparative example

Step 1. Synthesis of 3 '-chloro-2', 5 '-difluoro- [1,1' -biphenyl]-2-alcohol: a suspension of 1-bromo-3-chloro-2, 5-difluorobenzene (10.0 g,44.0 mmol), (2-hydroxyphenyl) boric acid (6.67 g,48.4 mmol) and potassium carbonate (15.2 g,110 mmol) in 1, 4-dioxane (100 mL) and water (100 mL) was bubbled with nitrogen for 10 min. Pd (PPh) was added ₃ ) ₄ (1.52 g,1.32 mmol) and the reaction mixture was stirred at 105℃for 6 hours. The reaction mixture was cooled to room temperature, poured into ice water (500 mL) and extracted with EtOAc (3×300 mL). The combined organics were washed with brine (200 mL), dried over MgSO ₄ Dried, filtered and pre-adsorbed onto silica gel. Purification by flash column chromatography (silica gel, 330g short column, solid support, 0-20% EtOAc/isohexane) afforded 3 '-chloro-2', 5 '-difluoro- [1,1' -biphenyl as a colorless oil]2-alcohol (9.65 g,39.6mmol,90% yield, > 98% UPLC purity).

Step 2, synthesizing 4-chloro-2-fluorodibenzo [ b, d ] furan: a suspension of 3 '-chloro-2', 5 '-difluoro- [1,1' -biphenyl ] -2-ol (16.0 g,66.5 mmol) and potassium carbonate (13.8 g,100 mmol) in NMP (200 mL) was stirred under nitrogen at 150℃for 4 hours. The reaction mixture was cooled to room temperature and poured into ice water (800 mL) and stirred for 30 min. The precipitate was collected by filtration and the filter cake was rinsed with water (500 mL). The wet cake was dissolved in DCM (800 mL), filtered through a short pad of silica and concentrated to give 4-chloro-2-fluorodibenzo [ b, d ] furan (11.5 g,51.0mmol,77% yield, 98% uplc purity) as a white solid.

Steps 3 and 4: synthesis of 4- (tert-butyl) -2- (2-fluorodibenzo [ b, d)]Furan-4-yl) pyridine: potassium acetate (18.9 g,193 mmol), bis (pinacolato) diboron (29.4 g,116 mmol), XPhos (2.94 g,6.16 mmol) and 4-chloro-2-fluorodibenzo [ b, d]A suspension of furan (2) (17.0 g,77 mmol) in 1, 4-dioxane (170 mL) was bubbled with nitrogen for 10 min. Pd addition ₂ (dba) ₃ (2.82g，3.08 mmol) and the reaction mixture was stirred at 100℃for 3 hours. The reaction was cooled to room temperature, diluted with water (300 mL), and extracted with EtOAc (500 mL followed by 2X 300 mL). The combined organics were washed with brine (500 mL), dried over MgSO ₄ Dried, filtered and concentrated. The residue was dissolved in a mixture of 1, 4-dioxane (170 mL) and water (170 mL), followed by the addition of 4- (tert-butyl) -2-chloropyridine (13.7 g,81.0 mmol) and K ₃ PO ₄ (40.9 g,193 mmol). The resulting mixture was bubbled with nitrogen for 10 minutes and Pd (PPh) was added ₃ ) ₄ (3.56 g,3.08 mmol). The reaction mixture was stirred at 100deg.C for 16 hours, cooled to room temperature, poured into ice water (500 mL), and extracted with EtOAc (3X 500 mL). The combined organics were washed with water (300 mL) and brine (300 mL) then concentrated. Purification by flash chromatography (silica gel, 330g short column, 0-30% EtOAc/isohexane) afforded 4- (tert-butyl) -2- (2-fluorodibenzo [ b, d) as an off-white solid ]Furan-4-yl) pyridine (22.5 g,66.9mmol,87% yield, 97% uplc purity).

Step 5. Synthesis of 4- (tert-butyl) -2- (2-methoxydibenzo [ b, d ] furan-4-yl) pyridine: a suspension of 4- (tert-butyl) -2- (2-fluorodibenzo [ b, d ] furan-4-yl) pyridine (3) (23.5 g,73.6 mmol) and sodium methoxide (15.9 g, 254 mmol) in anhydrous DMSO (150 mL) was stirred at 100deg.C under nitrogen for 18 hours. The reaction mixture was cooled to room temperature, poured into ice water (500 mL) and extracted with EtOAc (3×500 mL). The combined organics were washed with water (200 mL) and brine (300 mL) then concentrated. Purification by flash chromatography (silica gel, 330g stub, solid supported on silica, 0-20% etoac/isohexane) afforded 4- (tert-butyl) -2- (2-methoxydibenzo [ b, d ] furan-4-yl) pyridine (16.5 g,49.3mmol,67% yield, 98% hplc purity) as a white solid.

Step 6 synthesis of 4- (4-tert-butyl) pyridin-2-yl) dibenzo [ b, d ] furan-2-ol: sodium ethanethiolate (2.16 g,25.65mmol,3.4 eq.) is added to a solution of 4- (tert-butyl) -2- (2-methoxydibenzo [ b, d ] furan-4-yl) pyridine (2.5 g,7.54mmol,1.0 eq.) in N-methyl-2-pyrrolidone (10 mL) and the reaction mixture is heated at 100deg.C. After 2 hours a large amount of solid formed and the stirring by the stirring bar was stopped. The reaction mixture was cooled to room temperature, followed by the addition of ethyl acetate (50 mL) and saturated aqueous ammonium chloride (50 mL). The separated organic layer was washed with saturated brine (50 mL), dried over sodium sulfate (50 g), filtered and concentrated under reduced pressure. The residue was purified on an intel automated system (80 g silica gel stub), eluting with 0-70% ethyl acetate/heptane, to give 4- (4- (tert-butyl) pyridin-2-yl) -dibenzo [ b, d ] furan-2-ol (1.52 g,64% yield, 98% lc purity) as a white solid.

Step 7. Synthesis of 9- (4- (tert-butyl) pyridin-2-yl) -2- ((4- (4- (tert-butyl) pyridin-2-yl) dibenzo [ b, d ] -furan-2-yl) oxy) -9H-carbazole: copper (I) iodide (0.037 g,0.194mmol,0.06 eq.) was added to a mixture of 4- (4- (tert-butyl) pyridin-2-yl) dibenzo- [ b, d ] furan-2-ol (1.233 g,3.88mmol,1.2 eq.), 9- (4- (tert-butyl) pyridin-2-yl) -2-iodo-9H-carbazole (1.38 g,3.24mmol,1.0 eq.), picolinic acid (0.048 g, 0.3838 mmol,0.12 eq.) and potassium phosphate (1.443 g,6.80mmol,2.1 eq.) in dimethyl sulfoxide (12 mL). The reaction mixture was heated at 120 ℃ for 2 hours. LCMS analysis showed the reaction mixture contained 70% product, 15% unreacted material, and 15% unknown impurities. 4- (4- (tert-butyl) -pyridin-2-yl) dibenzo [ b, d ] furan-2-ol (0.2 g,0.63mmol,0.2 eq.) was added and heating continued without further reaction taking place. The reaction mixture was cooled to room temperature, followed by addition of ethyl acetate (50 mL) and saturated brine (50 mL). The organic layer was separated and the aqueous layer was extracted with ethyl acetate (50 mL). The combined organic layers were washed with saturated brine (50 mL), dried over sodium sulfate (50 g), filtered and concentrated under reduced pressure. The residue was purified on an intel automation system (120 g silica gel stub) eluting with a gradient of 0-50% ethyl acetate/heptane to give 9- (4- (tert-butyl) -pyridin-2-yl) -2- ((4- (4- (tert-butyl) -pyridin-2-yl) dibenzo [ b, d ] furan-2-yl) oxy) -9H-carbazole (1.33 g,67% yield, 98.5% lc purity) as a white solid.

Step 8. Synthesis of platinum Complex of 9- (4- (tert-butyl) pyridin-2-yl) -2- ((4- (4- (tert-butyl) pyridin-2-yl) dibenzo [ b, d ] furan-2-yl) oxy) -9H-carbazole: a mixture of 9- (4- (tert-butyl) pyridin-2-yl) -2- ((4- (4- (tert-butyl) pyridin-2-yl) dibenzo [ b, d ] furan-2-yl) oxy) -9H-carbazole (1.33 g,2.16mmol,1.0 eq.) and platinum (II) acetylacetonate (0.85 g,2.16mmol,1.0 eq.) in acetic acid (10 mL) was bubbled with nitrogen for 10 min followed by heat reflux. The reaction mixture was cooled to room temperature and water (10 mL) was added. The solid was filtered and washed sequentially with water (2X 2 mL) and methanol (3X 1 mL) to give a brown solid. The crude product was purified on an Interhim automated system (80 g silica gel short column) eluting with a gradient of 0-70% dichloromethane/heptane. The recovered material was wet-milled with dichloromethane/methanol to give a platinum complex of 9- (4- (tert-butyl) pyridin-2-yl) -2- ((4- (4- (tert-butyl) pyridin-2-yl) dibenzo [ b, d ] furan-2-yl) -oxy) -9H-carbazole (0.45 g,26% yield, 99.7% uplc purity) as a yellow solid.

TABLE 1 sublimation Profile

The present examples successfully sublimated at a temperature of 350 ℃. Whereas the comparative example decomposed during sublimation at a temperature of 330 ℃. It was unexpectedly found that the inventive examples had better thermal properties than the comparative examples. Since the comparative examples failed to sublimate, the comparative example compounds could not be used to manufacture OLEDs, and there were no device test results for the comparative examples.

Device instance

All example devices were operated under high vacuum<10 ^-7 Tray) is thermally evaporated. The anode electrode beingIndium Tin Oxide (ITO). The cathodes are sequentially->Liq (lithium 8-hydroxyquinoline) and +.>Al composition of (c). All devices were capped with epoxy-sealed glass immediately after manufacture in a nitrogen glove box<1ppm of H ₂ O and O ₂ ) And packaging, and filling a moisture absorbent in the package. The organic stack of the device example consisted of, in order from the ITO surface: />HAT-CN as a Hole Injection Layer (HIL); />HTM as Hole Transport Layer (HTL); />As Electron Blocking Layer (EBL), of thickness ofIs an emission layer (EML). The emissive layer contains an H-host (H1) E-host (H2) and 12 wt% green emitter in a 6:4 ratio. />Is doped with 40% ETM as ETL. The device structure is shown in table 2 below. Table 2 shows an exemplary device structure. The chemical structure of the device material is shown below. />

After manufacture, EL, JVL measurements have been performed on the device and measured at DC 80mA/cm ² Life testing was performed as follows. Assuming that the acceleration factor is 1.8, LT95 of 1,000 nits is calculated from 80mA/cm2 LT data. The device performance is shown in table 3 below.

TABLE 2 schematic device architecture

Table 3: device performance

For emissive transition metal chelates, a typical framework comprises at least one bidentate chelate as chromophore. There is growing interest in using multidentate chromophores (see conventional bidentate chromatography) to extend conjugation and enhance the stabilization energy of metal chelates. This strategy appears to be quite successful for platinum (II) systems, where chelating agents are used in OLED material applications; by using their square planar coordination geometry. Our invention applies this strategy to yellow dopant designs. The requirement of a yellow dopant is a maximum emission of 550nm. The present examples show 550nm emission in an OLED device under CIE of (0.45,0.54); which is well suited for yellow dopant applications.

Claims

1. A compound selected from the group consisting of compounds k-Si-j; wherein k is 1, i is an integer of 1 to 8, 13 to 20, 25 to 32, 37 to 44, and 49 to 57, and j is an integer of 1 to 16, and for each Si, the compound has a structure defined in the following list 1, wherein X in the structure is O:

wherein for each j R ¹ To R ⁵ The definition is as follows:

。

2. an organic light emitting device OLED comprising:

anode

A cathode; and

an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the compound of claim 1.

3. A consumer product comprising an organic light emitting device OLED, the organic light emitting device comprising:

anode

A cathode; and