Metal complex containing a first ligand, a second ligand, and a third ligand

Abstract

A metal complex containing three different ligands which may be used as a light-emitting material in a light-emitting layer of an organic electroluminescent device. These new complexes can not only achieve device performed desired to be adjusted or improved by adjusting substituents but also have the effect of effectively controlling increase of the evaporation temperature. Further disclosed are an electroluminescent device and a compound formulation including the metal complex.

Claims

1. A metal complex, having a general formula of M(L.sub.a).sub.m(L.sub.b).sub.n(L.sub.c).sub.q, wherein L.sub.a, L.sub.b and L.sub.c are a first ligand, a second ligand and a third ligand coordinated to the metal M respectively; wherein m is selected from an integer greater than or equal to 1, n is selected from an integer greater than or equal to 1, q is selected from an integer greater than or equal to 1, and m+n+q equals the oxidation state of the metal M; wherein L.sub.a and L.sub.b are ligands with different structures, and each independently represented by Formula 1: ##STR00052## wherein X.sub.1 to X.sub.4 are each independently selected from CR.sub.1 or N; wherein Y.sub.1 to Y.sub.6 are each independently selected from CR.sub.2 or N, and at least one of Y.sub.1 to Y.sub.6 is CR.sub.2; wherein R.sub.1 and R.sub.2 are each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; in Formula 1, for substituents R.sub.1 only, adjacent substituents can be optionally joined to form a ring which has a number of ring atoms less than or equal to 6; in the ligands L.sub.a and/or L.sub.b, at least one R.sub.2 is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; wherein L.sub.c has a structure represented by Formula 2: ##STR00053## wherein R.sub.t, R.sub.u, R.sub.v, R.sub.w, R.sub.x, R.sub.y and R.sub.z are each independently selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.

2. The metal complex of claim 1, wherein the metal M is selected from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir and Pt; preferably, the metal M is selected from Pt or Ir.

3. The metal complex of claim 1, wherein at least one of X.sub.1 to X.sub.4 is selected from CR.sub.1.

4. The metal complex of claim 1, wherein X.sub.1 and X.sub.4 are each independently selected from CR.sub.1, and/or Y.sub.1 to Y.sub.6 are each independently selected from CR.sub.2.

5. The metal complex of claim 1, wherein X.sub.1 is each independently CR.sub.1 and/or X.sub.3 is each independently CR.sub.1, and R.sub.1 is independently selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; preferably, R.sub.1 is independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms; more preferably, R.sub.1 is independently selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms.

6. The metal complex of claim 1, wherein Y.sub.1 is each independently CR.sub.2 and/or Y.sub.4 is each independently CR.sub.2, and R.sub.2 is independently selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; preferably, R.sub.2 is independently selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms; more preferably, R.sub.2 is independently selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms or substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms.

7. The metal complex of claim 1, wherein Y.sub.1 is CD, Y.sub.4 is CR.sub.2, and R.sub.2 is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms; preferably, R.sub.2 is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms or substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, and Y.sub.2, Y.sub.3, Y.sub.5 and Y.sub.6 are each CH.

8. The metal complex of claim 1, wherein Y.sub.1, Y.sub.2, Y.sub.3, Y.sub.4 and Y.sub.6 are each CH, Y.sub.5 is CR.sub.2, and R.sub.2 is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms.

9. The metal complex of claim 1, wherein Y.sub.2, Y.sub.3, Y.sub.4, Y.sub.5 and Y.sub.6 are each CH, Y.sub.1 is CR.sub.2, and R.sub.2 is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms.

10. The metal complex of claim 1, wherein R.sub.2 is each independently selected from the group consisting of: hydrogen, deuterium, methyl, isopropyl, 2-butyl, isobutyl, t-butyl, pent-3-yl, cyclopentyl, cyclohexyl, 4,4-dimethylcyclohexyl, neopentyl, 2,4-dimethylpent-3-yl, 3,3,3-trifluoro-2,2-dimethylpropyl, 1,1-dimethylsilacyclohex-4-yl, cyclopentylmethyl, cyanomethyl, cyano, trifluoromethyl, bromine, chlorine, trimethylsilyl, phenyldimethylsilyl, phenyl and 3-pyridyl.

11. The metal complex of claim 1, wherein L.sub.a and L.sub.b have different structures and are each independently selected from the group consisting of: ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181## ##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186## ##STR00187## ##STR00188## ##STR00189## ##STR00190## ##STR00191## ##STR00192## ##STR00193## ##STR00194## ##STR00195## ##STR00196## ##STR00197## ##STR00198## ##STR00199## ##STR00200## ##STR00201## ##STR00202## ##STR00203## ##STR00204## ##STR00205## ##STR00206## ##STR00207## ##STR00208## ##STR00209## ##STR00210## ##STR00211## ##STR00212## ##STR00213## ##STR00214## ##STR00215## ##STR00216## ##STR00217## ##STR00218## ##STR00219## ##STR00220## ##STR00221## ##STR00222## ##STR00223## ##STR00224## ##STR00225## ##STR00226## ##STR00227## ##STR00228## ##STR00229## ##STR00230## ##STR00231## ##STR00232## ##STR00233## ##STR00234## ##STR00235## ##STR00236## ##STR00237## ##STR00238## ##STR00239## ##STR00240## ##STR00241## ##STR00242## ##STR00243## ##STR00244## ##STR00245## ##STR00246## ##STR00247## ##STR00248## ##STR00249## ##STR00250## ##STR00251## ##STR00252## ##STR00253## ##STR00254## ##STR00255## ##STR00256## ##STR00257## ##STR00258## ##STR00259## ##STR00260## wherein x in numbers of the above specific structures of ligands represents a or b.

12. The metal complex of claim 1, wherein in Formula 2, R.sub.1, R.sub.u, R.sub.V, R.sub.w, R.sub.x, R.sub.y and R.sub.z are each independently selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, and combinations thereof; preferably, R.sub.t is selected from hydrogen, deuterium or methyl, and R.sub.u to R.sub.z are each independently selected from hydrogen, deuterium, methyl, ethyl, propyl, cyclobutyl, cyclopentyl, cyclohexyl, 3-methylbutyl, 3-ethylpentyl or combinations thereof.

13. The metal complex of claim 11, wherein L.sub.c is selected from the group consisting of: ##STR00261## ##STR00262## ##STR00263## ##STR00264## ##STR00265## ##STR00266## ##STR00267## ##STR00268## ##STR00269## ##STR00270## ##STR00271## ##STR00272## ##STR00273## ##STR00274## ##STR00275##

14. The metal complex of claim 13, wherein hydrogen in any one, any two or three of the ligands L.sub.a, L.sub.b and L.sub.c is partially or fully substituted by deuterium.

15. The metal complex of claim 13, wherein the metal complex is IrL.sub.aL.sub.bL.sub.c, wherein L.sub.a and L.sub.b have different structures, L.sub.a is any one selected from L.sub.a1 to L.sub.a1065, L.sub.b is any one selected from L.sub.b1 to L.sub.b1065, and L.sub.c is any one selected from L.sub.1 to L.sub.c84; preferably, L.sub.a is any one selected from L.sub.a1 to L.sub.a108, L.sub.a112 to L.sub.a144, L.sub.a148 to L.sub.a288, L.sub.a292 to L.sub.a362, L.sub.a364 to L.sub.a432, L.sub.a436 to L.sub.a720 and L.sub.a757 to L.sub.a1065, L.sub.b is any one selected from L.sub.b1 to L.sub.b1065, and L.sub.c is any one selected from L.sub.c1 to L.sub.c84; more preferably, the metal complex is selected from the group consisting of: ##STR00276## ##STR00277## ##STR00278## ##STR00279## ##STR00280## ##STR00281## ##STR00282## ##STR00283## ##STR00284## ##STR00285## ##STR00286## ##STR00287##

16. An electroluminescent device, comprising: an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the metal complex of claim 1.

17. The device of claim 16, wherein the organic layer is a light-emitting layer, and the metal complex is a light-emitting material; preferably, the organic layer further comprises a host material; preferably, the host material comprises at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, aza-dibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof.

18. The device of claim 16, wherein the device emits red light or white light.

19. A compound formulation, comprising the metal complex of claim 1.

20. The metal complex of claim 1, wherein R.sub.2 is selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof; in Formula 1, for substituents R.sub.1 only, adjacent substituents can be optionally joined to form a ring which has a number of ring atoms less than or equal to 6; in the ligands L.sub.a and/or L.sub.b, at least one R.sub.2 is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a schematic diagram of an organic light-emitting apparatus that may include a compound and a compound formulation disclosed by the present disclosure.

(2) FIG. 2 is a schematic diagram of another organic light-emitting apparatus that may include a compound and a compound formulation disclosed by the present disclosure.

DETAILED DESCRIPTION

(3) OLEDs can be fabricated on various types of substrates such as glass, plastic, and metal foil. FIG. 1 schematically shows an organic light emitting device 100 without limitation. The figures are not necessarily drawn to scale. Some of the layers in the figures can also be omitted as needed. Device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, an emissive layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180 and a cathode 190. Device 100 may be fabricated by depositing the layers described in order. The properties and functions of these various layers, as well as example materials, are described in more detail in U.S. Pat. No. 7,279,704 at cols. 6-10, the contents of which are incorporated by reference herein in its entirety.

(4) More examples for each of these layers are available. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. Pat. No. 5,844,363, which is incorporated by reference herein in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F.sub.4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. Pub. No. 2003/0230980, which is incorporated by reference herein in its entirety. Examples of host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which is incorporated by reference herein in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li at a molar ratio of 1:1, as disclosed in U.S. Pub. No. 2003/0230980, which is incorporated by reference herein in its entirety. U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference herein in their entireties, disclose examples of cathodes including composite cathodes having a thin layer of metal such as Mg:Ag with an overlying transparent, electrically-conductive, sputter-deposited ITO layer. The theory and use of blocking layers are described in more detail in U.S. Pat. No. 6,097,147 and U.S. Pub. No. 2003/0230980, which are incorporated by reference herein in their entireties. Examples of injection layers are provided in U.S. Pub. No. 2004/0174116, which is incorporated by reference herein in its entirety. A description of protective layers may be found in U.S. Pub. No. 2004/0174116, which is incorporated by reference herein in its entirety.

(5) The layered structure described above is provided by way of non-limiting examples. Functional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted entirely. It may also include other layers not specifically described. Within each layer, a single material or a mixture of multiple materials can be used to achieve optimum performance. Any functional layer may include several sublayers. For example, the emissive layer may have two layers of different emitting materials to achieve desired emission spectrum.

(6) 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 multiple layers.

(7) An OLED can be encapsulated by a barrier layer. FIG. 2 schematically shows an organic light emitting device 200 without limitation. FIG. 2 differs from FIG. 1 in that the organic light emitting device include a barrier layer 102, which is above the cathode 190, to protect it from harmful species from the environment such as moisture and oxygen. Any material that can provide the barrier function can be used as the barrier layer such as glass or organic-inorganic hybrid layers. The barrier layer should be placed directly or indirectly outside of the OLED device. Multilayer thin film encapsulation was described in U.S. Pat. No. 7,968,146, which is incorporated by reference herein in its entirety.

(8) Devices fabricated in accordance with embodiments of the present disclosure can be incorporated into a wide variety of consumer products that have one or more of the electronic component modules (or units) incorporated therein. Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, smart phones, tablets, phablets, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicles displays, and vehicle tail lights.

(9) The materials and structures described herein may be used in other organic electronic devices listed above.

(10) As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a first layer is described as “disposed over” a second layer, the first layer is disposed further away from the substrate. There may be other layers between the first and second layers, unless it is specified that the first layer is “in contact with” the second layer. For example, a cathode may be described as “disposed over” an anode, even though there are various organic layers in between.

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

(12) A ligand may be referred to as “photoactive” when it is believed that the ligand directly contributes to the photoactive properties of an emissive material. A ligand may be referred to as “ancillary” when it is believed that the ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the properties of a photoactive ligand.

(13) It is believed that the internal quantum efficiency (IQE) of fluorescent OLEDs can exceed the 25% spin statistics limit through delayed fluorescence. As used herein, there are two types of delayed fluorescence, i.e. P-type delayed fluorescence and E-type delayed fluorescence. P-type delayed fluorescence is generated from triplet-triplet annihilation (TTA).

(14) On the other hand, E-type delayed fluorescence does not rely on the collision of two triplets, but rather on the transition between the triplet states and the singlet excited states. Compounds that are capable of generating E-type delayed fluorescence are required to have very small singlet-triplet gaps to convert between energy states. Thermal energy can activate the transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as thermally activated delayed fluorescence (TADF). A distinctive feature of TADF is that the delayed component increases as temperature rises. If the reverse intersystem crossing rate is fast enough to minimize the non-radiative decay from the triplet state, the fraction of back populated singlet excited states can potentially reach 75%. The total singlet fraction can be 100%, far exceeding 25% of the spin statistics limit for electrically generated excitons.

(15) E-type delayed fluorescence characteristics can be found in an exciplex system or in a single compound. Without being bound by theory, it is believed that E-type delayed fluorescence requires the luminescent material to have a small singlet-triplet energy gap (ΔE.sub.S-T). Organic, non-metal containing, donor-acceptor luminescent materials may be able to achieve this. The emission in these materials is generally characterized as a donor-acceptor charge-transfer (CT) type emission. The spatial separation of the HOMO and LUMO in these donor-acceptor type compounds generally results in small AEST. These states may involve CT states. Generally, donor-acceptor luminescent materials are constructed by connecting an electron donor moiety such as amino- or carbazole-derivatives and an electron acceptor moiety such as N-containing six-membered aromatic rings.

(16) Definition of Terms of Substituents

(17) Halogen or halide—as used herein includes fluorine, chlorine, bromine, and iodine.

(18) Alkyl—contemplates both straight and branched chain alkyl groups. Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, neopentyl group, 1-methylpentyl group, 2-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group, and 3-methylpentyl group. Additionally, the alkyl group may be optionally substituted. The carbons in the alkyl chain can be replaced by other hetero atoms. Of the above, preferred are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, and neopentyl group.

(19) Cycloalkyl—as used herein contemplates cyclic alkyl groups. Preferred cycloalkyl groups are those containing 4 to 10 ring carbon atoms and includes cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcylcohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like. Additionally, the cycloalkyl group may be optionally substituted. The carbons in the ring can be replaced by other hetero atoms.

(20) Alkenyl—as used herein contemplates both straight and branched chain alkene groups. Preferred alkenyl groups are those containing 2 to 15 carbon atoms. Examples of the alkenyl group include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butandienyl group, 1-methylvinyl group, styryl group, 2,2-diphenylvinyl group, 1,2-diphenylvinyl group, 1-methylallyl group, 1,1-dimethylallyl group, 2-methylallyl group, 1-phenylallyl group, 2-phenylallyl group, 3-phenylallyl group, 3,3-diphenylallyl group, 1,2-dimethylallyl group, 1-phenyl1-butenyl group, and 3-phenyl-1-butenyl group. Additionally, the alkenyl group may be optionally substituted.

(21) Alkynyl—as used herein contemplates both straight and branched chain alkyne groups. Preferred alkynyl groups are those containing 2 to 15 carbon atoms. Additionally, the alkynyl group may be optionally substituted.

(22) Aryl or aromatic group—as used herein includes noncondensed and condensed systems. Preferred aryl groups are those containing six to sixty carbon atoms, preferably six to twenty carbon atoms, more preferably six to twelve carbon atoms. Examples of the aryl group include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group may be optionally substituted. Examples of the non-condensed aryl group include phenyl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4-yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, p-t-butylphenyl group, p-(2-phenylpropyl)phenyl group, 4′-methylbiphenylyl group, 4″-t-butyl p-terphenyl-4-yl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, 2,3-xylyl group, 3,4-xylyl group, 2,5-xylyl group, mesityl group, and m-quarterphenyl group.

(23) Heterocyclic group or heterocycle—as used herein includes aromatic and non-aromatic cyclic groups. Hetero-aromatic also means heteroaryl. Preferred non-aromatic heterocyclic groups are those containing 3 to 7 ring atoms which include at least one hetero atom such as nitrogen, oxygen, and sulfur. The heterocyclic group can also be an aromatic heterocyclic group having at least one heteroatom selected from nitrogen atom, oxygen atom, sulfur atom, and selenium atom.

(24) Heteroaryl—as used herein includes noncondensed and condensed hetero-aromatic groups that may include from one to five heteroatoms. Preferred heteroaryl groups are those containing three to thirty carbon atoms, preferably three to twenty carbon atoms, more preferably three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group may be optionally substituted.

(25) Alkoxy—it is represented by —O-Alkyl. Examples and preferred examples thereof are the same as those described above. Examples of the alkoxy group having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, and hexyloxy group. The alkoxy group having 3 or more carbon atoms may be linear, cyclic or branched.

(26) Aryloxy—it is represented by —O-Aryl or —O-heteroaryl. Examples and preferred examples thereof are the same as those described above. Examples of the aryloxy group having 6 to 40 carbon atoms include phenoxy group and biphenyloxy group.

(27) Arylalkyl—as used herein contemplates an alkyl group that has an aryl substituent. Additionally, the arylalkyl group may be optionally substituted. Examples of the arylalkyl group include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl group, alpha.-naphthylmethyl group, 1-alpha.-naphthylethyl group, 2-alpha-naphthylethyl group, 1-alpha-naphthylisopropyl group, 2-alpha-naphthylisopropyl group, beta-naphthylmethyl group, 1-beta-naphthylethyl group, 2-beta-naphthylethyl group, 1-beta-naphthylisopropyl group, 2-beta-naphthylisopropyl group, p-methylbenzyl group, m-methylbenzyl group, o-methylbenzyl group, p-chlorobenzyl group, m-chlorobenzyl group, o-chlorobenzyl group, p-bromobenzyl group, m-bromobenzyl group, o-bromobenzyl group, p-iodobenzyl group, m-iodobenzyl group, o-iodobenzyl group, p-hydroxybenzyl group, m-hydroxybenzyl group, o-hydroxybenzyl group, p-aminobenzyl group, m-aminobenzyl group, o-aminobenzyl group, p-nitrobenzyl group, m-nitrobenzyl group, o-nitrobenzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-hydroxy-2-phenylisopropyl group, and 1-chloro-2-phenylisopropyl group. Of the above, preferred are benzyl group, p-cyanobenzyl group, m-cyanobenzyl group, o-cyanobenzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, and 2-phenylisopropyl group.

(28) The term “aza” in azadibenzofuran, aza-dibenzothiophene, etc. means that one or more of the C—H groups in the respective aromatic fragment are replaced by a nitrogen atom. For example, azatriphenylene encompasses dibenzo[f,h]quinoxaline, dibenzo[f,h]quinoline and other analogues with two or more nitrogens in the ring system. One of ordinary skill in the art can readily envision other nitrogen analogs of the aza-derivatives described above, and all such analogs are intended to be encompassed by the terms as set forth herein.

(29) In the present disclosure, unless otherwise defined, when any term of the group consisting of substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted arylalkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted amine, substituted acyl, substituted carbonyl, substituted carboxylic acid group, substituted ester group, substituted sulfinyl, substituted sulfonyl and substituted phosphino is used, it means that any group of alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, alkenyl, aryl, heteroaryl, alkylsilyl, arylsilyl, amine, acyl, carbonyl, carboxylic acid group, ester group, sulfinyl, sulfonyl and phosphino may be substituted with one or more groups (including two groups) selected from the group consisting of deuterium, an unsubstituted alkyl group having 1 to 20 carbon atoms, an unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, an unsubstituted heteroalkyl group having 1 to 20 carbon atoms, an unsubstituted arylalkyl group having 7 to 30 carbon atoms, an unsubstituted alkoxy group having 1 to 20 carbon atoms, an unsubstituted aryloxy group having 6 to 30 carbon atoms, an unsubstituted alkenyl group having 2 to 20 carbon atoms, an unsubstituted aryl group having 6 to 30 carbon atoms, an unsubstituted heteroaryl group having 3 to 30 carbon atoms, an unsubstituted alkylsilyl group having 3 to 20 carbon atoms, an unsubstituted arylsilyl group having 6 to 20 carbon atoms, an unsubstituted amino group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.

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

(31) In the compounds mentioned in the present disclosure, the hydrogen atoms can be partially or fully replaced by deuterium. Other atoms such as carbon and nitrogen can also be replaced by their other stable isotopes. The replacement by other stable isotopes in the compounds may be preferred due to its enhancements of device efficiency and stability.

(32) In the compounds mentioned in the present disclosure, multiple substitutions refer to a range that includes a double substitution, up to the maximum available substitutions. When a substitution in the compounds mentioned in the present disclosure represents multiple substitutions (including di, tri, tetra substitutions etc.), that means the substituent may exist at a plurality of available substitution positions on its linking structure, the substituents present at a plurality of available substitution positions may be the same structure or different structures.

(33) In the compounds mentioned in the present disclosure, adjacent substituents in the compounds cannot be joined to form a ring unless otherwise explicitly defined, for example, adjacent substituents can be optionally joined to form a ring. In the compounds mentioned in the present disclosure, when adjacent substituents can be optionally joined to form a ring, the ring formed may be monocyclic or polycyclic, as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic. In such expression, adjacent substituents may refer to substituents bonded to the same atom, substituents bonded to carbon atoms which are directly bonded to each other, or substituents bonded to carbon atoms which are more distant from each other. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms which are directly bonded to each other.

(34) The expression that adjacent substituents can be optionally joined to form a ring is also intended to mean that two substituents bonded to the same carbon atom are joined to each other via a chemical bond to form a ring, which can be exemplified by the following formula:

(35) ##STR00012##

(36) The expression that adjacent substituents can be optionally joined to form a ring is also intended to mean that two substituents bonded to carbon atoms which are directly bonded to each other are joined to each other via a chemical bond to form a ring, which can be exemplified by the following formula:

(37) ##STR00013##

(38) Furthermore, the expression that adjacent substituents can be optionally joined to form a ring is also intended to mean that, in the case where one of the two substituents bonded to carbon atoms which are directly bonded to each other represents hydrogen, the second substituent is bonded at a position at which the hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following formula:

(39) ##STR00014##

(40) According to an embodiment of the present disclosure, disclosed is a metal complex, having a general formula of M(L.sub.a).sub.m(L.sub.b).sub.n(L.sub.c).sub.g, wherein L.sub.a, L.sub.b and L.sub.e are a first ligand, a second ligand and a third ligand coordinated to the metal M respectively;

(41) wherein m is selected from an integer greater than or equal to 1 (for example, m is selected from 1 or 2), n is selected from an integer greater than or equal to 1 (for example, n is selected from 1 or 2), q is selected from an integer greater than or equal to 1 (for example, q is selected from 1 or 2), and m+n+q equals the oxidation state of the metal M;

(42) wherein L.sub.a and L.sub.b are ligands with different structures, and each independently represented by Formula 1:

(43) ##STR00015##

(44) wherein X.sub.1 to X.sub.4 are each independently selected from CR.sub.1 or N;

(45) wherein Y.sub.1 to Y.sub.6 are each independently selected from CR.sub.2 or N, and at least one of Y.sub.1 to Y.sub.6 is CR.sub.2;

(46) wherein R.sub.1 and R.sub.2 are each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

(47) in Formula 1, for substituents R.sub.1 only, adjacent substituents can be optionally joined to form a ring which has a number of ring atoms less than or equal to 6;

(48) in the ligands L.sub.a and/or L.sub.b, at least one R.sub.2 is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

(49) wherein L.sub.c has a structure represented by Formula 2:

(50) ##STR00016##

(51) wherein R.sub.t, R.sub.u, R.sub.v, R.sub.w, R.sub.x, R.sub.y and R.sub.z are each independently selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.

(52) In an embodiment of the present disclosure, the expression in Formula 1 that “for substituents R.sub.1 only, adjacent substituents can be optionally joined to form a ring” refers to that in the structure of Formula 1, merely adjacent substituents R.sub.1 can be optionally joined to form a ring, but adjacent substituents R.sub.2 are not joined to form a ring, and adjacent substituents R.sub.1 and R.sub.2 are not joined to form a ring. When adjacent substituents R.sub.1 are joined to form a ring, the number of ring atoms of the resulting ring should be less than or equal to 6. In some embodiment, adjacent substituents R.sub.1 are not joined to form a ring. In Formula 2, adjacent substituents R.sub.x, R.sub.y, R.sub.z, R.sub.t, R.sub.u, R.sub.v and R.sub.w are not joined to form a ring.

(53) In embodiments of the present disclosure, in the ligands L.sub.a and/or L.sub.b, at least one R.sub.2 is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof. The above definition is intended to include the following three cases: (1) at least one of all substituents R.sub.2 in ligand L.sub.a and ligand L.sub.b is selected from the above range, or (2) at least one of all substituents R.sub.2 in ligand L.sub.a alone is selected from the above range, or (3) at least one of all substituents R.sub.2 in ligand L.sub.b alone is selected from the above range. That is to say, when one or more of Y.sub.1 to Y.sub.6 in the ligands L.sub.a and L.sub.b are selected from CR.sub.2, the case where all R.sub.2 in the ligands L.sub.a and L.sub.b are hydrogen does not exist.

(54) In embodiments of the present disclosure, no matter which substituent (for example includes, but is not limited to substituted alkyl) in their defined range R.sub.t, R.sub.u, R.sub.v, R.sub.w, R.sub.x, R.sub.y and R.sub.z in Formula 2 are each independently selected from, none of R.sub.t, R.sub.u, R.sub.v, R.sub.w, R.sub.x, R.sub.y and R.sub.z contains halogen, especially fluorine.

(55) According to an embodiment of the present disclosure, the metal M is selected from the group consisting of Cu, Ag, Au, Ru, Rh, Pd, Os, Ir and Pt.

(56) According to an embodiment of the present disclosure, the metal M is selected from Pt or Ir.

(57) According to an embodiment of the present disclosure, the metal M is selected from Ir.

(58) According to an embodiment of the present disclosure, at least one of X.sub.1 to X.sub.4 is selected from CR.sub.1.

(59) According to an embodiment of the present disclosure, X.sub.1 and X.sub.4 are each independently selected from CR.sub.1, and/or Y.sub.1 to Y.sub.6 are each independently selected from CR.sub.2.

(60) According to an embodiment of the present disclosure, X.sub.1 is each independently CR.sub.1 and/or X.sub.3 is each independently CR.sub.1, and R.sub.1 is independently selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.

(61) According to an embodiment of the present disclosure, X.sub.1 is each independently CR.sub.1, X.sub.3 is each independently CR.sub.1, and R.sub.1 is independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms.

(62) According to an embodiment of the present disclosure, X.sub.1 is each independently CR.sub.1, X.sub.3 is each independently CR.sub.1, and R.sub.1 is independently selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms.

(63) According to an embodiment of the present disclosure, Y.sub.1 is each independently CR.sub.2 and/or Y.sub.4 is each independently CR.sub.2, and R.sub.2 is independently selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.

(64) According to an embodiment of the present disclosure, Y.sub.1 is each independently CR.sub.2, Y.sub.4 is each independently CR.sub.2, and R.sub.2 is independently selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms.

(65) According to an embodiment of the present disclosure, Y.sub.1 is each independently CR.sub.2, Y.sub.4 is each independently CR.sub.2, and R.sub.2 is independently selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms or substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms.

(66) According to an embodiment of the present disclosure, Y.sub.1 is CD, Y.sub.4 is CR.sub.2, and R.sub.2 is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms and substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms; preferably, R.sub.2 is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms or substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms.

(67) According to an embodiment of the present disclosure, Y.sub.2, Y.sub.3, Y.sub.5 and Y.sub.6 are each CH, Y.sub.1 is CD, Y.sub.4 is CR.sub.2, and R.sub.2 is selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms or substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms.

(68) According to an embodiment of the present disclosure, Y.sub.1, Y.sub.2, Y.sub.3, Y.sub.4 and Y.sub.6 are each CH, Y.sub.5 is CR.sub.2, and R.sub.2 is independently selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms.

(69) According to an embodiment of the present disclosure, Y.sub.2, Y.sub.3, Y.sub.4, Y.sub.5 and Y.sub.6 are each CH, Y.sub.1 is CR.sub.2, and R.sub.2 is independently selected from substituted or unsubstituted alkyl having 1 to 20 carbon atoms.

(70) According to an embodiment of the present disclosure, R.sub.2 is independently selected from the group consisting of: hydrogen, deuterium, methyl, isopropyl, 2-butyl, isobutyl, t-butyl, pent-3-yl, cyclopentyl, cyclohexyl, 4,4-dimethylcyclohexyl, neopentyl, 2,4-dimethylpent-3-yl, 3,3,3-trifluoro-2,2-dimethylpropyl, 1,1-dimethylsilacyclohex-4-yl, cyclopentylmethyl, cyanomethyl, cyano, trifluoromethyl, bromine, chlorine, trimethylsilyl, phenyldimethylsilyl, phenyl and 3-pyridyl.

(71) According to an embodiment of the present disclosure, L.sub.a and L.sub.b have different structures and are each independently selected from the group consisting of L.sub.x1 to L.sub.x1065. For specific structures of L.sub.x1 to L.sub.x165, see claim 11. In the numbers of the specific structures of the ligands described above, x represents a or b. That is, a ligand

(72) ##STR00017##
numbered L.sub.x1 not only represents a ligand

(73) ##STR00018##
numbered L.sub.a1 but also represents a ligand

(74) ##STR00019##
numbered L.sub.b1. Ligand numbers L.sub.x2 to L.sub.x1065 have the same meaning as L.sub.x1.

(75) According to an embodiment of the present disclosure, in Formula 2, R.sub.t, R.sub.u, R.sub.v, R.sub.w, R.sub.x, R.sub.y and R.sub.z are each independently selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, and combinations thereof.

(76) According to an embodiment of the present disclosure, in Formula 2, R.sub.t is selected from hydrogen, deuterium or methyl, and R.sub.u to R.sub.z are each independently selected from hydrogen, deuterium, methyl, ethyl, propyl, cyclobutyl, cyclopentyl, cyclohexyl, 3-methylbutyl, 3-ethylpentyl or combinations thereof.

(77) According to another embodiment of the present disclosure, L.sub.c is selected from the group consisting of L.sub.c1 to L.sub.c84. Wherein, for specific structures of L.sub.c1 to L.sub.c84, see claim 13.

(78) According to an embodiment of the present disclosure, hydrogen in any one, any two or three of the ligands L.sub.a, L.sub.b and L.sub.e may be partially or fully substituted by deuterium.

(79) According to an embodiment of the present disclosure, the metal complex is IrL.sub.aL.sub.bL.sub.c, wherein L.sub.a and L.sub.b have different structures, L.sub.a is any one selected from L.sub.a to L.sub.a1065, L.sub.b is any one selected from L.sub.b1 to L.sub.b1065, and L.sub.c is any one selected from L.sub.c1 to L.sub.c84.

(80) According to an embodiment of the present disclosure, the metal complex is IrL.sub.aL.sub.bL.sub.c, wherein L.sub.a and L.sub.b have different structures, L.sub.a is any one selected from L.sub.a1 to L.sub.a108, L.sub.a112 to L.sub.a144, L.sub.a148 to L.sub.a288, L.sub.a292 to L.sub.a362, L.sub.a364 to L.sub.a432, L.sub.a436 to L.sub.a720 and L.sub.a757 to L.sub.a1065, L.sub.b is any one selected from L.sub.b1 to L.sub.b1065, and L.sub.c is any one selected from L.sub.c1 to L.sub.c84.

(81) According to an embodiment of the present disclosure, the metal complex is IrL.sub.aL.sub.bL.sub.c, wherein L.sub.a and L.sub.b have different structures, L.sub.a is selected from L.sub.a39, L.sub.b is any one selected from L.sub.b1 to L.sub.b1065, and L.sub.c is any one selected from L.sub.c1 to L.sub.c84.

(82) According to an embodiment of the present disclosure, the metal complex is selected from the group consisting of:

(83) ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031## ##STR00032## ##STR00033##

(84) According to an embodiment of the present disclosure, further disclosed is an electroluminescent device, which includes:

(85) an anode,

(86) a cathode, and

(87) an organic layer disposed between the anode and the cathode, wherein the organic layer includes a metal complex having a general formula of M(L.sub.a).sub.m(L.sub.b).sub.n(L.sub.c).sub.q, wherein L.sub.a, L.sub.b and L.sub.c are a first ligand, a second ligand and a third ligand coordinated to the metal M respectively;

(88) wherein m is selected from an integer greater than or equal to 1, n is selected from an integer greater than or equal to 1, q is selected from an integer greater than or equal to 1, and m+n+q equals the oxidation state of the metal M;

(89) wherein L.sub.a and L.sub.b are ligands with different structures, and each independently represented by Formula 1:

(90) ##STR00034##

(91) wherein X.sub.1 to X.sub.4 are each independently selected from CR.sub.1 or N;

(92) wherein Y.sub.1 to Y.sub.6 are each independently selected from CR.sub.2 or N, and at least one of Y.sub.1 to Y.sub.6 is CR.sub.2;

(93) wherein R.sub.1 and R.sub.2 are each independently selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

(94) in Formula 1, adjacent substituents R.sub.1 can be optionally joined to form a ring;

(95) in the ligands L.sub.a and/or L.sub.b, at least one R.sub.2 is selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;

(96) wherein L.sub.c has a structure represented by Formula 2:

(97) ##STR00035##

(98) wherein R.sub.t to R.sub.z are each independently selected from the group consisting of: hydrogen, deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted arylalkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof.

(99) According to an embodiment of the present disclosure, the device emits red light.

(100) According to an embodiment of the present disclosure, the device emits white light.

(101) According to an embodiment of the present disclosure, in the device, the organic layer is a light-emitting layer, and the metal complex is a light-emitting material.

(102) According to an embodiment of the present disclosure, in the device, the organic layer further includes a host material.

(103) According to an embodiment of the present disclosure, the host material includes at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, aza-dibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof.

(104) According to another embodiment of the present disclosure, further disclosed is a compound formulation which includes the metal complex whose specific structure is as shown in any one of the embodiments described above.

(105) Combination with Other Materials

(106) The materials described in the present disclosure for a particular layer in an organic light emitting device can be used in combination with various other materials present in the device. The combinations of these materials are described in more detail in U.S. Pat. App. No. 20160359122 at paragraphs 0132-0161, which is incorporated by reference herein in its entirety. The materials described or referred to the disclosure are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

(107) The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a variety of other materials present in the device. For example, light emitting dopants disclosed herein may be used in combination with a wide variety of hosts, transport layers, blocking layers, injection layers, electrodes and other layers that may be present. The combination of these materials is described in detail in paragraphs 0080-0101 of U.S. Pat. App. No. 20150349273, which is incorporated by reference herein in its entirety. The materials described or referred to the disclosure are non-limiting examples of materials that may be useful in combination with the compounds disclosed herein, and one of skill in the art can readily consult the literature to identify other materials that may be useful in combination.

(108) In the embodiments of material synthesis, all reactions were performed under nitrogen protection unless otherwise stated. All reaction solvents were anhydrous and used as received from commercial sources. Synthetic products were structurally confirmed and tested for properties using one or more conventional equipment in the art (including, but not limited to, nuclear magnetic resonance instrument produced by BRUKER, liquid chromatograph produced by SHIMADZU, liquid chromatograph-mass spectrometry produced by SHIMADZU, gas chromatograph-mass spectrometry produced by SHIMADZU, differential Scanning calorimeters produced by SHIMADZU, fluorescence spectrophotometer produced by SHANGHAI LENGGUANG TECH., electrochemical workstation produced by WUHAN CORRTEST, and sublimation apparatus produced by ANHUI BEQ, etc.) by methods well known to the persons skilled in the art. In the embodiments of the device, the characteristics of the device were also tested using conventional equipment in the art (including, but not limited to, evaporator produced by ANGSTROM ENGINEERING, optical testing system produced by SUZHOU FATAR, life testing system produced by SUZHOU FATAR, and ellipsometer produced by BEIJING ELLITOP, etc.) by methods well known to the persons skilled in the art. As the persons skilled in the art are aware of the above-mentioned equipment use, test methods and other related contents, the inherent data of the sample can be obtained with certainty and without influence, so the above related contents are not further described in this patent.

Material Synthesis Example

(109) A method for preparing a compound in the present disclosure is not limited herein. Typically, the following compounds are taken as examples without limitations, and synthesis routes and preparation methods thereof are described below.

Synthesis Example 1: Synthesis of Compound Ir(L.SUB.a39.)(L.SUB.b291.)(L.SUB.c55.)

Step 1: synthesis of ethyl 2-ethyl-2-methylbutyrate

(110) ##STR00036##

(111) Ethyl 2-ethylbutyrate (50.0 g, 346 mmol) was dissolved in 600 mL of tetrahydrofuran, N.sub.2 was bubbled into the obtained solution for 3 min, and then the solution was cooled to −78° C. 190 mL of 2 M di-isopropylamide lithium in tetrahydrofuran was added dropwise into the solution under N.sub.2 protection at −78° C. After the dropwise addition was finished, the reaction solution was kept reacting at −78° C. for 30 min, and then iodomethane (58.9 g, 415 mmol) was slowly added. After the dropwise addition was finished, the reaction was slowly warmed to room temperature for overnight. Then, a saturated ammonium chloride solution was slowly added to quench the reaction, and then liquid layers were separated. The organic phase was collected, and the aqueous phase was extracted twice with dichloromethane. The organic phases were combined and dried and rotary evaporated to dryness to obtain the desired ethyl 2-ethyl-2-methylbutyrate (52.2 g with a yield of 95%).

Step 2: Synthesis of 2-ethyl-2-methylbutyric acid

(112) ##STR00037##

(113) Ethyl 2-ethyl-2-methylbutyrate (52.2 g, 330 mmol) was dissolved in methanol, sodium hydroxide (39.6 g, 990 mmol) was added to the solution, and then the obtained reaction mixture was heated to reflux for 12 h and cooled then to room temperature. Methanol was removed by rotary evaporation, the pH of the reaction solution was adjusted to 1 by adding 3M hydrochloric acid, and then extraction was performed several times with dichloromethane. The organic phases were combined and dried and rotary evaporated to dryness to obtain 2-ethyl-2-methylbutyric acid (41.6 g with a yield of 97%).

Step 3: Synthesis of 3-ethyl-3-methylpentan-2-one

(114) ##STR00038##

(115) 2-Ethyl-2-methylbutyric acid (13.0 g, 100 mmol) was dissolved in 200 mL of tetrahydrofuran, N.sub.2 was bubbled into the obtained solution for 3 min, and then the solution was cooled to 0° C. 230 mL of methyl lithium (1.3 M) in ether was added dropwise into the solution under N.sub.2 protection at 0° C. After the dropwise addition was finished, the reaction solution was kept reacting at 0° C. for 2 h, and then was warmed to room temperature for overnight. After TLC showed that the reaction was finished, 1 M hydrochloric acid was slowly added to quench the reaction, and then liquid layers were separated. The organic phase was collected, and the aqueous phase was extracted twice with dichloromethane. The organic phases were combined and dried and rotary evaporated to dryness to obtain the target product, 3-ethyl-3-methylpentan-2-one (11.8 g with a yield of 92%).

Step 4: Synthesis of 2-ethylbutyryl chloride

(116) ##STR00039##

(117) 2-Ethylbutyric acid (11.6 g, 100 mmol) was dissolved in dichloromethane, 1 drop of DMF was added as a catalyst, and then N.sub.2 was bubbled into the obtained solution for 3 min. The reaction was then cooled to 0° C., and oxalyl chloride (14.0 g, 110 mmol) was added dropwise thereto. After the dropwise addition was finished, the reaction was warmed to room temperature. When no gas was evolved from the reaction system, the reaction solution was rotary evaporated to dryness. The obtained crude 2-ethylbutyryl chloride was used directly in the next reaction without further purification.

Step 5: Synthesis of 3,7-diethyl-3-methylnonane-4,6-dione

(118) ##STR00040##

(119) 3-Ethyl-3-methylpentan-2-one (11.8 g, 92 mmol) was dissolved in tetrahydrofuran, N.sub.2 was bubbled into the obtained solution for 3 min, and then the solution was cooled to −78° C. 55 mL of 2 M di-isopropylamide lithium in tetrahydrofuran was added dropwise to the solution. After the dropwise addition was finished, the reaction solution was kept reacting at −78° C. for 30 min, and then 2-ethylbutyryl chloride (100 mmol) was slowly added. After the dropwise addition was finished, the reaction was slowly warmed to room temperature for overnight. 1 M hydrochloric acid was slowly added to quench the reaction, and then liquid layers were separated. The organic phase was collected, and the aqueous phase was extracted twice with dichloromethane. The organic phases were combined and dried and rotary evaporated to dryness to obtain a crude product. The crude product was purified by column chromatography (with an eluent of petroleum ether) and distilled under reduced pressure to obtain the target product 3,7-diethyl-3-methylnonane-4,6-dione (4.7 g with a yield of 23%).

Step 6: Synthesis of 1-(3,5-dimethylphenyl)-6-cyclopentylisoquinoline

(120) ##STR00041##

(121) A 250 mL three-neck flask was degassed and purged with nitrogen, and then cyclopentylmagnesium bromide (64 mL, 64 mmol) was added. A solution of zinc chloride (19.5 mL, 32 mmol) was added dropwise at 0° C. After the addition was finished, the mixture was reacted at room temperature for 30 min to prepare a cyclopentyl zinc reagent. 6-Bromo-1-(3,5-dimethylphenyl)isoquinoline (10 g, 32 mmol) and Pd(dppf)Cl.sub.2 (702 mg, 0.96 mmol) were added in a 500 ml three-neck flask. The system was degassed and purged with nitrogen. THF (136 mL) was added and then the prepared zinc reagent was added. The mixture was reacted overnight at room temperature. After GC-MS detected that the reaction was finished, water was added to quench the reaction. The organic phase was separated, and the aqueous phase was extracted with ethyl acetate. The organic phases were combined, washed with saturated brine, dried with anhydrous sodium sulfate, filtered and concentrated, mixed with Celite, and separated by chromatography to obtain 1-(3,5-dimethylphenyl)-6-cyclopentylisoquinoline (8.2 g with a yield of 85%) as a colorless oily product.

Step 7: Synthesis of 1-(3,5-dimethylphenyl)-6-methylisoquinoline

(122) ##STR00042##

(123) 6-Bromo-1-(3,5-dimethylphenyl)isoquinoline (5 g, 16 mmol), Pd(dppf)Cl.sub.2 (535 mg, 0.8 mmol), K.sub.2CO.sub.3 (5.3 g, 40 mmol) and DMF (80 mL) were added in a 500 ml three-neck flask. The reaction system was degassed and purged with nitrogen, added with a solution of Me.sub.2Zn in toluene (24 mL, 24 mmol), and reacted overnight at room temperature. After GC-MS detected that the reaction was finished, water was added to quench the reaction. The organic phase was separated, and the aqueous phase was extracted with ethyl acetate. The organic phases were combined, washed with saturated brine, dried with anhydrous sodium sulfate, filtered and concentrated, mixed with Celite, and separated by column chromatography to obtain 1-(3,5-dimethylphenyl)-6-methylisoquinoline (3.2 g with a yield of 81%) as a white solid.

(124) Step 8: synthesis of compound Ir(L.sub.a39)(L.sub.b291)(L.sub.c55)

(125) ##STR00043##

(126) 1-(3,5-Dimethylphenyl)-6-cyclopentylisoquinoline (3.62 g, 12 mmol), 1-(3,5-dimethylphenyl)-6-methylisoquinoline (2.96 g, 12 mmol), IrCl.sub.3.3H.sub.2O (2.11 g, 6 mmol), ethoxyethanol (63 mL) and water (21 mL) were added in a 500 mL single-neck flask. The system was degassed and purged with nitrogen, and refluxed for 24 h. The reaction was cooled to room temperature, filtered, and the filter cake was washed with ethanol to obtain an iridium dimer.

(127) 3,7-Diethyl-3-methylnonane-4,6-dione (2.716 g, 12 mmol), K.sub.2CO.sub.3 (4.15 g, 30 mmol) and ethoxyethanol (84 mL) were added to the iridium dimer (4.78 g). The mixture was reacted overnight at 45° C. under a nitrogen atmosphere. After TLC detected that the reaction was finished, stirring was stopped and the reaction solution was cooled to room temperature. The reaction solution was filtered through Celite, the filter cake was washed with an appropriate amount of EtOH, and the crude product was washed with DCM into a 500 mL eggplant-shaped flask. EtOH (about 60 mL) was added in the crude product, and DCM was removed by rotary evaporation at room temperature until a large amount of solids was precipitated. The solids were filtered and dried to obtain 4.4 g of crude product, which was separated by chromatography to obtain the target product, compound Ir(L.sub.a39)(L.sub.b291)(L.sub.c55) (0.99 g with purity of 99.9%). The product was confirmed as the target product with a molecular weight of 964.

Synthesis Example 2: Synthesis of Compound Ir(L.SUB.a111.)(L.SUB.b291.)(L.SUB.c55.)

(128) ##STR00044##

(129) 1-(3,5-Dimethylphenyl)-6-cyclopentylisoquinoline (3 g, 9.95 mmol), 1-(3,5-dimethylphenyl)-6-isopropylisoquinoline (2.74 g, 9.95 mmol), IrCl.sub.3.3H.sub.2O (1.76 g, 4.975 mmol), ethoxyethanol (60 mL) and water (20 mL) were added in a 500 mL single-neck flask. The system was degassed and purged with nitrogen, and refluxed for 24 h. The reaction was cooled to room temperature, filtered, and the filter cake was washed with ethanol to obtain an iridium dimer.

(130) 3,7-Diethyl-3-methylnonane-4,6-dione (2.25 g, 9.95 mmol), K.sub.2CO.sub.3 (3.44 g, 24.9 mmol) and ethoxyethanol (60 mL) were added to the iridium dimer. The mixture was reacted overnight at 45° C. under a nitrogen atmosphere. After TLC detected that the reaction was finished, the reaction solution was no longer stirred and was cooled to room temperature. The reaction solution was filtered through Celite, the filter cake was washed with an appropriate amount of EtOH, and the crude product was washed with DCM into a 500 mL eggplant-shaped bottle. EtOH (about 60 mL) was added in the crude product, and DCM was removed by rotary evaporation at room temperature until a large amount of solids was precipitated. The solids were filtered and dried to obtain 3.8 g of crude product, which was separated by chromatography to obtain the target product, compound Ir(L.sub.a111)(L.sub.b291)(L.sub.c55) (0.53 g with purity of 98.7%). The product was confirmed as the target product with a molecular weight of 992.

Synthesis Example 3: Synthesis of Compound Ir(L.SUB.a39.)(L.SUB.b65.)(L.SUB.c55.)

Step 1: synthesis of 1-(3,5-dimethylphenyl)-6-trimethylsilylisoquinoline

(131) ##STR00045##

(132) 6-Bromo-1-(3,5-dimethylphenyl)isoquinoline (48.05 mmol, 15 g) was dissolved in 160 mL of THF. The reaction system was evacuated and purged with nitrogen three times. The reaction flask was placed in a dry ice-ethanol system to be cooled to −72° C., and n-BuLi (2.5 M, 57.7 mmol, 23.1 mL) was slowly added dropwise to the system. After the dropwise addition was finished, the mixture was reacted for 30 min, and then trimethylchlorosilane (7.82 g, 72.1 mmol) was added dropwise to the system. After the dropwise addition was finished, the reaction was slowly returned to room temperature for overnight. The reaction was monitored by TLC until it was finished. Water was added to quench the reaction. A layer of tetrahydrofuran was separated, and the aqueous phase was extracted three times with ethyl acetate. The organic phases were combined, dried, subjected to rotary evaporation and purified by column chromatography to obtain 1-(3,5-dimethylphenyl)-6-trimethylsilylisoquinoline (11.7 g with a yield of 79%) as a colorless oily liquid.

Step 2: Synthesis of Compound Ir(L.SUB.a39.)(L.SUB.b65.)(L.SUB.c55.)

(133) ##STR00046##

(134) A mixture of 1-(3,5-dimethylphenyl)-6-trimethylsilylisoquinoline (3.14 g, 10.3 mmol), 1-(3,5-dimethylphenyl)-6-methylisoquinoline (6.36 g, 25.7 mmol), iridium trichloride trihydrate (3.17 g, 9.0 mmol), 2-ethoxyethanol (96 mL) and water (32 mL) was refluxed under a nitrogen atmosphere for 40 h. The reaction solution was cooled to room temperature and filtered. The obtained solid was washed several times with methanol and dried to obtain an iridium dimer.

(135) Under a nitrogen atmosphere, the iridium dimer (4.48 g) in the above step, 3,7-diethyl-3-methylnonane-4,6-dione (1.96 g, 8.65 mmol), and K.sub.2CO.sub.3 (3.98 g, 28.8 mmol) were heated in 2-ethoxyethanol (83 mL) to 40° C. and stirred for 24 h. After the reaction was finished, the reaction system was naturally cooled to room temperature, and the precipitate was filtered through Celite and washed with ethanol. The obtained solid was added with dichloromethane, and the filtrate was collected. The solvent was removed in vacuum, and the residual was mixed with Celite and separated by column chromatography to obtain Ir(L.sub.a39)(L.sub.b615)(L.sub.c55) (0.83 g with a purity of 99.4%). The product was confirmed as the target product with a molecular weight of 968.

Comparative Example 1: Synthesis of Comparative Compound Ir(L.SUB.a291.).SUB.2.(L.SUB.c55.)

(136) ##STR00047##

(137) 1-(3,5-Dimethylphenyl)-6-cyclopentylisoquinoline (3.2 g, 10.7 mmol), IrCl.sub.3.3H.sub.2O (1.27 g, 3.6 mmol), ethoxyethanol (45 mL) and water (15 mL) were added in a 250 mL single-neck flask. The system was evacuated and purged with nitrogen, and refluxed for 24 h. The reaction solution was cooled to room temperature and the resultant red solid was filtered. The red solid was washed with EtOH and dried to obtain an iridium dimer (2.3 g, 77%).

(138) The iridium dimer (1.05 g, 0.62 mmol), 3,7-diethyl-3-methylnonane-4,6-dione (562 mg, 2.48 mmol), K.sub.2CO.sub.3 (857 mg, 6.2 mmol) and ethoxyethanol (20 mL) were added in a 250 mL single-neck flask and reacted for 18 h at room temperature under a nitrogen atmosphere. The reaction solution was filtered through Celite, the filter cake was washed with an appropriate amount of EtOH, and the crude product was washed with DCM into a 250 mL eggplant-shaped bottle. EtOH (about 30 mL) was added in the crude product, and DCM was removed by rotary evaporation at room temperature until a large amount of solids was precipitated. The solids were filtered, washed with an appropriate amount of EtOH, and dried to obtain Ir(L.sub.a291).sub.2(L.sub.c55) (750 mg with purity of 99.9%). The obtained product was confirmed as a target product with a molecular weight of 1018.

Comparative Example 2: Synthesis of Comparative Compound Ir(L.SUB.a65.).SUB.2.(L.SUB.c55.)

(139) ##STR00048##

(140) A mixture of 1-(3,5-dimethylphenyl)-6-(trimethylsilyl)isoquinoline (2.70 g, 8.8 mmol), iridium trichloride trihydrate (1.03 g, 2.93 mmol), 2-ethoxyethanol (30 mL) and water (10 mL) was refluxed under a nitrogen atmosphere for 24 h. The reaction solution was cooled to room temperature and filtered. The obtained solid was washed several times with methanol and dried to obtain an iridium dimer (1.93 g with a yield of 78).

(141) Under a nitrogen atmosphere, the iridium dimer (1.93 g, 1.15 mmol) in the above step, 3,7-diethyl-3-methylnonane-4,6-dione (0.79 g, 3.5 mmol), K.sub.2CO.sub.3 (1.59 g, 11.5 mmol) and 2-ethoxyethanol (33 mL) were heated to 30° C. and stirred for 24 h. After TLC detected that the reaction was finished, the reaction system was naturally cooled to room temperature, and the precipitate was filtered through Celite and washed with ethanol. The obtained solid was added with dichloromethane, and the filtrate was collected. Ethanol was then added and the obtained solution was concentrated, but not to dryness. The solution was filtered and pumped to dry to obtain Ir(L.sub.a615).sub.2(L.sub.c55) which was refluxed in acetonitrile, cooled, filtered, and further purified to obtain compound Ir(L.sub.a615).sub.2(L.sub.c55) (2.0 g with purity of 99.9%). The obtained product was confirmed as a target product with a molecular weight of 1027.

(142) Those skilled in the art will appreciate that the above preparation method is merely illustrative, and those skilled in the art can obtain other compound structures of the present disclosure through the improvements of the preparation method.

Device Example 1

(143) First, a glass substrate having an Indium Tin Oxide (ITO) anode with a thickness of 120 nm was cleaned, and then treated with oxygen plasma and UV ozone. After the treatment, the substrate was dried in a glovebox to remove water. The substrate was mounted on a substrate holder and loaded into a vacuum chamber. Organic layers specified below were sequentially deposited through vacuum thermal evaporation on the ITO anode at a rate of 0.2 to 2 Angstroms per second at a vacuum degree of about 10.sup.−8 torr. Compound HI was used as a hole injection layer (HIL). Compound HT was used as a hole transporting layer (HTL). Compound EB was used as an electron blocking layer (EBL). The compound Ir(L.sub.a39)(L.sub.b291)(L.sub.c55) of the present disclosure was doped in a host compound RH to be used as an emissive layer (EML). Compound HB was used as a hole blocking layer (HBL). On the HBL, a mixture of Compound ET and 8-hydroxyquinolinolato-lithium (Liq) was deposited as an electron transporting layer (ETL). Liq with a thickness of 1 nm was deposited as an electron injection layer, and Al with a thickness of 120 nm was deposited as a cathode. The device was transferred back to the glovebox and encapsulated with a glass lid and a moisture getter to complete the device.

Device Example 2

(144) The preparation method in Device Example 2 was the same as that in Device Example 1, except that the compound Ir(L.sub.a39)(L.sub.b291)(L.sub.c55) of the present disclosure in the emissive layer (EML) was substituted by the compound Ir(L.sub.a39)(L.sub.b615)(L.sub.c55) of the present disclosure.

Device Comparative Example 1

(145) The preparation method in Device Comparative Example 1 was the same as that in Device Example 1, except that the compound Ir(L.sub.a39)(L.sub.b291)(L.sub.c55) of the present disclosure in the emissive layer (EML) was substituted by the comparative compound Ir(L.sub.a39).sub.2(L.sub.c55).

Device Comparative Example 2

(146) The preparation method in Device Comparative Example 2 was the same as that in Device Example 1, except that the compound Ir(L.sub.a39)(L.sub.b291)(L.sub.c55) of the present disclosure in the emissive layer (EML) was substituted by the comparative compound Ir(L.sub.a291).sub.2(L.sub.c55).

Device Comparative Example 3

(147) The preparation method in Device Comparative Example 3 was the same as that in Device Example 1, except that the compound Ir(L.sub.a39)(L.sub.b291)(L.sub.c55) of the present disclosure in the emissive layer (EML) was substituted by the comparative compound Ir(L.sub.a615).sub.2(L.sub.c55).

(148) Detail structures and thicknesses of part of layers of the device are shown in the following table. A layer using more than one material is obtained by doping different compounds in their weight proportions as described.

(149) TABLE-US-00001 TABLE 1 Device structure Device No. HIL HTL EBL EML HBL ETL Example 1 Compound Compound Compound Compound RH: Compound Compound HI HT EB compound HB ET: Liq (100 Å) (400 Å) (50 Å) Ir(L.sub.a39)(L.sub.b291)(L.sub.c55) (50 Å) (40:60) (98:2) (350 Å) (400 Å) Example 2 Compound Compound Compound Compound RH: Compound Compound HI HT EB compound HB ET: Liq (100 Å) (400 Å) (50 Å) Ir(L.sub.a39)(L.sub.b615)(L.sub.c55) (50 Å) (40:60) (98:2) (350 Å) (400 Å) Comparative Compound Compound Compound Compound RH: Compound Compound Example 1 HI HT EB compound HB ET: Liq (100 Å) (400 Å) (50 Å) Ir(L.sub.a39).sub.2(L.sub.b615) (50 Å) (40:60) (98:2) (350 Å) (400 Å) Comparative Compound Compound Compound Compound RH: Compound Compound Example 2 HI HT EB compound HB ET: Liq (100 Å) (400 Å) (50 Å) Ir(L.sub.a291).sub.2(L.sub.c55) (50 Å) (40:60) (98:2) (350 Å) (400 Å) Comparative Compound Compound Compound Compound RH: Compound Compound Example 3 HI HT EB compound HB ET: Liq (100 Å) (400 Å) (50 Å) Ir(L.sub.a615).sub.2(L.sub.c55) (50 Å) (40:60) (98:2) (350 Å) (400 Å)

(150) Structures of the materials used in the device are shown as follows:

(151) ##STR00049## ##STR00050## ##STR00051##

(152) Current-voltage-luminance (IVL) and lifetime characteristics of the device were measured at different current densities and voltages. Table 2 shows external quantum efficiency (EQE), maximum emission wavelength λmax and voltage (V) measured at 1000 nits. Table 3 shows evaporation temperatures (T.sub.evap @ 0.5 Å/s) of the materials at an evaporation rate of 0.5 Å/s at a vacuum degree of 2×10.sup.−7 torr or below.

(153) TABLE-US-00002 TABLE 2 Device data Device No. λmax (nm) Voltage (V) EQE (%) Example 1 624 3.88 25.59 Comparative Example 1 625 4.13 24.72 Comparative Example 2 623 3.91 26.67 Example 2 634 3.94 24.31 Comparative Example 3 638 4.00 24.72

(154) TABLE-US-00003 TABLE 3 Data on the evaporation temperatures Device No. The substituent at The substituent T.sub.evap using a 6-position of a at 6-position of a Molecular @ 0.5 compound Compound ligand ligand Weight Å/s Example 1 Ir(L.sub.a39)(L.sub.b291)(L.sub.c55) methyl cyclopentyl 964 232 Comparative Ir(L.sub.a39).sub.2(L.sub.c55) methyl methyl 910 219 Example 1 Comparative Ir(L.sub.a291).sub.2(L.sub.c55) cyclopentyl cyclopentyl 1018 252 Example 2 Example 2 Ir(L.sub.a39)(L.sub.b615)(L.sub.c55) methyl trimethylsilyl 968 215 Comparative Ir(L.sub.a615).sub.2(L.sub.c55) trimethylsilyl trimethylsilyl 1027 231 Example 3

(155) Generally, in researches focused on improving material performance, mono- or multi-substitution is introduced on phenyl isoquinoline, or modification is further introduced on the substituent(s) in order to adjust performance such as efficiency and emission wavelength. However, this will increase the molecular weight of the material and require a higher evaporation temperature, which may cause a decrease in evaporation stability. The present disclosure forms an asymmetric complex structure by coordinating iridium with two different isoquinoline ligands, and thus can effectively control the increase of the evaporation temperature while obtaining desired performance such as the efficiency and the emission wavelength of the material. As shown in Tables 2 and 3, with the derivation from Ir(L.sub.a39).sub.2(L.sub.c55) containing two methyl groups to Ir(L.sub.a39)(L.sub.b291)(L.sub.c55) containing one methyl group and one cyclopentyl group, the molecular weight increased by 54 g/mol, from 910 g/mol to 964 g/mol, and the evaporation temperature increased by 13° C., from 219° C. to 232° C.; and, with the derivation to Ir(L.sub.a291).sub.2(L.sub.c55) containing two cyclopentyl groups, the molecular weight increased by 108 g/mol, from 910 g/mol to 1018 g/mol, and the evaporation temperature increased by 36° C., from 219° C. to 252° C. Related device performance comparisons showed that both Example 1 and Comparative Example 2 achieved higher EQE than Comparative Example 1, which demonstrated that the two different ligands of the present disclosure can not only effectively control the evaporation temperature but also achieve the device performance of improved efficiency due to substituents with larger molecular weights. In addition, Example 1 also achieved a lower voltage than Comparative Examples 1 and 2.

(156) With the derivation from Ir(L.sub.a39).sub.2(L.sub.c55) containing two methyl groups to Ir(L.sub.a39)(L.sub.b615)(L.sub.c55) containing one methyl group and one trimethylsilyl group, the molecular weight increased by 58 g/mol, from 910 g/mol to 968 g/mol, and the evaporation temperature unexpectedly decreased by 4° C., from 219° C. to 215° C.; and, with the derivation to Ir(L.sub.a615).sub.2(L.sub.c55) containing two trimethylsilyl groups, the molecular weight increased by 117 g/mol, from 910 g/mol to 1027 g/mol, and the evaporation temperature increased by 12° C., from 219° C. to 231° C. Related device performance comparisons showed that both Example 2 and Comparative Example 3 achieved a significant red-shift λmax with respect to Comparative Example 1, which demonstrated that the two different ligands of the present disclosure can not only achieve a lower evaporation temperature but also achieve the device performance of emission wavelength red-shift due to trimethylsilyl substituents. In addition, Example 2 also achieved a lower voltage than Comparative Examples 1 and 3.

(157) The above data significantly shows that the complex structure with two different phenylisoquinoline ligands of the present disclosure has a clear effect on controlling the increase of the evaporation temperature and can also maintain the device performance due to corresponding substituents. The complex structure is of great help for the industry to both control or improve device performance and control the evaporation temperature to cooperate with production, for example, to reduce the evaporation temperature to prevent material aging, and to finely adjust evaporation to optimize mixed evaporation, etc.

(158) It should be understood that various embodiments described herein are merely examples and not intended to limit the scope of the present disclosure. Therefore, it is apparent to those skilled in the art that the present disclosure as claimed may include variations from specific embodiments and preferred embodiments described herein. Many of materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the present disclosure. It should be understood that various theories as to why the present disclosure works are not intended to be limitative.