Spirocyclic metallated iridium emitters for oled applications

Abstract

Disclosed herein are spiro-metalated iridium emitters and their preparation, OLED devices comprising the spiro-metalated iridium emitters, and methods relating thereto.

Description

Technical Field

[0001] This article discloses a spiro-metallized iridium emitter, its fabrication, an OLED device including the spiro-metallized iridium emitter, and related methods. Background Technology

[0002] Due to their superior photophysical and electroluminescent properties, iridium(III) complexes are currently among the most promising candidates for practical phosphorescent OLED (organic light-emitting diode) emitting materials for flat panel displays and solid-state lighting applications. Tridentate-didentate iridium(III) complexes containing bicyclic and tricyclic metallized complexes are the most mature Ir(III) OLED emitters. However, the inherent fragility of geometric isomerization under the harsh conditions associated with these emitters has become a well-known problem. In the context of molecular structure, assembling chelate ligands with higher dentation (e.g., tridentate, tetradentate, hexadentate) in the construction of iridium(III) phosphors has been considered as a way to address this problem, with the potential benefits of improved thermal and chemical stability. Therefore, research on Ir(III) phosphors with multidentate ring metallized ligands for OLED applications has increased in recent years. Numerous reports have been made on iridium(III) phosphors with two distinct [3+3] coordination modes of tridentate ligands and a set of monodentate, dipentate, and tridentate ligands with [3+2+1] coordination modes. In terms of chelating effect, tetradentate iridium(III) chelates, including those with [4+1+1] and [4+2] patterns, are in principle superior to tridentate analogs; however, examples of tetradentate chelates, especially those with [4+2] patterns that require non-planar tetradentate ligands, are rare. Summary of the Invention

[0003] To provide a basic understanding of some aspects of the invention, a brief overview of the invention is set forth below. This overview is not a comprehensive summary of the invention. It is neither intended to identify key or essential elements of the invention nor to describe its scope. Its sole purpose is to introduce some concepts of the invention in a concise form as a prelude to the more detailed description that follows.

[0004] In one embodiment, this document describes an iridium-containing emitter comprising a coordination complex containing a central iridium atom and a tetradentate ring metallized ligand comprising at least one spirocyclic bond and a bidentate ligand.

[0005] In another embodiment, an organic light-emitting device (OLED) is described herein, comprising: an anode; a cathode; and an organic layer disposed between the anode and the cathode, the organic layer comprising an iridium-containing emitter layer containing 0.1 wt% to 25 wt% of a coordination complex, the coordination complex comprising a central iridium atom and a tetradentate ring metallized ligand containing at least one spirocyclic bond and a bidentate ligand. In yet another embodiment, the organic layer comprises an iridium-containing emitter layer containing 1 wt% to 20 wt% of a coordination complex.

[0006] To address the foregoing and related problems, the present invention includes features fully described below and particularly pointed out in the claims. The following description and drawings illustrate certain illustrative aspects and implementations of the invention in detail. However, these are merely indications of some of the various ways in which the principles of the invention can be employed. Other objects, advantages, and novel features of the invention will become apparent from the following detailed description when considered in conjunction with the accompanying drawings. Attached Figure Description

[0007] Figure 1 The chemical structure of the new Ir(III) emitter was described.

[0008] Figure 2 X-ray crystal structures of two Ir(III) emitters according to two different embodiments are depicted.

[0009] Figure 3 A table showing the photophysical data of the new iridium(III) emitter is presented.

[0010] Figure 4 Representative from Figure 3 Graphical data in a table.

[0011] Figure 5 A table reporting device data was provided.

[0012] Figure 6 Device data represented in graphical form.

[0013] Figure 7 Represents device lifetime data in graphical form.

[0014] Figure 8 X-ray crystal structures of four Ir(III) complexes according to various embodiments are depicted.

[0015] Figure 9-18 Graphical data representing various embodiments of the new iridium(III) emitter. Detailed Implementation

[0016] This paper describes a novel molecular design method for phosphorescent iridium(III) emitters for OLED applications, characterized by a [4+2] coordination structure combining a tripod-arranged cruciate four-tooth ring metallized ligand framework and auxiliary bidentate ligands. This novel type of Ir(III) emitter exhibits superior performance, including one or more of the following: emission dopant materials that offer easy emission color tuning, high thermal and / or stereochemical stability, high emission quantum efficiency, and short radiative lifetime. Prototype devices fabricated using one of the Ir(III) emitters achieved 109,000 cd / m². 2 Maximum brightness and 17.0% EQE (external quantum efficiency).

[0017] The novelty and non-obviousness of the emitters described herein lie in one or more of the following aspects: (i) the spatial and morphological design of a nonplanar tetradentate ligand with a tripod-like coordination pattern formed by connecting three equatorial coordination sites to the apical coordination site through the introduction of helical bonds, and / or (ii) the rare evidence of using tetradentate ligands in combination with bidentate ligands to construct an octahedral iridium (III) emitter with a [4+2] coordination structure as a high-performance OLED material.

[0018] The rigid structure of the cruciform tetradentate ring metallized ligand with a stable predetermined coordination geometry provides high stereochemical stability to the Ir(III) emitter described in this invention, counteracting fac-mer stereoisomerism. Due to enhanced chelation, the [4+2] molecular structure also allows for stronger ligand coordination, resulting in iridium(III) emitters with higher chemical and thermal stability, which is advantageous for practical applications.

[0019] refer to Figure 1 The chemical structure of the novel Ir(III) emitter is shown. The rigid, cruciform tetradentate ring metallized ligand contains at least one spiroaryl bond, including spirofluorene, spirotriphenylamine, and spirodimethylacridine, resulting in a stable tripod-like coordination environment. The bidentate ligands described herein are commonly used as auxiliary ligands for Ir(III) emitters and can be readily modified into various monoanion ligands, which can be used to tune the photophysical properties of the Ir(III) emitter, as needed or specified for specific applications.

[0020] As used herein, ppy is 2-phenylpyridine; dfppy is 2-(2,4-difluorophenyl)pyridine; piq is 1-phenylisoquinoline; acac is acetylacetonate; acac-tBu is 2,2,6,6-tetramethylheptane-3,5-diketone; acac-mes is 1,3-dimestrimethylpropane-1,3-diketone; SPN is tetraphenyldithioimino diphosphonate; acNac is phenyl-substituted β-ketoiminate; NacNac is phenyl-substituted β-diketoiminate; dpfiq is 1-(dibenzo[b,d]furan-4-yl)isoquinoline; mpq is 4-phenylquinazoline; and pic is pyridinecarboxylic acid.

[0021] refer to Figure 2 , showed Figure 1 X-ray crystal structures of two Ir(III) emitters.

[0022] refer to Figure 3 A table reporting photophysical data for the new iridium(III) emitter is shown. As can be observed, the Ir(III) emitter exhibits a high phosphorus photon yield of up to 75% and / or 4.4 × 10⁻⁶. 5 s -1 The radiation rate constant is attractive for use as an emission dopant.

[0023] refer to Figure 4 The report was submitted. Figure 3 The table describes the data of iridium(III) emitters in graphical form.

[0024] refer to Figure 5 A table of device data was presented. Devices constructed using Ir(L1)ppy with different doping concentrations exhibited efficient yellow electroluminescence. The maximum luminance and EQE of these devices were measured to be as high as 109,000 cd / m². 2 and 17.0%.

[0025] refer to Figure 6 The report stated that... Figure 5 The data is supplemented by graphical representations of the tabular data.

[0026] refer to Figure 7 The device lifetime was reported. Notably, the device evaluation revealed a lifespan of 1000 cd / m². -2At actual initial brightness, the operating lifetime of the Ir(L1)ppy device is more than five times that of the Ir(ppy)3 device with the same device construction. These results highlight the unique stability advantages of the iridium(III) emitters described herein for practical OLED applications. The emitters of the present invention can be formed as thin films by vacuum deposition, spin coating, inkjet printing, or other known fabrication methods. Various multilayer OLEDs have been fabricated using the compounds of the present invention as luminescent materials or as dopants in the emitting layer. Typically, OLEDs are comprised of an anode and a cathode, with a hole transport layer, a luminescent layer, and an electron transport or injection layer in between. The present invention utilizes an additional carrier confinement layer to improve device performance. In one embodiment, the OLED is fabricated by vacuum deposition.

[0027] In another embodiment, OLEDs are manufactured via solution processes, including spin coating and printing.

[0028] The term "alkyl" refers to a straight-chain or branched saturated hydrocarbon group having 1-20 carbon atoms. In some embodiments, C 1-10 Alkyl groups are preferred. In some embodiments, C 1-6 Alkyl groups are preferred. In some embodiments, C 1-4 Alkyl groups are preferred. C 1-6 Examples of alkyl groups include methyl (C1), ethyl (C2), n-propyl (C3), isopropyl (C3), n-butyl (C4), tert-butyl (C4), sec-butyl (C4), isobutyl (C4), n-pentyl (C5), 3-pentyl (C5), pentyl (C5), neopentyl (C5), 3-methyl-2-butyl (C5), tert-pentyl (C5), and n-hexyl (C6). Alkyl groups may be optionally substituted with one or more substituents, for example, 1-5 substituents, 1-3 substituents, or 1 substituent. Common abbreviations for alkyl groups include Me(-CH3), (-CH2CH3), iPr(-CH(CH3)2), nPr(-CH2CH2CH3), n-Bu(-CH2CH2CH2CH3), or i-Bu(-CH2CH(CH3)2).

[0029] The term "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br), and iodine (I).

[0030] The term "haloalkyl" refers to the "C" group described above that has been substituted with one or more halogen groups. 1-20"Alkyl". Examples include mono-, di-, and polyhalogenated alkyl groups, including fully halogenated alkyl groups. Monohalogen substituents may have one iodine, bromine, chlorine, or fluorine atom in the group; dihalogen and polyhalogen substituents may have two or more identical halogen atoms or combinations of different halogens. Preferred examples of haloalkyl groups include monofluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, pentafluoroethyl, heptafluoropropyl, difluorochloromethyl, dichlorofluoromethyl, difluoroethyl, difluoropropyl, dichloroethyl, and dichloropropyl. The haloalkyl group may be substituted at any available junction with, for example, 1-5 substituents, 1-3 substituents, or 1 substituent.

[0031] The term "alkoxy" refers to the -OR group, where R has the same meaning as the terms "alkyl" and "haloalkyl".

[0032] The term "amino" refers to the -NRR' group, where R and R' are independently selected from H, alkyl groups as defined above, and haloalkyl groups.

[0033] The term "acyl" refers to the -C(O)R group, where R is selected from alkyl and haloalkyl groups as defined above.

[0034] The term "acyloxy group" refers to the -OC(O)R group, where R is selected from alkyl and haloalkyl groups as defined above.

[0035] The term "acylamino" refers to -NR'-C(O)R group, where R is selected from alkyl and haloalkyl groups as defined above, and R' is selected from H, alkyl and haloalkyl groups as defined above.

[0036] The term "carboxyl group" refers to the -C(O)OH group.

[0037] The term "thiol" refers to the -SR group, where R is selected from alkyl and haloalkyl groups as defined above.

[0038] The term "carbonyl" is represented by -C(O)-, whether used alone or in combination with other terms (e.g., aminocarbonyl).

[0039] The term "aminocarbonyl" refers to the -C(O)-NRR' group, where R and R' are independently selected from H, alkyl groups as defined above, and haloalkyl groups.

[0040] The term "carbamoyl" refers to the -C(O)-NH2 group.

[0041] The term "alkoxycarbonyl" refers to a -C(O)-OR group, where R has the same meaning as the terms "alkyl" and "haloalkyl".

[0042] The term "aryl" refers to a monocyclic or polycyclic (e.g., bicyclic) 4n+2 aromatic ring system having 6-14 ring carbon atoms and 0 heteroatoms (e.g., 6, 10, or 14 shared π electrons in a ring array). In some embodiments, the aryl group has 6 carbon atoms ("C6 aryl"; e.g., phenyl). In some embodiments, the aryl group has 10 ring carbon atoms ("C... 10 "Aryl"; for example, naphthyl, such as 1-naphthyl and 2-naphthyl). The aryl group also includes a ring system in which the aryl ring described above is fused with one or more cycloalkyl or heterocyclic groups and the connection point is on the aryl ring, in which case the number of carbon atoms continues to represent the number of carbon atoms in the aryl ring system. The aryl group may be substituted by one or more substituents, for example, optionally substituted by 1-5 substituents, 1-3 substituents or 1 substituent.

[0043] The term "heteroaryl" refers to a 5- to 14-membered monocyclic or bicyclic 4n+2 aromatic ring system having a ring carbon atom and 1-4 ring heteroatoms (e.g., having 6, 10, or 14 shared π electrons in a ring array), wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur. In heteroaryl groups containing one or more nitrogen atoms, the bonding point can be a carbon or nitrogen atom, provided the valence state allows. Heteroaryl bicyclic systems may contain one or more heteroatoms in one or both rings. Heteroaryls also include ring systems in which the heteroaryl ring described above is fused with one or more cycloalkyl or heterocyclic groups and the bonding point is on the heteroaryl ring. In such cases, the number of carbon atoms continues to represent the number of carbon atoms in the heteroaryl ring system. In some embodiments, 5- to 6-membered heteroaryl groups are particularly preferred, and these groups are 5- to 6-membered monocyclic or bicyclic 4n+2 aromatic ring systems having a ring carbon atom and 1-4 ring heteroatoms. Exemplary 5-membered heteroaryl groups containing one heteroatom include, but are not limited to, pyrroleyl, furanyl, and thiopheneyl. Exemplary 5-membered heteroaryl groups containing two heteroatoms include, but are not limited to, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, and isothiazolyl. Exemplary 5-membered heteroaryl groups containing three heteroatoms include, but are not limited to, triazolyl, oxadiazolyl (e.g., 1,2,4-oxadiazolyl), and thiazolyl. Exemplary 5-membered heteroaryl groups containing four heteroatoms include, but are not limited to, tetrazolyl. Exemplary 6-membered heteroaryl groups containing one heteroatom include, but are not limited to, pyrazolyl. Exemplary 6-membered heteroaryl groups containing two heteroatoms include, but are not limited to, pyridazinyl, pyrimidinyl, and pyrazinyl. Exemplary 6-membered heteroaryl groups containing three or four heteroatoms include, but are not limited to, triazinyl and tetraazinyl, respectively. Exemplary 7-membered heteroaryl groups containing one heteroatom include, but are not limited to, azazolyl. basic, oxygen thia Exemplary 5,6-bicyclic heteroaryl groups include, but are not limited to, indolyl, isoindolyl, indazole, benzotriazolyl, benzothiophenyl, isobenzothiophenyl, benzofuranyl, benzoisofuranyl, benzoimidazolyl, benzoxazolyl, benzoisoxazolyl, benzoxadiazolyl, benzothiazolyl, benzoisothiazolyl, benzothiadiazolyl, indazinyl, and purinyl. Exemplary 6,6-bicyclic heteroaryl groups include, but are not limited to, naphthidyl, pteridyl, quinolinyl, isoquinolinyl, cenolinyl, quinoxalinyl, phthalazinyl, and quinazolinyl. The heteroaryl group may be substituted with one or more substituents, for example, optionally substituted with 1-5 substituents, 1-3 substituents, or 1 substituent.

[0044] The term "aralkyl" refers to a -R-R' group, where R has the same meaning as the terms "alkyl" and "haloalkyl" as defined above, and R' has the same meaning as the term "aralkyl" as defined above.

[0045] "Aromatic" and "hybrid aromatic" have the same meaning.

[0046] The term “aryloxycarbonyl” refers to the -C(O)-OR group, where R has the same meaning as the terms “aryl” and “heteroaryl” defined above.

[0047] Examples of structures for iridium(III) emitters described herein include one or more of the following:

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055] Example

[0056] Unless otherwise stated in the examples and elsewhere in the specification and claims, all fractions and percentages are based on weight, all temperatures are in degrees Celsius, and all pressures are at or near atmospheric pressure.

[0057] Synthesis of tetradentate ligand-iridium complex

[0058]

[0059] Scheme 1. Synthesis of L1, L2, and L3

[0060] The synthesis of (6-phenylpyridin-2-yl)(pyridin-2-yl)methyl ketone was reported in Synthesis 2001, 16, 2484.

[0061] General Synthesis of Tetradentate Ligands L1, L2, and L3

[0062] A solution of 2-iodobiphenyl (600 mg, 2.14 mmol) in anhydrous THF (20 mL) was treated with n-BuLi (1.0 mL, 2.5 M, in n-hexane) under argon atmosphere at -78 °C. After 1 hour, a solution of (6-phenylpyridin-2-yl)(pyridin-2-yl)methyl ketone (532 mg, 2.0 mmol) in THF (5 mL) was added dropwise. The resulting mixture was stirred at -78 °C for 30 min and then warmed to room temperature. After 12 hours, the organic layer was washed with water and brine, then extracted with DCM and dried over anhydrous MgSO4. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography using (EA:PE = 1:5) as the eluent to give the intermediate tertiary alcohol (500 mg, 60%).

[0063] The intermediate tertiary alcohol was added to a mixture of concentrated HCl aqueous solution (1 mL) and acetic anhydride (50 mL). After reflux for 24 hours, the reaction was quenched with cold water after cooling to room temperature and neutralized to alkalinity with NaHCO3 (aqueous solution). The mixture was then extracted with DCM, dried over anhydrous MgSO4, and the residue was purified by silica gel column chromatography using (EA:PE = 1:4) as the eluent to give a white solid L1 (430 mg, 90%). 1 H NMR (500MHz, chloroform-d) δ8.63(d,J=4.3Hz,1H),7.96(d,J=7.7Hz,2H),7.93(d,J=7.3Hz,2H),7.84(d, J=7.5Hz,2H),7.57(d,J=7.8Hz,1H),7.54-7.33(m,9H),7.15-7.08(m,2H),7.01(d,J=7.6Hz,1H). 13 C NMR (126MHz, CDCl3) δ 164.5, 163.6, 156.2, 149.3, 148.1, 140.8, 139.4, 137.0, 136.0, 128.6, 128.4, 127.9, 127.6, 127.4, 126.7, 121.3, 121.1, 120.0, 119.1, 117.9, 68.9. HR-MS (ESI) m / z: calculated as C 29 H 20 N2[M+H] +,397.1705; observed [M+H] + ,397.1698.

[0064] L2 is prepared following the procedure described above for L1, replacing 2-iodobiphenyl with 2-bromotriphenylamine. 1 H NMR (500MHz, chloroform-d) δ8.69 (d, J=4.7Hz, 1H), 7.86 (d, J=6.8Hz, 2H), 7.64 (t, J= 7.8Hz,1H),7.62-7.55(m,4H),7.48(t,J=7.4Hz,1H),7.39-7.30(m,3H),7.2 5-7.21(m,2H),7.16(dd,J=6.7,4.9Hz,1H),7.12(d,J=8.0Hz,1H),7.07-6.9 9 (m, 4H), 6.94 (d, J = 7.6 Hz, 1H), 6.86 (t, J = 7.0 Hz, 2H), 6.36 (d, J = 8.2 Hz, 2H). 13 C NMR (126MHz, CDCl3) δ 166.2, 164.8, 155.1, 148.9, 141.6, 140.9, 139.3, 136.6, 135.4, 131.4, 131.1, 130.6, 128.6, 128.4, 128.2, 127.0, 126.9, 126.8, 125.3, 122.9, 120.8, 120.0, 116.9, 113.9, 60.5. HR-MS (ESI) m / z: calculated as C 35 H 25 N3[M+H] + ,488.2127; observed [M+H] + , 488.2125.

[0065] L3 is prepared following the procedure described above for L1, with 2-iodobiphenyl replaced by 1-bromo-2-(2-phenylprop-2-yl)benzene. 1 ¹H NMR (400MHz, chloroform-d) δ 8.64–8.59 (m, 1H), 7.86–7.80 (m, 2H), 7.62 (dd, J = 8.0, 1.1 Hz, 2H), 7.55–7.46 (m, 3H), 7.38–7.26 (m, 5H), 7.20 (dd, J = 8.0, 1.4 Hz, 2H), 7.15–7.04 (m, 3H), 7.01 (d, J = 8.1 Hz, 1H), 6.83–6.77 (m, 1H), 1.70 (s, 3H), 1.50 (s, 3H).

[0066]

[0067] Scheme 2. Synthesis of the [IrL(CO)Cl] and [IrL(MeCN)Cl] complex

[0068] Preparation of [Ir(L1)(CO)Cl]

[0069] A mixture of L1 (100 mg, 0.25 mmol) and IrCl3 (90 mg, 0.30 mmol) in glycerol (6 mL) was stirred at 290 °C for 2 h. After cooling to room temperature, the mixture was washed with water and extracted with DCM (3 × 20 mL). The organic layer was dried over anhydrous MgSO4, and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography using (EA:PE = 1:2) as the eluent to give a yellow solid [Ir(L1](CO)Cl] (105 mg, 65%). 1 ¹H NMR (400MHz, methylene chloride-d²) δ 9.33 (d, J = 4.8 Hz, 1H), 8.27 (d, J = 7.4 Hz, 1H), 8.06–7.95 (m, 2H), 7.86 (d, J = 7.2 Hz, 1H), 7.80 (t, J = 7.7 Hz, 1H), 7.75–7.62 (m, 3H), 7.62–7.51 (m, 4H), 7.34 (d, J = 7.4 Hz, 1H), 7.28 (t, J = 6.3 Hz, 1H), 7.22 (t, J = 7.2 Hz, 1H), 7.07 (t, J = 7.5 Hz, 1H), 6.97 (t, J = 7.4 Hz, 1H). 13 C NMR (126MHz, CDCl3) δ 170.2, 167.2, 157.3, 153.8, 152.9, 147.4, 144.4, 143.9, 143.9, 139.4, 139.3, 139.2, 137.0, 136.8, 136.1, 130.9, 129.9, 129.0, 128.4, 128.0, 126.8, 125.0, 124.5, 123.6, 122.3, 122.2, 118.2, 117.8, 115.9, 73.0. HR-MS (ESI) m / z: calculated as C 30 H 18 ClIrN2O[M-Cl] + ,615.1048; [M-Cl] was observed. + , 615.1016.

[0070] Preparation of [Ir(L2)(CO)Cl]

[0071] A mixture of L2 (120 mg, 0.25 mmol) and [Ir(cod)Cl]2 (190 mg, 0.28 mmol) in 1,2,4-trichlorobenzene (6 mL) was stirred at 190 °C for 2 hours. After cooling to room temperature, the residue was purified by silica gel column chromatography using (EA:DCM = 1:10) as the eluent to give a yellow solid [Ir(L2](CO)Cl] (110 mg, 60%). 1 H NMR (500MHz, chloroform-d) δ9.48 (d, J = 5.4Hz, 1H), 8.02 (d, J = 7.4Hz, 1H), 7.79-7.75 (m, 1H),7.66(d,J=8.3Hz,1H),7.61-7.54(m,4H),7.54-7.45(m,4H),7.34(d,J=7.9 Hz,1H),7.31-7.26(m,2H),7.25-7.15(m,4H),7.10(t,J=7.4Hz,1H),7.01(t,J= 7.5Hz, 1H), 6.49 (t, J = 7.8Hz, 1H), 6.39 (d, J = 8.5Hz, 1H), 5.76 (d, J = 8.1Hz, 1H). 13 C NMR (126MHz, CDCl3) δ 171.0, 167.9, 159.6, 157.8, 156.7, 151.0, 144.5, 141.9, 140.5, 139.0, 138.8, 138.8, 136.6, 135.2, 134.9, 132.4, 131.2, 130.9, 130.8, 129.8, 128.6, 127.3, 126.5, 124.8, 123.8, 123.4, 121.7, 118.6, 118.5, 117.7, 116.1, 115.4, 112.0, 65.3. HR-MS (ESI) m / z: calculated as C 36 H 23 IrN3O[M-Cl] + , 706.1470; [M-Cl] was observed. + , 706.1458.

[0072] Preparation of [Ir(L1)(MeCN)Cl]

[0073] [Ir(L1)(CO)Cl] (50 mg, 0.07 mmol), trimethylamine N oxide (12 mg, 0.16 mmol), and MeCN (4 mL) were stirred at 65 °C under an Ar atmosphere for approximately 24 hours. After cooling to room temperature, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography using EA / DCM = 1:5 as the eluent to give a yellow-green solid [Ir(L1)(MeCN)Cl] (40 mg, 80%).

[0074] 1 ¹H NMR (500MHz, chloroform-d) δ 9.32 (d, J = 5.2Hz, 1H), 8.23 ​​(d, J = 7.3Hz, 1H), 7.93 (d, J = 7.4Hz, 1H), 7.88 (d, J = 8.1Hz, 1H), 7.81 (d, J = 7.3Hz, 1H), 7.70–7.57 (m, 3H), 7.52 (d, J = 7.7Hz, 1H), 7.49 (d, J = 7.4Hz, 1H), 7.47–7.36 (m, 3H), 7.25–7.18 (m, 3H), 6.99 (t, J = 7.4Hz, 1H), 6.92 (t, J = 7.4Hz, 1H), 2.75 (s, 3H). HR-MS (ESI) m / z: calculated as C 31 H 21 ClIrN3[M-Cl] + ,628.1365; [M-Cl] was observed. + , 628.1360.

[0075] Preparation of [Ir(L2)(MeCN)Cl]

[0076] [Ir(L2)(MeCN)Cl] is prepared following the procedure described above for [Ir(L1)(MeCN)Cl], except that [Ir(L1)(CO)Cl] is replaced with [Ir(L2)(CO)Cl].

[0077] 1 H NMR (500MHz, chloroform-d) δ9.41 (s, 1H), 7.91 (d, J = 7.3Hz, 1H), 7.68 (t, J = 7.5Hz, 1H), 7.62-7.51 (m, 4H), 7.49-7.42 (m, 3H), 7.25-7.13 (m, 8H), 7.07 (t, J = 7.4Hz, 1H), 6.99 (t, J = 7.4Hz, 1H), 6.45 (t, J = 7.7Hz, 1H), 6.34 (d, J = 8.4Hz, 1H), 5.64 (d, J = 8.0Hz, 1H), 2.66 (s, 3H). 13C NMR (126MHz, CDCl3) δ 170.7, 160.7, 158.8, 157.4, 153.5, 146.4, 142.2, 140.9, 138.1, 137.0, 136.5, 135.2, 133.3, 131.1, 129.9, 129.7, 129.4, 129.0, 128.3, 126.3, 125.6, 124.2, 123.2, 122.0, 121.0, 118.8, 118.2, 116.5, 116.5, 115.8, 110.2, 64.9, 29.3. HR-MS (ESI) m / z: calculated as C 37 H 26 ClIrN4[M-Cl] + ,719.1787; [M-Cl] was observed. + , 719.1779.

[0078]

[0079] Scheme 3. Synthesis of the [Ir(L1)(O^O)] complex

[0080] Preparation of [Ir(L1)(acac)]

[0081] A mixture of L1 (100 mg, 0.25 mmol) and [Ir(cod)Cl]2 (180 mg, 0.27 mmol) in ethylene glycol (8 mL) was stirred at 200 °C under an Ar atmosphere for about 5 hours. After cooling to room temperature, the mixture was washed with water and extracted with DCM, and the organic layer was dried over anhydrous MgSO4. The crude intermediate mixture was treated with sodium 2,4-pentanedione hydrate (90 mg, 0.74 mmol) in ethylene glycol (10 mL) and stirred at 150 °C under an Ar atmosphere for about 8 hours. After cooling to room temperature, the mixture was washed with water and extracted with DCM, and the organic layer was dried over anhydrous MgSO4. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography with PE / DCM = 1:1 as the eluent to give a yellow solid [Ir(L1)(acac)] (40 mg, 23%).

[0082] 1H NMR (500MHz, chloroform-d) δ8.37(d,J=4.9Hz,1H),8.20(d,J=7.0Hz,1H),7.88(d,J=8.1Hz,1H),7.80(d,J=6.8Hz,1H),7.67-7.54(m,4H),7.52(d,J=7.4Hz ,1H),7.44(d,J=7.6Hz,1H),7.38-7.30(m,3H),7.22-7.14(m,2H),7.12(t ,J=7.3Hz,1H),6.99-6.90(m,2H),5.44(s,1H),2.21(s,3H),1.58(s,3H). 13 C NMR (126MHz, CDCl3) δ 184.6, 184.4, 170.8, 157.8, 156.8, 155.9, 152.0, 146.9, 146.2, 145.1, 140.3, 137.0, 135.6, 134.8, 134.2, 133.8, 130.8, 129.2, 129.1, 127.8, 126.6, 125.7, 123.9, 123.6, 122.0, 121.9, 121.6, 117.1, 115.7, 113.9, 101.4, 72.4, 28.2. HR-MS (ESI) m / z: calculated as C 34 H 25 IrN2O2[M+H] + ,687.1624; observed [M+H] + , 687.1619.

[0083] Preparation of [Ir(L1)(acac-tBu)]

[0084] The intermediate mixture, along with 2,2,6,6-tetramethyl-3,5-heptadecane (170 mg, 0.96 mmol) and KOtBu (230 mg, 2 mmol) in ethylene glycol (10 mL), was stirred overnight at 100 °C under an Ar atmosphere. After cooling to room temperature, the mixture was washed with water and extracted with DCM. The organic layer was dried over anhydrous MgSO4. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography using PE / DCM = 5:1 as the eluent to give a yellow solid [Ir(L1)(acac-tBu)] (15 mg, 48%). 1HNMR (500MHz, chloroform-d) δ8.24-8.19(m,1H),8.15(d,J=5.2Hz,1H),7.89(d,J=8.1H z,1H),7.80(d,J=7.3Hz,1H),7.64-7.48(m,5H),7.42(d,J=7.6Hz,1H),7.38(m– 7.30,3H),7.17(d,J=7.3Hz,1H),7.15-7.07(m,1H),7.03(t,J=7.4Hz,1H),6.94 (t,J=7.3Hz,1H),6.89(t,J=7.4Hz,1H),5.68(s,1H),1.35(s,9H),0.71(s,9H).

[0085] Preparation of [Ir(L1)(acac-mes)]

[0086] The intermediate mixture, along with 1,3-dimethyltrimethylpropane-1,3-dione (15 mg, 0.05 mmol) and KOtBu (5 mg, 0.05 mmol) in ethylene glycol (10 mL), was stirred overnight at 100 °C under an Ar atmosphere. After cooling to room temperature, the mixture was washed with water and extracted with DCM. The organic layer was dried over anhydrous MgSO4. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography using Hex / DCM = 3:1 as the eluent to give a yellow solid [Ir(L1)(acac-mes)] (17 mg, 80%). 1 ¹H NMR (500 MHz, methylene chloride-d²) δ 8.98 (d, J = 5.0 Hz, 1H), 8.21 (d, J = 7.3 Hz, 1H), 7.92–7.86 (m, 2H), 7.75 (d, J = 7.3 Hz, 1H), 7.67 (t, J = 7.6 Hz, 1H), 7.60–7.50 (m, 2H), 7.43 (d, J = 7.6 Hz, 1H), 7.39–7.29 (m, 4H). 7.24-7.17(m,1H),7.10(d,J=7.2Hz,1H),7.06(t,J=7.3Hz,1H),6.94(t,J=7.4Hz,1H),6.81(d,J =4.5Hz,4H),6.53(s,2H),5.54(s,1H),2.41(s,6H),2.16-2.24(m,6H),2.05(s,3H),1.18(s,3H).

[0087]

[0088] Scheme 4. Synthesis of the [Ir(L1)(C^N)] complex

[0089] Preparation of [Ir(L1)(ppy)]

[0090] The intermediate mixture and 2-phenylpyridine (120 mg, 0.77 mmol) in ethylene glycol (10 mL) were stirred at 150 °C under an Ar atmosphere for about 8 hours. After cooling to room temperature, the mixture was washed with water and extracted with DCM. The organic layer was dried over anhydrous MgSO4. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography with PE / DCM = 1:1 as the eluent to give a yellow solid [Ir(L1)(ppy)] (46 mg, 25%). 1 H NMR (500MHz, chloroform-d) δ8.43(d,J=7.4Hz,1H),8.30(d,J=6.9Hz,1H),8.04(d,J=7.2H z,1H),8.00(d,J=8.0Hz,1H),7.90(t,J=8.5Hz,2H),7.84(d,J=6.9Hz,1H),7.64-7 .55(m,3H),7.57-7.38(m,7H),7.26(t,J=6.6Hz,2H),7.20(t,J=7.1Hz,1H),7.05 (t,J=7.3Hz,1H),6.96(d,J=8.1Hz,1H),6.70-6.61(m,3H),6.58(t,J=6.2Hz,1H). HR-MS(ESI)m / z: calculated as C 40 H 26 IrN3[M+H] + , 742.1834; observed [M+H] + , 742.1828.

[0091] Preparation of [Ir(L1)(SPN)]

[0092] The intermediate mixture and K(SPN) (94 mg, 0.20 mmol) in ethylene glycol (10 mL) were stirred overnight at room temperature. After cooling to room temperature, the mixture was washed with water and extracted with DCM, and the organic layer was dried over anhydrous MgSO4. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography to give a yellow solid [Ir(L1)(SPN)] (50 mg, 50%). 1H NMR (400MHz, chloroform-d) δ9.53-9.45(m,1H),8.18(d,J=6.7Hz,1H),8.14(d,J=7.5H z,1H),8.10-8.00(m,2H),7.97-7.87(m,2H),7.79-7.71(m,2H),7.68-7.42(m ,9H),7.41-7.30(m,6H),7.27(s,1H),7.25-7.15(m,5H),7.15-7.07(m,4H),6 .87(t,J=7.4Hz,1H),6.76-6.69(m,1H),6.57-6.49(m,1H),6.48-6.40(m,1H).

[0093] Preparation of [Ir(L1)(piq)]

[0094] The intermediate mixture and 1-phenylisoquinoline (14 mg, 0.07 mmol) in ethylene glycol (10 mL) were stirred overnight at 100 °C under an Ar atmosphere. After cooling to room temperature, the mixture was washed with water and extracted with DCM. The organic layer was dried over anhydrous MgSO4. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography using Hex / DCM = 1:1 as the eluent to give a yellow solid [Ir(L1)(piq)] (7 mg, 15%). 1H NMR (400MHz, chloroform-d) δ 9.07 (d, J = 8.5Hz, 1H), 8.56–8.49 (m, 1H), 8.47–8.40 (m, 1H), 8.35–8.30 (m, 1H), 8.07 (d, J = 7.3Hz, 1H), 8.02 (d, J = 8.0Hz, 1H), 7.87–7.82 (m, 1H), 7.71–7.65 (m, 2H), 7.65–7.53 (m, 6H) ),7.51(dd,J=5.5,1.3Hz,1H),7.46(td,J=7.9,1.7Hz,1H),7.39-7.34(m,1H),7.32(d,J=6.1Hz,1H) ,7.27-7.21(m,3H),7.10-7.03(m,2H),6.99(d,J=6.1Hz,1H),6.68-6.58(m,2H),6.55-6.50(m,1H).

[0095] Preparation of [Ir(L1)(dpfiq)]

[0096] The intermediate mixture and 1-(dibenzo[b,d]furan-4-yl)isoquinoline (24 mg, 0.08 mmol) in ethylene glycol (10 mL) were stirred overnight at 100 °C under an Ar atmosphere. After cooling to room temperature, the mixture was washed with water and extracted with DCM, and the organic layer was dried over anhydrous MgSO4. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography with Hex / DCM = 2:1 as the eluent to give a red solid [Ir(L1)(dpfiq)] (7 mg, 20%). 1 ¹H NMR (500MHz, chloroform-d) δ 8.98–8.93 (m, 1H), 8.51 (d, J = 7.9 Hz, 1H), 8.33 (d, J = 7.1 Hz, 1H), 8.10 (d, J = 7.2 Hz, 1H), 8.06–7.98 (m, 2H), 7.86 (d, J = 7.7 Hz, 2H), 7.70–7.50 (m, 8H), 7.50–7.30 (m, 8H), 7.14–7.06 (m, 3H), 6.59–6.54 (m, 2H), 6.50–6.46 (m, 1H).

[0097]

[0098] Scheme 5. Synthesis of the [Ir(L1)(pic)] complex

[0099] Preparation of [Ir(L1)(pic)]

[0100] [Ir(L1)(MeCN)Cl] (30 mg, 0.045 mmol), 2-pyridinecarboxylic acid (13 mg, 0.10 mmol), and NaHCO3 (15 mg, 0.18 mmol) were stirred in 4 mL of ethylene glycol at 130 °C under an Ar atmosphere for approximately 2 hours. After cooling to room temperature, the mixture was washed with water and extracted with DCM, then dried over MgSO4. The solvent was removed under vacuum, and the residue was purified by silica gel column chromatography using DCM / EA = 5:1 as the eluent to give a yellow-green solid [Ir(L1)(pic)] (20 mg, 63%).

[0101] 1H NMR (400MHz, chloroform-d) δ8.28(d,J=7.8Hz,1H),8.23(d,J=6.6Hz,1H),7.99(d,J=4.7Hz,1H),7.89(dd,J=11.3,7.8Hz,2H),7.85-7.75(m,3H),7.6 5-7.54(m,3H),7.53-7.46(m,3H),7.38(d,J=6.9Hz,2H),7.23(d,J=7.5Hz,1H),7.15-7.08(m,1H),7.05-6.90(m,3H),6.81(t,J=7.4Hz,1H).

[0102]

[0103] Scheme 6. Synthesis of the [Ir(L2)(acac)] and [Ir(L2)(pic)] complex

[0104] Preparation of [Ir(L2)(acac)]

[0105] [Ir(L2)(MeCN)Cl] (30 mg, 0.04 mmol), sodium 2,4-pentanedione hydrate (10 mg, 0.08 mmol), and 4 mL of ethylene glycol were stirred at 150 °C under an Ar atmosphere for approximately 8 hours. After cooling to room temperature, the mixture was washed with water and extracted with DCM, then dried over MgSO4. The solvent was removed under vacuum, and the residue was purified by silica gel column chromatography using PE / DCM = 1:1 as the eluent to give a yellow-green solid [Ir(L2)(acac)] (5 mg, 16%).

[0106] 1 H NMR (400MHz, chloroform-d) δ8.36(d,J=5.3Hz,1H),7.65(t,J=7.8Hz,1H),7.60(d,J=7.5 Hz,2H),7.57-7.49(m,4H),7.48-7.41(m,3H),7.28(d,J=4.8Hz,1H),7.23-7.08 (m,6H),7.03(t,J=7.3Hz,1H),6.97(t,J=7.5Hz,1H),6.48(t,J=7.7Hz,1H),6.3 5(d,J=8.5Hz,1H),5.56(d,J=8.0Hz,1H),5.46(s,1H),2.17(s,3H),1.64(s,4H). 13C NMR (126MHz, CDCl3) δ184.8,184.7,171.2,161.9,161.3,160.3,151.6,146.7 ,142.6,141.2,139.6,137.5,136.4,135.3,135.2,133.6,131.2,130.9,129. 6,129.1,128.1,127.5,125.9,125.7,123.4,123.3,121.5,121.1,119.4,117.6,116.9,115.8,115.6,110.0,101.4,64.9,28.3,28.2.HR-MS(ESI)m / z: calculated as C 40 H 30 IrN3O2[M+H] + , 778.2046; observed [M+H] + , 778.2033.

[0107] Preparation of [Ir(L2)(pic)]

[0108] [Ir(L2)(MeCN)Cl] (37 mg, 0.045 mmol), 2-pyridinecarboxylic acid (12 mg, 0.10 mmol), and NaHCO3 (17 mg, 0.18 mmol) were stirred in 4 mL of ethylene glycol at 130 °C under an Ar atmosphere for approximately 2 hours. After cooling to room temperature, the mixture was washed with water and extracted with DCM, then dried over MgSO4. The solvent was removed under vacuum, and the residue was purified by silica gel column chromatography to give a yellow-green solid [Ir(L2)(pic)] (34 mg, 94%). 1 H NMR (500MHz, chloroform-d) δ8.29(d,J=7.5Hz,1H),8.00(d,J=4.9Hz,1H),7.79(t, J=7.1Hz,1H),7.76-7.65(m,3H),7.65-7.50(m,6H),7.50-7.35(m,4H),7. 25-7.12(m,4H),7.06(t,J=7.3Hz,1H),7.04-6.90(m,2H),6.82(t,J=7.2H z, 1H), 6.51 (t, J = 7.6Hz, 1H), 6.38 (d, J = 8.5Hz, 1H), 5.63 (d, J = 7.9Hz, 1H).

[0109]

[0110] Scheme 7. Synthesis of [Ir(L2)(ppy)]

[0111] Preparation of [Ir(L2)(ppy)]

[0112] [Ir(L2)(MeCN)Cl] (30 mg, 0.04 mmol), 2-phenylpyridine (0.12 mmol), and 4 mL of ethylene glycol were stirred at 150 °C under an Ar atmosphere for approximately 10 hours. After cooling to room temperature, the mixture was washed with water and extracted with DCM, then dried over MgSO4. The solvent was removed under vacuum, and the residue was purified by silica gel column chromatography using (PE / DCM = 1:1 - EA / DCM = 1:10) as the eluent to give [Ir(L2)(ppy)] (10%). 1 ¹H NMR (400 MHz, chloroform-d) δ 8.18–8.11 (m, 1H), 7.89 (d, J = 8.6 Hz, 2H), 7.73–7.40 (m, 14H), 7.24–7.14 (m, 4H), 7.05–6.99 (m, 1H), 6.90–6.83 (m, 1H), 6.75–6.63 (m, 3H), 6.57–6.49 (m, 2H), 6.34 (d, J = 8.4 Hz, 1H), 5.62 (d, J = 7.9 Hz, 1H). HR-MS (ESI) m / z: calculated as C₄₆H₃₁IrN₄[M+H]⁺, 833.2256; observed [M+H]⁺, 833.2247.

[0113]

[0114] Scheme 8. Synthesis of [Ir(L3)(acac)]

[0115] Preparation of [Ir(L3)(acac)]

[0116] A mixture of L3 (150 mg, 0.34 mmol) and [Ir(cod)Cl]2 (250 mg, 0.37 mmol) in ethylene glycol (8 mL) was stirred at 190 °C under an Ar atmosphere for approximately 20 hours. After cooling to room temperature, the mixture was washed with water and extracted with DCM, and the organic layer was dried over anhydrous MgSO4. The crude intermediate mixture and sodium 2,4-pentanedione hydrate (125 mg, 1.0 mmol) in ethylene glycol (15 mL) were stirred overnight at 100 °C under an Ar atmosphere. After cooling to room temperature, the mixture was washed with water and extracted with DCM, and the organic layer was dried over anhydrous MgSO4. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography using PE / DCM = 1:1 as the eluent to give a yellow solid [Ir(L3)(acac)] (35 mg, 14%). 1H NMR (500MHz, chloroform-d) δ8.34(d,J=4.7Hz,1H),7.79(d,J=8.0Hz,1H),7.63(d,J=7.4Hz,1H),7.59 (dd,J=12.4,7.5Hz,2H),7.54-7.42(m,4H),7.40(d,J=7.9Hz,1H),7.31(t,J=8.0Hz,1H),7.1 1(q,J=6.9,6.1Hz,2H),7.05(d,J=8.3Hz,1H),6.97(dd,J=11.8,7.6Hz,2H),6.86(d,J=8.0Hz ,1H),6.80(t,J=7.5Hz,1H),5.47(s,1H),2.18(s,3H),1.65(s,3H),1.56(s,3H),1.54(s,3H).

[0117]

[0118] Scheme 9. Synthesis of L4 and L5.

[0119] L4 was prepared following the same procedure as L1, except that (6-phenylpyridin-2-yl)(pyridin-2-yl) methyl ketone was replaced with (4-(tert-butyl)pyridin-2-yl)(6-phenylpyridin-2-yl) methyl ketone. 1 H NMR (300MHz, CDCl3) δ8.46(d,J=5.2Hz,1H),7.90(d,J=7.6Hz,2H),7.86(dd,J=7.8,1.6Hz,2H),7.79(d,J=7 .4Hz,2H),7.54-7.25(m,9H),7.19(s,1H),7.07(dd,J=5.2,1.7Hz,1H),6.93(d,J=7.2Hz,1H),1.17(s,9H).

[0120] L5 was prepared following the same procedure as L1, except that (6-phenylpyridin-2-yl)(pyridin-2-yl) methyl ketone was replaced with (6-(2,4-difluorophenyl)pyridin-2-yl)(pyridin-2-yl) methyl ketone. 1H NMR(500MHz, CDCl3)δ8.59(d,J=4.1Hz,1H),7.84(d,J=7.6Hz,2H),7.82-7.75(m ,3H),7.61(dd,J=7.9,1.5Hz,1H),7.51(t,J=7.8Hz,1H),7.46(td,J=7.8,1.9Hz, 1H),7.41(td,J=7.5,1.0Hz,2H),7.32(td,J=7.5,1.0Hz,2H),7.09(ddd,J=7.5, 4.8, 0.9Hz, 1H), 7.05 (d, J = 8.0Hz, 1H), 6.98 (d, J = 7.8Hz, 1H), 6.90-6.81 (m, 2H). 19 F NMR (377MHz, CDCl3) δ = -110.1, -112.0.

[0121]

[0122] Preparation of [Ir(L4)(CO)Cl]

[0123] [Ir(L4)(CO)Cl] is prepared following the procedure described above for [Ir(L2)(CO)Cl], except that L2 is replaced with L4. 1 HNMR (500MHz, CDCl3) δ9.24(d,J=6.0Hz,1H),8.22(d,J=7.4Hz,1H),8.04(d,J=7.4Hz,1H),7.99( d,J=1.8Hz,1H),7.85(d,J=7.3Hz,1H),7.69(dt,J=7.6,3.9Hz,1H),7.64(t,J=7.5Hz,1H),7.59( t,J=7.8Hz,2H),7.53(t,J=7.0Hz,2H),7.48(d,J=7.6Hz,1H),7.33(d,J=7.3Hz,1H),7.24(d,J=2 .0Hz,1H),7.21(td,J=7.5,1.0Hz,1H),7.03(t,J=7.5Hz,1H),6.98(t,J=7.4Hz,1H),1.22(s,9H).

[0124] Preparation of [Ir(L5)(CO)Cl]

[0125] [Ir(L5)(CO)Cl] is prepared following the procedure described above for [Ir(L2)(CO)Cl], except that L2 is replaced with L5. 1HNMR (400MHz, chloroform-d) δ9.38(d,J=5.1Hz,1H),8.25(d,J=7.2Hz,1H),8.02(t,J=8.2Hz,2H),7.88(d,J=7.0Hz,1H),7.82(td,J=7.9,1. 6Hz,1H),7.77-7.64(m,3H),7.64-7.52(m,3H),7.39(d,J=7.0Hz,1H),7.35-7.29(m,1H),7.05(t,J=7.5Hz,1H),6.61-6.52(m,1H). 19 F NMR (377MHz, CDCl3) δ = -106.7, -108.6.

[0126] Preparation of [Ir(L4)(MeCN)Cl]

[0127] [Ir(L4)(MeCN)Cl] is prepared following the procedure described above for [Ir(L1)(MeCN)Cl], except that [Ir(L1)(CO)Cl] is replaced with [Ir(L4)(CO)Cl].

[0128] 1 H NMR (400MHz, CDCl3) δ9.24(d,J=6.0Hz,1H),8.22(d,J=7.4Hz,1H),8.05(d,J=7.5Hz,1H),7.99(d,J=1.9Hz,1H),7.86(d,J=7.0Hz,1H),7.73-7.57 (m,6H),7.53-7.49(m,1H),7.33(d,J=7.4Hz,1H),7.25-7.20(m,2H),7.0 7(t,J=7.6Hz,1H), 6.99(dd,J=8.5,6.3Hz,1H), 2.01(s,3H), 1.22(s,9H).

[0129] Preparation of [Ir(L5)(MeCN)Cl]

[0130] [Ir(L5)(MeCN)Cl] is prepared following the procedure described above for [Ir(L1)(MeCN)Cl], except that [Ir(L1)(CO)Cl] is replaced with [Ir(L5)(CO)Cl].

[0131] 1H NMR (500MHz, CDCl3) δ9.30 (d, J=5.1Hz, 1H), 8.26 (d, J=7.1Hz, 1H), 7.91 (d, J= 8.0Hz,1H),7.84(d,J=6.0Hz,2H),7.72(t,J=7.9Hz,1H),7.65(dt,J=23.5,7. 4Hz,2H),7.53(t,J=7.9Hz,1H),7.48(d,J=7.7Hz,2H),7.41(d,J=6.6Hz,1H), 7.28-7.25(m,2H),6.98(t,J=7.4Hz,1H),6.48(t,J=10.1Hz,1H),2.80(s,3H).

[0132]

[0133] Preparation of Ir(L1)(dfppy)]

[0134] [Ir(L1)(MeCN)Cl] (30 mg, 0.045 mmol) and 2-(2,4-difluorophenyl)pyridine (dfppy) (26 mg, 0.0136 mmol) were stirred overnight at 120 °C under an Ar atmosphere in 4 mL of ethylene glycol. After cooling to room temperature, the mixture was washed with water and extracted with DCM, and dried over MgSO4. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography with Hex / DCM = 1:1 as the eluent to give a yellow-green solid [Ir(L1)(dfppy)] (20 mg, 57%). 1 H NMR (400MHz, CD2Cl2) δ8.36(t,J=8.3Hz,2H),8.07(d,J=7.8Hz,1H),8.00(dd,J= 7.2,1.1Hz,1H),7.93-7.82(m,3H),7.77-7.63(m,5H),7.63-7.56(m,2H),7.47(d ,J=4.7Hz,1H),7.32(d,J=7.4Hz,1H),7.08(t,J=7.4Hz,1H),6.82(ddd,J=7.0,5. 6,1.1Hz,1H),6.78-6.66(m,2H),6.46(dd,J=8.9,2.4Hz,1H),6.29-6.20(m,1H). 19 F NMR (377MHz, CDCl3) δ = -110.1, -111.0.

[0135] Preparation of [Ir(L1)(mpq)]

[0136] [Ir(L1)(MeCN)Cl] (21 mg, 0.032 mmol) and 4-phenylquinazoline (mpq) (13 mg, 0.10 mmol) were stirred overnight at 130 °C under an Ar atmosphere in 4 mL of ethylene glycol. After cooling to room temperature, the mixture was washed with water and extracted with DCM, and dried over MgSO4. The solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography with Hex / DCM = 2:3 as the eluent to give a yellow-green solid [Ir(L1)(mpq)] (15 mg, 60%). 1 H NMR (500MHz, CD2Cl2) δ8.99(d,J=8.4Hz,1H),8.61(d,J=7.9Hz,1H),8.56(d,J=7.3Hz,1H),8.41(d ,J=7.4Hz,1H),8.09(d,J=8.1Hz,1H),8.07(s,1H),7.99(d,J=7.3Hz,1H),7.89(d,J=7.4Hz,2H),7 .83(t,J=7.5Hz,1H),7.81-7.76(m,1H),7.73-7.61(m,5H),7.58-7.53(m,1H),7.50-7.44(m,2H), 7.36-7.28(m,3H),7.06(t,J=7.4Hz,1H),6.95-6.90(m,1H),6.74-6.65(m,2H),6.66-6.61(m,1H).

[0137]

[0138] Preparation of [Ir(L4)(ppy)]

[0139] [Ir(L4)(ppy)] is prepared following the procedure described above for [Ir(L1)(dfppy)], replacing [Ir(L1)(MeCN)Cl] and dfppy with [Ir(L1)(MeCN)Cl] and ppy.

[0140] 1H NMR (500MHz, CD2Cl2) δ8.26(d,J=7.4Hz,1H),8.23(d,J=7.0Hz,1H),7.95(d,J=1.8Hz,1H),7.83(d d,J=11.9,6.9Hz,3H),7.76(d,J=7.2Hz,1H),7.57(dt,J=7.4,3.8Hz,1H),7.55-7.42(m,5H),7.40- 7.31(m,3H),7.16(d,J=7.2Hz,1H),7.12(td,J=7.3,1.3Hz,1H),7.08(dd,J=10.5,4.2Hz,1H),6.9 0(t,J=7.3Hz,1H),6.82(dd,J=7.3,1.3Hz,1H),6.65-6.59(m,2H),6.59-6.53(m,1H),1.00(s,9H).

[0141]

[0142] [Ir(L5)(dfppy)] is prepared following the procedure described above for [Ir(L1)(dfppy)], except that [Ir(L1)(MeCN)Cl] is replaced with [Ir(L5)(MeCN)Cl]. 1 H NMR (400MHz, CD2Cl2) δ8.36(t,J=8.3Hz,2H),8.07(d,J=7.8Hz,1H),8.00(dd,J= 7.2,1.1Hz,1H),7.93-7.82(m,3H),7.77-7.63(m,5H),7.63-7.56(m,2H),7.47(d ,J=4.7Hz,1H),7.32(d,J=7.4Hz,1H),7.08(t,J=7.4Hz,1H),6.82(ddd,J=7.0,5. 6,1.1Hz,1H),6.78-6.66(m,2H),6.46(dd,J=8.9,2.4Hz,1H),6.29-6.20(m,1H).

[0143] [Ir(L5)(pic)] is prepared following the procedure described above for [Ir(L1)(pic)], except that [Ir(L1)(MeCN)Cl] is replaced with [Ir(L5)(MeCN)Cl]. 1H NMR (500MHz, CD2Cl2) δ8.35(t,J=5.4Hz,1H),8.29(t,J=5.4Hz,1H),7.98(dd,J= 8.2,3.5Hz,1H),7.95(t,J=4.4Hz,1H),7.92(td,J=7.8,1.4Hz,1H),7.88(dd,J= 8.2,2.2Hz,1H),7.75-7.63(m,1H),7.58-7.54(m,1H),7.32-7.22(m,1H),7.04( dt,J=5.6,2.1Hz,1H),7.00(t,J=7.4Hz,1H),6.40(ddd,J=11.8,7.2,2.5Hz,1H). 19 F NMR (377MHz, CDCl3) δ = -105.8, -111.0.

[0144] Table 1. Photophysical properties of the Ir(III) complex

[0145]

[0146]

[0147]

[0148]

[0149] For any figure or range of values ​​for a specified feature, a figure or parameter from one range can be combined with another figure or parameter from a different range for the same feature to produce a range of values.

[0150] Except as otherwise provided in the working examples or otherwise described, all figures, values ​​and / or expressions relating to amounts of components, reaction conditions, etc., used in the specification and claims should be understood to be modified by the term “about” in all cases.

[0151] Although the invention has been explained with reference to certain embodiments, it should be understood that various modifications will become apparent to those skilled in the art upon reading the specification. Therefore, it should be understood that the invention disclosed herein is intended to cover such modifications that fall within the scope of the appended claims.

Claims

1. An iridium-containing emitter, comprising the following general formula: In (R1)4 and (R2)3, each R1 and R2 independently represents hydrogen; D represents a bond, NPh, or C(Me)2; A1-A 11 B1 and B2 independently represent C or CR 4b , where R 4b Represents hydrogen or optionally substituted C1-C4 alkyl groups, or halogens; X1 and X4 independently represent C; X2 and X3 independently represent N; and L^L is selected from the following structure: 。 2. An iridium-containing emitter, wherein the emitter comprises at least one of the following structures: 。 3. An iridium-containing emitter, wherein the emitter comprises at least one of the following structures: 。 4. An organic light-emitting device, comprising: anode; cathode; An organic layer disposed between the anode and the cathode, the organic layer comprising an iridium-containing emitter layer containing 0.1 wt% to 25 wt% of a coordination complex selected from any one of claims 1-3.

5. The organic light-emitting device of claim 4, wherein the iridium-containing emitter layer comprises 1 wt% to 20 wt% of the coordination complex.

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