TWI238819B - Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such compounds - Google Patents

Abstract

The present invention is generally directed to electroluminescent Ir(III) compounds, the substituted 2-phenylpyridines, phenylpyrimidines, and phenylquinolines that are used to make the Ir(III) compounds, and devices that are made with the Ir(III) compounds.

Description

1238819 A7 B7 V. Description of the invention (彳) Related applications This application is currently being filed and requested to be filed on June 12, 2GG1. National patent application serial number G9 / 879, part of the continuation application for G14, two years in 2000. On June 30, 2014, Lashan You), the principal 々 ', and Lang Nai M said that they had the right to apply for Wu Guo ’s provisional application serial number 60 / 215,362, and claimed to apply on August 1 (), 2_ Υ Right to US Provisional Application Serial No. 60 / 224,273. Background of the Invention Invention of the invention Fan Hei The present invention "is about an electroluminescent complex with a fluorinated phenyl sigma lake, a phenyl mouth bite, and a phenyl iridium (III) iridium. It also relates to an active layer including an electrode Electronic devices that emit Ir (III) complexes. Related Art Description Organic electronic devices that emit light, such as the light-emitting diodes that make up a display, exist in many different kinds of electronic equipment. In all of these devices, one The organic active layer is sandwiched between two electrical contact layers. At least one electrical contact layer is light transmissive so that light can pass through the electrical contact layer. When power is applied to both ends of the electrical contact layer, the organic active layer transmits the light through the electrical contact layer Emission of light. It is well known to use organic electroluminescent compounds as active ingredients in light emitting diodes. It is known that simple organic molecules such as anthracene, thiadiazole derivatives, and humulin derivatives will exhibit electroluminescence. Conjugated polymers have also been used as electroluminescent components, as disclosed in, for example, US Patent No. 5,247,190 to Friend et al., US Patent No. 5,408,109 to Heeger et al., And Nakano et al. Continent patent application 443 861. The complex of 8-hydroxyphosphonium with trivalent metal ions (especially aluminum) is widely used as -4- This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1238819 A7 B7 V. Description of the invention (2 Electroluminescent component, as disclosed in, for example, US Patent 5,552,678 to Tang et al.

Burrows and Thompson have published that they can use the surface (fac) _ginseng (2-phenylpyridine) watch as an active ingredient in organic light emitting devices. (^ [To? /. Corpse / 2 less ^ LWi. 1999, 75, 4.) When the iridium compound is present in the main conductive material, the performance is maximized. Thompson also announced that the active layer is a poly (N-vinylcarbazole) doped surface-[[(2,4,5'-difluorophenyl) pyridine-C'2, N] iridium (III) )installation. (Polymer Preprints 2000, 41 (1), 770 °) However, there is a continuing need for electroluminescent compounds with improved efficiency. SUMMARY OF THE INVENTION The present invention relates to a silver compound (commonly referred to as a "Iγ (III) compound") having at least two 2-phenylσ specific bite ligands, wherein the ligand has at least one fluorine or fluorinated group group. The iridium compound has the following first chemical formula ...

IrLaLbLcxL, yL "z (first chemical formula) where: X = 0 or 1, y = 0, 1 or 2, and Z = 0 or 1, the restrictions are: X = 0 or y + z = 0 and when y = 2, then z = 0; L = double- or single-group ligand, and it is not benzylpyridine, phenylpyrimidine, or phenylpyridinium; For monodentate ligands, y + z == 2 and -5- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 1238819 A7 B7 V. Description of the invention (3 When L1 is For double-group ligands, z = 〇; L " = single-group ligands, and it is not a phenyl group, a phenyl group bite, or a phenyl group quinine; and L, L, and Lc are Similar to or different from each other, and each La, Lb & LC has the following structure (I):

Wherein: adjacent pairs of 1 to 114 and R5 to h can be combined to form a five- or six-membered ring, and at least one of R! To R8 is selected from F, CnF2n + i, 〇CnF2n + 1, and 〇CF2X, where n Is an integer from 丨 to 6, and X = Η, C1, or Br, and A-C or N, and the restriction is that when a = n, there is no ri. In another embodiment, the present invention relates to substituted 2-benzyl groups used to make the above Ir (III) compounds. Ratio: Phenyl, phenyl squeak, and phenyl p-quelin precursor compounds. The precursor compound has the structure (11) or (111):

(Π) -6- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1238819 A7 B7 V. Description of the invention (4) Wherein A and 1 to 8 are structured as above (I) And R9 is Η.

Rl4 where:

At least one of Rio to Ri9 is selected from F, CnF2n + 1, OCnF2n + i, and OCF2X, where η = an integer between 1 and 6, and X is Η, C1, or Br, and R2O is 2 . It is clear that free rotation exists for phenylpyridine, phenyl-pyrimidine and phenyl-quinoline bonds. However, with regard to the discussion in the text, the compounds will be explained in a specific direction. In another specific embodiment, the present invention relates to an organic electronic device having at least one emitting layer including the above Ir (III) compound, or a combination of the above Ir (III) compounds. As used herein, the term "compound" refers to an uncharged substance composed of molecules, which are further composed of atoms, in which atoms cannot be physically separated. The term "ligand" refers to a molecule, ion, or atom attached to the coordination layer of a metal ion. The term 'complex', when used as a noun, refers to a compound having at least one metal ion and at least one ligand. The term "group" refers to a part of a compound, such as a substituent in an organic compound or a ligand in a complex. The term "face" refers to a complex with an octahedron. The size of this paper applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 1238819 A7 B7 V. Description of the invention

An isomer of Ma ^ 3, in which the three "a" groups are adjacent, that is, at the corner of one face of the octahedron. The term, "meridional" refers to an isomer of the octahedral complex Ma ^ 3, three of which are "a", and the group occupies three positions in which two groups are trans to each other . When using the phrase, “adjacent” to a layer in an indicating device does not necessarily mean that one layer is in close proximity to another. On the other hand, using the phrase “adjacent R group, is in an indication in the chemical formula. The R groups next to each other (ie, the ruler group on the atom bound by the bond). In the term, photoactive is any material that exhibits electroluminescence and / or photosensitivity. The term, (H + f), refers to all combinations of hydrogen and fluorine, including fully hydrogenated, partially fluorinated or perfluorinated substituents. The so-called "emission maximum value" refers to the wavelength in units of micrometers to obtain the maximum electroluminescence intensity. Electroluminescence is generally measured in a diode structure where the material to be tested is sandwiched between two electrical contact layers and applied Voltage. Light intensity and wavelength can be measured, for example, using photodiodes and spectrographs, respectively. 0 Schematic illustration of the schematic diagram of the light emitting device (LED) in Figure 1. Figure 2 is the schematic diagram of the LED test device. Example Note: The Ir (III) compound of the present invention has the above first chemical formula Ir (III) LaLbLcxL, y. The above Iγ (ΙΠ) compound is often referred to as a cyclometallation complex: Ir having the following second chemical formula (III) Compounds are also often referred to as bicyclic metallization complexes: -8-This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 1238819 A7 B7 Five invention descriptions (second chemical formula)

IrLaLbL, yL ,, z where: y, z, La are defined.

L is the _ chemical formula of the above having the following third chemical complex: The compound of the formula Ir (III) is also often referred to as the ring metal irL L L (third chemical formula) where:

La, Lb and L. It has the meaning of the first chemical formula described above. The preferred cyclometallated complexes are neutral and non-ionic and can be sublimated intact. Thin films of these materials made by vacuum deposition exhibit good to excellent electroluminescent properties. The introduction of a fluorine substituent into a ligand on the iridium atom can improve both the stability and volatility of the complex. As a result, vacuum deposition can be performed at a lower temperature, and decomposition of the complex can be avoided. The introduction of a fluorine substituent into a ligand usually reduces the non-radiative decay rate and self-quenching in the solid state. These reductions will lead to increased luminous efficiency. Changes in the substituents with electron donating and electron-drawing properties can fine-tune the electroluminescence properties of the compound, and therefore the brightness and efficiency in the electroluminescence device can be optimized. Although it is not based on theory, the emission from the silver compound is based on the ligand and is generated by the charge transfer from the metal to the ligand. Therefore, -9- This paper size applies Chinese National Standard (CNS) A4 (21 × 297 mm) 1238819 A7 B7 V. Description of the invention The compounds that can exhibit electroluminescence include the compounds of the second chemical formula IrLaLbL, vL ”zi and The compound of the second chemical formula IrLaLbLc above, wherein all of La, Lb, and Le in the third chemical formula are phenylpyridine, phenylpyrimidine, or benzylquinine. Structures (I) and (π) 1 ^ The groups R to R 19 to the trans 8 group and the above structure (III) may be selected from conventional substituents of organic compounds such as alkyl, alkoxy, halogen, nitro, and cyano, and fluoro, Fluorinated alkyl and fluorinated alkoxy. This group can be partially or fully fluorinated (perfluorinated). Preferred iridium compounds have all trans 1 to 118 and 111 () to 1119 substituents selected from Fluoro, perfluorinated alkyl (CnF2n + 1) and perfluorinated alkoxy (0CnF2n + i), where perfluorinated alkynyl and alkoxyl have from 1 to 6 carbon atoms, or of the chemical formula OCF2X Group, where X is fluorene, C1, or Br. It is found that when any one or more of the groups 1 to 8 and R10SR19 are nitrate At the same time, the electroluminescence properties of the cyclometalated iridium complex are poor. Therefore, it is better that the radicals to Rs and ㈠ to! ^ 9 are not nitro groups. It is found that the luminous efficiency of the cyclometallated iridium complex can be Improved by the use of phenylpyridine, phenylpyrimidine, and phenylphosphonium ligands, some or all of which is replaced by deuterium. The nitrogen-containing ring can be a pyridine ring, pyrimidine, or pyrimiline. At least one fluorinated substitution The base system is preferably on a nitrogen-containing ring; CF3 is the best. Any conventional ligand known in transition metal coordination chemistry is suitable for strong and L ligands. Examples of bidentate ligands include having two Ligand compounds, such as ethylenediamine and acetone acetone, which may be substituted. Examples of anionic bidentate ligands include butenol, such as acetamidine; anionic forms via base Such as 8_hydroxyquinoline, which can be substituted, and the size of -10- paper is applicable to China National Standard (CNS) A4 (210 X 297 public love) ~ ------- 1238819

V. Description of the invention (from the capture of the I group in 8; amine group acid group; imino carboxylic acid group, such as σ bipicanoate; Shui Yang St root; Liu Jun imine, such as 2 _ [(phenylimino)) ; And phosphine oxides, such as 3 phenylbenzene scale) + propoxide. Examples of monodentate ligands include gaseous and lithosterone ions, scales; isonitrile, nitric oxide, and monoamine. Iridium complexes are neutral and sublimable. Like using single-double? , It should have an electrostatic charge of]. If two monodentate ligands are used, they should have a combined electrostatic charge of -1. Bicyclic metallization complexes can be useful for preparing reference ring metallization complexes in which the ligands are not exactly the same. In a preferred embodiment, the silver compound has the third chemical formula IrLaLbLc as described above. In a more specific embodiment, La = Lb = Lc. These better compounds, as measured by single crystal X-ray diffraction, often exhibit planar shapes in which the nitrogen atom coordinated to iridium is trans with respect to the carbon atom coordinated to iridium. These more preferred compounds have the following fourth chemical formula: 凾 _Ir (La) 3 (fourth chemical formula) wherein La has the above structure (I). The compounds may also exhibit a meridian in which the two nitrogen atoms coordinated to iridium are trans relative to each other. These compounds have the following fifth chemical formula: The element f "mer) -Ir (La) 3 (fifth chemical formula) wherein La has the above structure (I). A4 specification (210X297 mm) 1238819 A7 B7 V. Description of the invention (Examples of the compounds of the fourth and fifth chemical formula above 9 are shown in the following Table 1: Table 1 Compound A Ri r2 Rs R4 Rs R6 R? Rs Chemical formula 1 -a CHH cf3 HHHHH fourth l_b CHH cf3 HHHFH fourth 1-c CHH cf3 HFHHH fourth 1-d CHHHHFHHH fourth 1-e CHH cf3 HH cf3 HH fourth 1-f CHHHHHH cf3 HH fourth ig CHHHHHHFH fourth 1 -h C Cl H CF3 HHHHH fourth 1-i CHH cf3 HHH och3 H fourth lj CHH cf3 HHFHH fourth 1-k CHH N02 HH cf3 HH fourth MCHH cf3 HHH ocf3 H fourth 1-m N surface cf3 HHHHFH 4th KCHH cf3 HH och3 HH 4th 1-r CH och3 HHHH cf3 H 4th 1-sc HHHHFHFH 4th and 5th 1-tc HH cf3 HHFHF 5th 12- This paper standard applies Chinese National Standard (CNS) A4 Specifications (210 X 297 mm) 1238819 A7 ... B7 V. Description of the invention (1〇1-u C Η cf3 Η F Η F Η 5th 1-ν C Η Η cf3 Η Η Η F Η 5th or more Examples of the compound of the formula IrLaLbLfyL "z include compounds having the following structures (IV), (V), (VI), (IX), and (X), respectively-1 -η ^ 1-〇 ^ 1 -ρ '1 -w And 1 _χ ^

(IV)

-13- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1238819 A7 B7

This paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm) 1238819 A7 B7 12 V. Description of the invention The silver complex of the third chemical formula I r La Lb Lc is generally replaced by the appropriate 2 -Phenyl. Than bite 'phenyl σ dense bite, or phenyl Junlin prepared. The substituted 2-phenylpyridine, phenylpyrimidine, and phenylphosphonium shown in the above structure (II) uses substituted 2-pyridine, 2-pyrimidine, or 2-pyridinoline and arylboronic acid. Suzuki Coupling, which was prepared in good to excellent yields, 'as described in 0. Lohse, P. Thevenin, E. Waldvogel, Office "/ di, 1999, 45-48. About pyridine derivatives (Where X and Y represent substituents) This reaction is illustrated in the following equation (i):

Examples of 2-phenylpyridine and 2-phenylpyrimidine compounds having the above structure (II) are shown in Table 2 below:

Table 2 Compound A Ri R2 Rs R4 R6 R7 R8 R9 2-a CHH cf3 HFHHHH 2-b CHH cf3 HH cf3 HHH 2_c c HH no2 HH cf3 HHH 2-dc HH cf3 HHFHHH 2-ec HH cf3 HHH CH3〇HH -15 -This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 1238819 A7 B7 V. Description of the invention (13

2-f C Cl H cf3 HHHHHH 2-g CHHH ch3 HHFHH 2-h N tank HHHHHFHH 2-i CHH cf3 HHH CF30 HH 2-j N • face cf3 HHFHHHH 2-k CHH cf3 HHHFHH 2-1 C cf3 HHHHHHHH 2- mc Cl H cf3 HHHFHH 2-nc cf3 HHHHHFHH 2-0 c cf3 HHHHH CH30 HH > pc Cl H cf3 HHH CH30 HH 2-q N _ cf3 HHHHFHH 2-rc Cl H cf3 HHHHHF 2-sc HH cf3 HHHHHH 2-tc Cl HHHFHHHH 2-vc HH cf3 HH CH30 HHH 2-wc H CH30 HHHH cf3 HH 2-xc HHHHHFFFFHH 2-yc HH cf3 HHFHFH 2-zc HH cf3 HFHFHH 2-aa c HH Br HHH Br HH has the above structure (III) An example of a substituted 2-phenylquinoline compound is Compound 2 -IX 'which has Rl7 as CF3 and Rio to R16 and R18 to R20 as -16- This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 1238819 A7 B7 V. Description of the invention (14) Η. The 2-phenyl group prepared in this way is used to synthesize a cyclometalated iridium complex. A convenient one-step process has been developed using commercially available trihydrated iridium hydrate and silver trifluoroacetate. The reaction is generally carried out without using a solvent, and in the presence of 3 equivalents of AgOCOCF3, using an excess of 2-phenylpyridine, pyrimidine, or quinoline. This reaction for 2-phenylpyridine is illustrated by the following equation (2):

The ring-ring metalized iridium complex was separated, purified, and fully characterized using elemental analysis, 4 and 19F NMR spectral data, and single crystal X-ray diffraction for compound 1: soil, l ^ c. ^, And l-e. In some cases, a mixture of isomers is made. Mixtures can often be used without separating the individual isomers. In some cases, the iridium complex having the above second chemical formula IrLaLbL'yL''z can be separated from the reaction mixture using the same synthetic step as the preparation of the complex having the third chemical formula IrLaLbLe above. The complex can also be prepared by first preparing an intermediate iridium dimer with the following structure (VII): This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1238819 A7 B7 V. Invention Description (

Wherein: B Η, CH3, or C2H5, and La, Lb, Lc, and Ld may be the same or different from each other, and each of La, Lb, Lc, and 1 / has the above structure (I). Iridium dimers are generally prepared by first reacting hydrated iridium trichloride with 2-phenylpyridine, phenylpyrimidine or phenylquinoline, and adding NaOB. A particularly useful iridium dimer is a hydroxyiridium dimer having the structure (VIII):

This intermediate can be used to prepare compound 1 by the addition of ethyl acetate-p ° Particularly important are the red regions of the visible spectrum from orange-red from 570 to 625 nm and red from 625 to 700 nm Complex with maximum emission. It was found that when L has a structure (XI) below derived from a phenylquinoline compound having the above structure (III), or when L has a structure (XII) below derived from a phenyliso4-line compound The paper size of the second and third chemical formula is in accordance with the Chinese National Standard (CNS) A4 (210 X 297 mm) 1238819 A7 B7 V. Description of the invention (The emission maximum of the 16 compound is shifted to red:

Wherein: at least one of R10 to R19 is selected from F, CnF2n + 1, 0CnF2n + 1, and OCF2X, where η is an integer from 1 to 6, and X is 及, C1, or Br;

Wherein, at least one of the feet 21 to R3 0 is selected from the group consisting of F, CnF2n + 1, 0CnF2n + 1, and OCF2X, where η is an integer from 1 to 6, and X is Η, C1, or Br. It has also been found that the ligands of the present invention may have perfluoroalkyl and perfluoroalkoxy substituents of up to 12 carbon atoms. In the second chemical formula, the L 'and L "ligands in the complex can be selected from the above -19- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1238819 A7 B7 __ _ V. Any of the ligands listed in the description of the invention (17), and it is better to choose the ligand so that the entire molecule is not charged. Z is 0, and L 'is not phenylpyridine, phenylpyrimidine, or phenyl The monoanionic bidentate ligand of quinoline is preferred. Although it is not good, when L is a phenylpyridine ligand having the above structure (I), and L 'is a bidentate hydroxypyridinate ligand At the position, the complex of the second chemical formula also has an emission maximum shifted to red. The second chemical formula (where La is the same as Lb, L 'is a bidentate ligand, y is 1, and z is Examples of compounds of 0) and compounds of the third chemical formula (where La, Lb, and Le are the same) are shown in Table 8 below. When L has the above structure (I), eight is (:. In this table ,, 〇 & (: "represents 2,4-pentanedione;" 81 ^ "represents 8-hydroxyquinolinate;" Me-8hq "represents 2-fluorenyl-8-hydroxyaqualine. Table 8 Compound Chemical structure of the complex compound R substituent L, 8-a Second I r3 = cf3 r7 = f Me-8hq 8_b Second I r3 = cf3 r7 = f 8hq 8-c second XI r18 = cf3 acac 8 -d Second XII R29 ~ CF3 acac 8-e Second XII R28 = cf3 acac 8-f Second XII R29 = F acac 8-g Second XII R27 = F R29 = F acac -20- This paper is for China National Standard (CNS) A4 specification (210 X 297 mm) 1238819 A7 B7 V. Description of invention (18 8-h second XII R27 two F acac R29 = F R30 two F 8-i second XII R28 two F acac R29 = F R30 two F 8-j second XII R28 = F acac R30 = F 8-k second XII R29 ~ CgFi7 acac 8-1 third XII R29 two: cf3 嶋 8_m third XII R28 = F-R29 two F R30 = F 8-n Third XII R27 = F-R29 = F R30 = F 8-0 Third XII R27 = F-R29 = F 8-p Third XII R28 ~: cf3 _ 8_q Third XII R28 = F -R30 = F 8_r Second XII ^ 27 = F acac R: 29 = F 8-s Ziyidi-XII R29 = OCF3 acac -21-This paper size applies to China National Standard (CNS) A4 (210 X 297 Mm) 1238819 A7 B7 five Description (19) of the invention in Table 8 complexes having an emission maximum in the range of from about 590 nm to the 55〇. In addition, 'particularly important is a complex having a maximum emission value in the blue region of the visible spectrum from about 450 to 500 nm. It was found that when the complex has a second chemical formula (where La and Lb are phenylpyridine ligands having an additional ligand selected from phosphine, isonitrile, and carbon monoxide), the photoluminescence and electrical properties of the complex Luminescence shifted to blue. A suitable complex has the following sixth chemical formula:

IrLaLbL'L "(sixth chemical formula) wherein L 'is selected from the group consisting of phosphine, isonitrile, and carbon monoxide;

L "is selected from F, C, Br, and I

La & Lb is similar or different, and each La & Lb has the above structure ⑴, where: Xin to ^ is selected from alkyl, alkoxy, halogen, nitro, cyano, fluoro, and fluorinated alkyl And fluorinated alkoxy, and at least one of 1 to 118 is selected from F, CnF2n + 1, 0cnF2n + 1, and 0CF2X, where η is an integer from 1 to 6, and χ is η, Cl , Or Br, and A is C. The phosphine ligand in the sixth chemical formula is preferably the seventh chemical formula having the following -22- This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) ---- 1238819 A7 B7 V. Invention Explanation (20) P (Ar) 3 (seventh chemical formula) wherein Ar is an aryl group, preferably a phenyl group, which may have an alkyl group or an aryl substituent. The AΓ group is preferably a phenyl group having at least one fluorine or fluorinated alkyl substituent. Examples of suitable phosphine ligands include (abbreviated in parentheses) ... Triphenylphosphine [PPh3] See [3,5-bis (trifluorofluorenyl) phenyl] phosphine [? 113] Some phosphine compounds are commercially available, or they can be prepared using any of a number of well-known synthetic procedures, such as the alkylation or aromatization of PC13 or other P-electrophile with organolithium or organomagnesium compounds. The isonitrile ligand in the sixth chemical formula preferably has an isonitrile substituent on an aryl group. Examples of suitable isonitrile ligands include (abbreviated in parentheses): isocyano 2,6-xylene [NC-1] isocyano 3-trifluorobenzene [NC-2] isocyan 4-toluenesulfonium Methane [NC-3] Some isonitrile compounds are commercially available. It can also be prepared using known procedures, such as the Hofmann reaction, in which di-gasified carbene is generated from a gas imitation and a base in the presence of a first amine. In the sixth chemical formula, L "is preferably a gaseous compound. La is preferably the same as Lb. Examples of compounds of the sixth chemical formula (where La is the same as Lb and L" is a chloride) are shown in Table 9 below, of which 1 The numbers from 118 to 118 are as shown in the above structure (I). _23 ,， This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 1238819 A7 B7 V. Description of invention (21 Table 9

Compound L, Ri r2 Rs R4 Rs Rt Rs 9-a NC-1 H ch3 HHFHFH 9-b NC-1 HH ch3 HFHFH 9_c NC-1 HHHHFHFH 9-d NC-1 HHHHH cf3 HH 9-e NC-1 H ch3 HHH cf3 HH 9_f NC-1 HH cf3 HHHFH 9-g NC-1 HH cf3 HH cf3 HH 9-h NC-2 HHHHH cf3 HH 9-i NC-3 HH cf3 HHHFH 9-j PPh3 HH cf3 HHHFH 9-k PtmPh3 HH cf3 HHHFH 9-1 CO HH cf3 HHHFH NC-1 is 2,6- (CH3) 2C6H3NC; NC-2 is 3-CF3C6H4NC; NC-3 is 4-CH3C6H4S02CH2NC; PPh3 is P (C6H5) 3;

PtmPh3 is (Arf) 3P, where Arf = 3,5- (CF3) 2C6H3. The complexes in Table 9 have an emission maximum in the range of about 450 to 550 nm. -24- This paper size applies to China National Standard (CNS) A4 (210X297 mm) 1238819

Electronic equipment The invention also relates to an electronic device comprising at least one photoactive layer disposed between two electrical contact layers, wherein at least one layer of the device comprises the iridium complex of the invention. Devices often have additional layers of hole transport and electron transport. Figure 1 shows a typical structure. The device 100 includes an anode layer no and an anode layer 150. Adjacent to the anode is a layer 120 that includes hole transport material. Adjacent to the cathode is a layer including an electron transport material. A photoactive layer 130 is provided between the hole transport layer and the electron transport layer. The layers 120, 130, and 140 are collectively referred to as an active layer. Depending on the application of the device 100, the photoactive layer 130 may be a light emitting layer activated by applying a voltage (such as in a light emitting diode or a light emitting electrochemical cell), responding to radiant energy, and producing A layer of material (such as in a photodetector) that does not have an externally biased signal. Examples of photodetectors include photoconductive cells, photoresistors, light-controlled switches, photoelectric crystals, and phototransistors, and photovoltaic cells. These terms are described in the Markus, John, Cf # and Dictionary of Physics (Electronics and Nucleonics). J, 470 and 476 (McGraw-Hill, Inc., 1966). The iridium compound of the present invention is particularly useful as a photoactive material in layer 130 or as an electron transporting material in layer 140. The iridium complex of the present invention It is better to use as a light emitting material in a diode. It has been found that in these applications, the fluorinated compound of the present invention does not need to be effective in a solid matrix diluent. It can be greater than 2 based on the total weight of the layer A layer of 0% by weight silver compound up to 100% by weight iridium compound is used as the emissive layer. This is related to the non-fluorinated iridium compound-ginseng (2-phenylpyridine) iridium (111) (which was found to -This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1238819 A7 B7 V. Description of the invention (23) 6 to 8% by weight in the emission layer to achieve maximum efficiency) relative. It is needed to reduce the self-quenching effect. Additional materials may be present with the iridium compound in the emitting layer. For example, a fluorescent dye may be present to change the color of the emission. A diluent may also be added. The diluent may be a polymeric material, Such as poly (N-vinylcarbazole) and polysilane. It can also be a small molecule such as 4,4'-N, N'-dicarbazole biphenyl or a third aromatic amine. When a diluent is used, Iridium compounds are generally present in small amounts, and are generally less than 20 weight percent, and preferably less than 10 weight percent, based on the total weight of the layer. In some cases, the iridium complex may exist in more than one isomeric form. Or, there may be mixtures of different complexes. When it is understood that in the above discussion of OLEDs, the term "iridium compound" means a mixture including compounds and / or isomers. In order to obtain high-efficiency LEDs, holes The HOMO (highest occupied molecular domain) of the transport material should match the work function of the anode, and the LUMO (lowest unoccupied molecular domain) of the electron transport material should match the work function of the cathode. The chemical compatibility and sublimation temperature of the material should also be matched. Select Electronics Important considerations for hole transport materials. Other layers in OLEDs can be made of any material known for these layers. The anode 110 is an electrode that is particularly efficient for injecting positive charge carriers. It can be made of, for example, metals, Mixed metal, alloy, metal oxide or mixed metal oxide material, or it may be a conductive polymer. Suitable metals include Group 11 metals, Groups 4, 5, and 6 metals, and Group 8 Transition metals from Groups 10 to 10. If the anode is to transmit light, mixed metal oxides of Groups 12, 13 and 14 metals, such as indium tin oxide, are generally used. -26- This paper applies Chinese National Standards (CNS) A4 specification (210 X 297 mm) 1238819 A7 __B7 V. Description of the invention (24) The IUPAC numbering system is used in the text, in which the family in the periodic table is numbered from 1 to 18 (CRC Handbook of Chemistry and Physics (CRC Handbook of Chemistry and Physics), 81st Edition, 2000). The anode 100 can also include organic materials such as polyaniline, as described in "Flexible light-emitting diodes made from soluble conducting polymer", , Vol. 357, pp. 477-479 (June 11, 1992). At least one of the anode and the cathode should be at least partially transparent so that the light produced can be viewed. Examples of hole-transporting materials for layer 120 are outlined in, for example, Kirk Othmer, Encyclopedia of Chemical Technology, Fourth Edition, Volume 18, pp. 837-860, 1996, Υ ·

By Wang. Holes can be used to transport both molecules and polymers. Common hole transport materials are: N, N'-diphenyl-N, N, bis (3-tolyl)-[ι, ι, _biphenyl] -4,4 '· diamine (TPD) , 1,1-bis [(di-4_fluoranilino) phenyl] cyclohexane (TAPC), N, N, bis (4-tolyl) -N, N'-bis (4-ethylphenyl) )-[1,1 '-(3,3'-dimethyl) biphenyl] -4,4'-diamine (£ ?? 0),-(3- (phenyl)-> 1 , ≫ ^, 1 ^ _2,5_phenylenediamine (? 08), & -phenyl-4-team] ^ diphenylaminostyrene (TPS), p- (diethylamino) benzaldehyde Diphenylhydrazone (DEH), triphenylamine (TPA), bis [4- (N, N-diethylamino) -2-tolyl] (4-tolyl) methane (MPMP), 1-phenyl_3_ [P- (diethylamino) styryl] -5- [p- (diethylamino) phenyl] pyrazoline (PPR or DEASP) '1,2-trans · bis (9H-carbazole-9- Group) cyclobutane (DCZB), N, N, N ', N'-(4-tolyl) · (1, Γ-biphenyl) -4,4f-diamine (TTB), and porphyrin (Porphyrinic) compounds, such as -27- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1238819 A7 ___ B7 _ ^, invention description (25) ^ ^ 酉 太Copper. Common hole-transporting polymers are polyvinylcarbazole, (phenylfluorenyl) polysilane, and polyaniline. Hole-transporting polymers can also be made by doping hole-transporting molecules, such as those previously mentioned, into polymers such as polystyrene and polycarbonate. Examples of the electron-transporting material of the layer 140 include metal-clamping 8 • oxinoid compounds, such as ginseng (quinine) aluminum (Alq3); phlenyl compounds, such as 2,9-dimethylformate -4,7-diphenyl-l, 10-morpholine (DDpA) or 4,7-monophenyl-i, 10-morphine (dpa), and. Compounds such as 2- (4-biphenyl) -5_ (4-tert-butylphenyl) -1,3,4 · humidazole (PBD) and% (anal biphenyl) -4 • phenyl- 5- (4-tert-butylphenyl) _12,4_triazole (τAZ). Layer 14 can promote electron transport and act as a buffer or confinement layer, while preventing the quenching of excitons at the layer interface. This layer preferably promotes electron mobility and reduces exciton quenching. The cathode 150 is an electrode that is particularly efficient for injecting electrons or negatively charged carriers. The cathode can be any metal or non-metal having a lower work function than the anode. The material of the cathode may be selected from the group of alkali metals (for example, u, Cs), group 2 (alkaline earth) metals, and group 12 metals (including rare earth elements and lanthanides, and actinides). Materials such as aluminum, indium, calcium, barium, scandium and magnesium, and combinations thereof can be used. It is also possible to deposit a lithium-containing organometallic compound between the organic layer and the cathode layer to reduce the operating voltage. It is known to have other layers in organic electronic devices. For example, there may be a layer (not shown) between the conductive polymer layer 120 and the active layer 130 to promote positive charge transport and / or band gap fit of the layer, or as a protective layer. Similarly, there may be an additional layer between the active layer 130 and the cathode layer 15-28-28-26 26l2388l9 A7 B7 Description of the invention (shown in the figure) to promote negative charge transport and / or band gap coordination between the layers 'Or as a protective layer. Layers known in the art can be used. In addition, any of the layers mentioned may be made of two or more layers. Alternatively, some or all of the inorganic anode layer 110, the conductive polymer layer 120, the active layer 130, and the cathode layer 150 may be surface-treated to improve the charge carrier transport efficiency. The choice of materials for each component layer is better determined by balancing the goal of providing a device with high device efficiency. It should be understood that each functional layer may be composed of more than one layer. The device can be prepared by successive vapor deposition of individual layers on a suitable substrate. Substrates such as glass and polymeric films can be used. Conventional gas deposition techniques such as thermal evaporation, chemical vapor deposition, and the like can be used. Alternatively, the ' organic layer may be coated from a suitable solution or dispersion in a cereal using any conventional coating technique. In general, the different layers will have the following thickness ranges: anode 110,500 to 5000 angstroms, preferably 1000 to 2000 angstroms; hole transport layer 1250, 50 to 10,000 angstroms, preferably 2000 to 800 angstroms; light-emitting layer 130, 10 to 1,000 angstroms, preferably 100 to 800 angstroms; electron transport layer 140, 50 to 1,000 angstroms, to 200 to 800 angstroms is preferred; 150, 200 to 10,000 angstroms are preferred, and 300 to 50,000 angstroms are more preferred. The position of the electron-hole recombination region in the device, and therefore the emission spectrum of the device, will be affected by the relative thickness of each layer. Therefore, the thickness of the electron-transporting layer should be selected so that the electron-hole recombination region is in the light-emitting layer. The desired ratio of layer thickness will depend on the exact nature of the materials used. It should be understood that the efficiency of a device made using the iridium compound of the present invention can be further improved by optimizing other layers in the device. For example, -29- this paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 1238819 A7 B7 V. Description of the invention (27) More efficient cathodes such as Ca, Ba or LiF can be used . Shaped substrates and novel hole-transporting materials that can reduce operating voltage or increase quantum efficiency can also be applied. Additional layers can also be added to adjust the energy levels of each layer and promote electroluminescence. The iridium complex of the present invention is generally phosphorescent and photoluminescent, and it can be used in applications other than OLEDs. For example, organometallic complexes of iridium have been used as oxygen-sensitive indicators, such as light barrier indicators in bioassays, and as catalysts. Bicyclic metallization complexes can be used in the synthesis of three ring ligands which are the same or different reference metallization complexes. Examples The following examples illustrate some of the features and advantages of the present invention. It is intended to illustrate the invention, not to limit it. Unless otherwise indicated, all percentages are by weight. Example 1 This example illustrates the preparation of 2-phenylpyridine and 2-phenylpyrimidine used to form iridium compounds. The general procedures used are described in 0. Lohse, P. Thevenin, E. Waldvogel, 1999, 45-48. In a typical experiment, 200 ml of degassed water, 20 g of potassium carbonate, 150 ml of 1,2-dioxoethane, 0.5 g of Pd (PPh3) 4, and 0.05 mol of substituted 2- A mixture of gaspyridine (quinoline or pyrimidine) and 0.05 mol of substituted phenylboronic acid is refluxed (80-90 ° C) for 16 to 30 hours. The resulting reaction mixture was diluted with 300 ml of water and extracted with CH2C12 (2 x 100 ml). The combined organic layers were dried over MgS04 and the solvent was removed using vacuum. Use vacuum separation -30- This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) 1238819 A7 B7 V. Description of the invention (28) Distillation purifies the liquid product. The solid material was recrystallized from alkane. The isolated substance has a typical purity of > 98%. The starting materials, yields, melting points and boiling points of the new materials are shown in Table 3. NMR data and analytical data are shown in Table 4 3 Table 3 Preparation compounds of 2-phenyl-pyridine, phenylpyrimidine, and phenyl 4-line_yield (%) __ stagnation point / mmHg (melting point) (° C) 2 -s 70 2-a 72 2-b 48 --- 2-u 75 (76-78) 2-c 41 (95-96) 2-d 38 (39-40) 2-6 55 74.5 / 0.1 2-g 86 71-73 / 0.07 2-t 65 77-78 / 0.046 2-k 50 (38-40) 2-m 80 72-73 / 0.01 2-f 22 52-33 / 0.12 2-v 63 95-96 / 13 2-w 72 -31-This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 1238819 A7 B7 V. Description of the invention (29 2-x 35 61-62 / 0.095 2_y 62 (68- 70) 2-z 42 66-67 / 0.06 (58-60) 2-aa 60

1H NMR 7.48 (3Η). 7.70 (1Η), 7.83 (1Η) · 7.90 (2Η × 8.75 (1Η) NMR -62.68 pure 1 ^ calculate) 2, a 7.19 (1Η), 7 · 30 (1Η), 7.43 (1Η), 7.98 (2Η), 8.07 (1Η) 9.00 (1Η) 2-b 7.58 (1Η), 7.66 (1Η), 7.88 (1Η), 8.03 (1Η). 8.23 (1Η) 1Η), 8.35 (1Η) 8.99 (1Η) 2-u 7.55 (1Η), 7.63 (1Η). 7.75 (2Η), 7.89 (2Η5, 8.28 (2Η) · 8.38 (1Η), 8 · 50 (1Η) -60.82 (3F, s), -116.96 (IF, m) -62.75 (3F (s), -63.10 (3F (s) 62.89 (s) C, 64.50 (64.57) H.3.49 (3.59) N, 6.07 (6.28) C, 59.56 (59.75) Η, 3.19 (2.90) N, 5.52 (5.81) C, 53.68 (53.60) H · 2.61 (2.40) N, 4.53 (4'S1) C · 69.17 ( 70.33) H, 3.79 (3.66) N, 4.88 (5.12) -32- This paper size applies Chinese National Standard (CNS) A4 (210 x 297 mm) 1238819 A7 B7 V. Description of the invention (3 Table 4 (continued) ) Analysis%, measured (calculated) Compound 1HNMR 19F NMR _ or MS (Μ) 2-c 2-d it /. \ M / VJ / \ J / \ m / vlf L) ^ r rlHHHHHHHH) i ^? H ) 340803 ^ 68115 .5.6.9.135.404809 77.7.8.8, 8 9 77.7.88. -62.14 (s) -62.78 (3F, s), ”112.61 (1F, m) C, 53.83 (53.73) H, 2.89 ( 2.61) N (9.99 (10,44) 2-e 3.80 (3H) 6.93 (2H), 7.68 (1 7.85 (1 H), 7.96 (2H). 8.82 (1H), -62.63 ⑼ C, 59.73 (59.75) H.2.86 (2.90) N? 5.70 (5.81) C. 61.66 (61.90 ) H, 3.95 (4.04) N, 5.53 (5.38〉 2 ^ g 2'70 (3H) 7.10 (3H), 7 * 48 (1H), 7.60 (1H) · 8.05 (2H), -114.03 (m) 24 7.10 (2H), 7.35 (2H) f 7.96 (1H), 8.78 (1H), 73s) .67m) 2F13F, -6 (3¾ 2-k \ IJ / vl / \ l —- \ ny HHHH 2 13 1 / _ \ 8 200 0698 A 77.8. -62,75 (3F's) -11149 (m) 2-m HHHH 2 211 / v / v / lv / v 0 00 5 1807 7.N188. -62.63 (3F , s) -111.24 (m) C, 76.56 (77.00) H.5.12 (5.30) N, 5.43 (7.50) C. 50.51 (52.17) H.1.97 (2-17) N, 5.09 (5.07) C, 60.39 ( 59 · 75), H, 3.38 (2.90), N, 5.53 (5.51) C, 52.13 (52.17) H, 2.16 (2.17) N, 4.85 (5.07) -33-

This paper size applies to Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 1238819 A7 B7 V. Description of the invention (31) Table 4 (continued) Analysis%, measured (calculated) Compound 1H NMR 19F NMR or MS (Μ , 2-f 7.55 (3H), -62.57 (3) 257 (Μ 'c12h7f3c, n + ^ 22i (M-CI) 7.77 (2Η), 8.06 (1 H), 8.87 (1H) 2-v 3, 8 < 3H), -62.70 ppm C, 61.66 (61,37), 6.95 (1H) 丨 Η, 3.98 (3.67), 7.30 (1H), 7.50 (1H), 7.58 (1H) (7.75 (1H) f 7.90 (1H), 8.87 (1H) N.5.53 (5.48) 2-w 8.54 (lH, d), 8.21 (2H, d), 7.70 (2H, d), 7.24 (1H, s) _ 6.82 (1H, dd ), 3.91 (3H, s) 6.9 (2H, m), -63.08 (3F, s) 2-x -109.70 (1F, m), 7.18 (2Η, γπ), 7,68 (2H, m) · 7 95 (1Η, m), 8.65 (1H, -113.35 (1F, m). 2-ym); 6.94 (1 H), -62.72 (3F, s), 7.62 (2Η), 7.82 ( 1Η) 8.03 (1H). 8.96 (1H); -109.11 (2F, m) 2-z 6.85 (1 H), -62.80 (3F, S), 6.93 (1H), -107.65 (IF · m), 7.80, 7.90, 8.05 (3H), 8.89 (1 H); -112.45 (1F, m). 2-aa 7.70 (3H, m), 7.85 (3H, m), 7.80, 7.90, 8.85 (1H, m) .-34- This paper size applies to China National Standard (CNS) A4 specifications ( 210 x 297 mm) 1238819 A7 B7 V. Description of the invention (32) Example 2 This example illustrates the preparation of the above iridium compound of the fourth chemical formula-Ir (La) 3. In a typical experiment, IrCl3. A mixture of nH20 (; 53-55% Ir), AgOCOCF3 (3.1 equivalents per Ir), 2-aryl roar (excess), and (optionally) a small amount of water in N2 is 180-195. (: (Oil bath) vigorously stir for 2 to 8 hours. The resulting mixture is thoroughly extracted with CHsCI2 until the extract becomes colorless. The extract is filtered and passed through a Shixi stone column to produce a clear yellow solution. This solution was evaporated to obtain a residue, which was treated with methanol to produce a colored crystalline ginseng metallized ir complex. The complex was separated by filtration, washed with methanol, dried in vacuum, and (if necessary) ) Purified by crystalline 'vacuum sublimation, or Soxhlet extraction. Yield: 82-82%. All materials were characterized by NMR spectral data and elemental analysis, and the results are shown in Table 5 below. For this series The X-ray structure of the single crystal was measured for the three complexes. Compound 1-b made IrCl3 nH20 (54% Ir; 508 mg), 2- (4_fluorophenyl) _5_trifluoromethylpyridine-compound kk (2.20 G), AgOCOCF3 (1.0 gram), and water (1 ml) were vigorously stirred in a stream of N2, and the temperature was slowly (30 minutes) raised to 185 ° C (oil bath). After 2 hours at 190t, the mixture solidified. The mixture was allowed to cool to room temperature.固体 Extract the solids until the extract is decolorized. The combined digas methane solution is passed through a short silica column and evaporated. After adding methanol (50 ml) to the residue, place the flask at -10 ° C Keep overnight. The yellow of the ring-shaped metallized complex is 35- This paper is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 1238819 A7 B7 V. Description of the invention Color precipitate-compound b-separation, It was washed with methanol and dried in vacuum. Yield: 1.07 g (82%). The x-ray quality crystals of the complex were prepared by slowly cooling the warm solution in dichloroethane. Compounds 1-e make 11 * (: 1311112〇 (54% 11 *; 5 04 mg), 2- (3-trifluorotolyl)-5-difluorofluorenylpyridine-compound bb (1.60 g) And a mixture of AgOCOCF3 (1.01 g) was vigorously stirred in a stream of N2 while slowly raising the temperature (15 minutes) to 192 ° C (oil bath). At 1 90 -1 95 ° C for 6 hours After that, the mixture solidified. The mixture was allowed to cool to room temperature. The solid was placed on a silica column, and then washed with a large amount of digas methane. After evaporation of the liquid, the residue was treated with methanol to give a yellow solid. The solid was collected and purified by extraction with dichloromethane in a 25 ml micro Soissler extractor. The yellow metal complex was mixed with a yellow ring Shen Dianwu-Compound e—Isolated, washed with methanol, and dried in vacuum. Yield: 0.59 g (39/0). X-ray quality of the complex was obtained by calcination with hot 12-digas. Crystal. Compound 1-d makes Ii * Cl3.nH20 (54% Ir; 508 mg) '2- (2-fluorophenyl) -5-trifluoromethylpyridine-compound aa (1.53 g), and AgOCOCF3 (1 • 01 g) of the mixture was stirred vigorously in a% stream at 190-195 T: (oil bath) for 6 hours and 15 minutes. The mixture was allowed to cool to room temperature and was then extracted with hot it. The extract was passed through a short stone tube column and evaporated. Treatment of the residue with methanol (20 ml) resulted in the precipitation of the desired product-compound d-, which was separated by filtration, washed with methanol and dried in vacuo. Yield: 0.63 g (49%). X-ray quality crystals of complexes made from digas methane / methanol. -36- ^ Paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) (34) " 1238819 A7 B7 uses IrCl3 nH20 (54% Ir; 503 mg), 2- (4-trifluoromethyl) Oxyphenyl) -5-trifluoromethylpyridine compound ee (2.00 g) and AgOCOCF3 (1.10 g) were stirred vigorously in a N2 stream at 190-195 ° C (oil bath) for 2 hours and 45 Minutes. The mixture was allowed to cool to room temperature and then extracted with methane. The extract was filtered through a short silica column and evaporated. Treatment of the residue with methanol (20 mL) resulted in precipitation of the desired product-compound i-through filtration , It was separated, washed with methanol, and dried in vacuum. The yield was 0.86 g. In addition, 0.27 g of the complex was prepared by evaporating the mother liquor and adding petroleum ether to the residue. Total yield 1.13 g (72%). Compound 1-q makes IrCl3.nH20 (54% Ir; 530 mg), 2- (3-methoxyphenyl) -5-trifluoromethylpyridine (2.50 g), AgOCOCF3 (1.12 g), and water (1 liter) was vigorously stirred in a Ns flow while slowly raising the temperature (30 minutes) to 185 ° C (oil bath). After 1 hour at 85 ° C, the mixture was solidified. The mixture was cooled to room temperature. The solid was extracted with methane gas until the extract was discolored. The combined methane solution was filtered through a short silica column and evaporated. The residue was washed with hexane and then recrystallized (twice) from 1,2-digasethane-hexane. Yield: 0.30 g. 19F NMR (CD2C12, 20 ° C), 5: -63 (s). 4 NMR (CD2C12, 20 ° C), 5: 8.1 (1Η), 7.9 (1Η), 7.8 (1Η ,, 7.4 (1Η), 6.6 (2Η), 4.8 (3Η). Χ-ray quality crystals of complexes made from 1,2-dichloroethane / hexane (1,2-dichloroethane, hexane solvate). This complex is phosphorescent in color. -37- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 public love) I2388l9 A7 __ 5. Description of the invention (35) Compounds IzA, LlC., Lii to lh are prepared in a similar manner 1- i to 1-51, and k. In the preparation of the compound Id, a mixture of isomers having fluorine at the R6 or R8 position is prepared. ----- _ 丨 丨 __ and _ ---- --- _ ----------- i Table 5 Compound analysis (calculated (measured) _R (CD? Cl9, 25 ° C) 1-a C: 50.3 (50.1) H: 2.5 (2.7) N: 4.9 (4.9) Cl: 0.0 (0 2) ^ H: 6.8 (1H), 6.9 (1H), 7.0 (1H)? 7.8 (2H), 7.95 (1H), 8.1 (1H) 19p; -63.4 170; 47.4 (47.3) H: 2.0 (2.1) N: 4,6 (4.4) 1H: 6.4 (1H ), 675 (1H). 7.7 (1H), 7.8 (1H), 7.95 (1H), 8.05 (1H) 19F: -63.4 ($); -109.5 (ddd) 1 ~ c C: 47,4 (47.2) H: 2.0 (2.0) N: 4.6 (4,5) 1H: 6,6 (1H). 67 (1H), 6.9 (1H), 7.8 (1H), 8.0 (1 H), 8.6 (1 H) 10F : ^ 63.5 (S); -112.8 (ddd) 1-d C: 55.9 (56.1) H: 3,0 (3.2) N: 5.9 (5.8) 1H: 6.6 (2H), 6.8 (1H) · 7.0 (1H ) · 7.6 (1H), 7.7 (1H), 8.4 (1H) 19p: -115.0 (ddd) 1-e C; 44.1 (43.3) H: 17 (2.1) N: 3.9 (3.0) 1H: 6.9 (1H) , 7.1 (1H), 7.8 (1H), 8,0 (2H), 8.2 (1H) 19F: ^ 63.0 (1F), -63.4 (1 F) 1-f C: 50.4 (50.5) H: 2.5 (2.7 ) N: 4.9 (4,9) ^ H: 6.9 (1H), 7.1 (2H), 7.6 (1H), 7.8 (1H), 7.9 (1H), 8.1 (1H) 1 ^ F: -62.4 Vg C: 55.9 (56.3) H: 3.0 (3.2) N; 5.9 (6.0) 1H; 6.4 (1H), 6.7 (1H) 7 7.0 (1H), 7.6 (1H), 7.7 (2H) I7.9 (1H) 19F: -112.6 (ddd) -38- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1238819 A7 B7 V. invention is described in (36)

Binding Table 5 (continued) Analytical NMR Compound 1 (calculated (measured) (CD9C19, 25 ° 〇1-h C: 51.0 (45.2) H: 2.1 (2.3) N: 4,9 (4 * 2) 1H: 6.8 ( 1H), 6.95 (1H), 7 05 (1H), 7.7 (1Η). 8.0 < 1Η > > 8'9 (1Η) -63.3 1-1 C: 49.4 (49.3) H: 2.9 (2.8) N: 4.4 (4.4) 1H: 3.6 (3H) · 6.3 (1H), 6 6 (1H) · 7.7 (2H), 7.65 (1 Η), 7.95 (1 Η) 19F: -63.2 1 -j C : 47.4 (47.4) H: 2.0 (2.3) N: 4.6 (4 7) 1Η: 6.7 (m), 7.1 (m), 7.5 (m), 7.6 (m), 1Ί (m), 8.0 (m), 8.2 (m) 19F: 8 s resonance (-63.0 — -63.6) and 8ddd resonance (_92.2 · -112 1-k C: 43.5 (44.0) H: 1.8 (2.1) N: 8.5 (8.4) 1H: 6.9 (1H), 7.15 (1H), 8.1 (1H) r 8.3 (1H), 8.45 (1H), 8.6 (1H) 19F: -62.9 1-1 C: 42.2 (42.1) H: 16. (1.8) N: 3.8 (3.7) 1H: 6.5 (1H), 6.7 (1H), 7.75 (1H), 7.85 (1H), 8.0 (1H), 8.1 (1H) 19F: -58.1 (1F), -63.4 (1F) 3

This example illustrates the preparation of the iridium complex of the second chemical formula 11 * 1/1 ^ 1 >% 1/4%. Compound 1-η is a compound of 11 ^ 1311112〇 (54% 11 :; 5 10 mg), 2- (3-trifluorotolyl) pyridinium (1.80 g), and silver trifluoroacetate (1.10 g). The mixture was stirred vigorously at 190-195 ° C for 4 hours. The resulting solid was chromatographed on silica using digas methane to produce a mixture of bicyclic metallization complexes and unreacted ligands. Unreacted ligands were removed from the mixture by extraction with warm hexane. After the extract turned colorless, collect the hexane-insoluble solids at -39- This paper size applies Chinese National Standard (CNS) A4 (210X 297 mm) '" 1238819 A7 B7 V. Description of the invention (37 ) Dry in vacuum. The yield was 0.29 g. 19F NMR: -63.5 (s, 6F), -76.5 (s, 3F). The structure of this complex was determined by single crystal X-ray diffraction studies. Compound 1-〇 $ IrCl3.nH20 (54% Ir; 500 mg), 2- (2-fluorophenyl) -3-chloro · 5-trifluorofluorenylpyridine (2.22 g), water (0.3 ml), and A mixture of silver trifluoroacetate (1000 g) was stirred at 1 90 ° C for 1.5 hours. The solid product was chromatographed on silica using dichloromethane to yield 0.33 g of bicyclic metallized water trifluoroacetic acid complex-compound 1-p, and a 2: 1 co-crystal adduct of unreacted ligand. . 19F NMR: -63.0 (9F), -76.5 (3F), -87.7 (2F), -114.4 (IF). The co-crystallized phenylpyridine ligand was removed via recrystallization from dichloromethane-hexane. The structure of adducts and complexes was determined by single crystal X-ray diffraction studies. Example 4 This example illustrates the preparation of a hydroxyiridium dimer having the above structure (VIII). 11 * (: 13111112 (54% 11 *; 5 10 mg), 2- (4-fluorophenyl) -5-trifluoromethylpyridine (725 mg), water (5 ml), and 2- The mixture of ethoxyethanol (20 ml) was stirred vigorously under reflux for 4.5 hours. After adding a solution of NaOH (2.3 g) in water (5 ml), and then 20 ml of water was added, the mixture was stirred under reflux for 2 Hours. The mixture was allowed to cool to room temperature, diluted with 50 ml of water, and filtered. The solid was stirred vigorously under reflux with 30 ml of 1,2-digasethane and NaOH aqueous solution (2.2 g in 8 ml of water). Hours. Allow the organic solvent to evaporate from the mixture, leaving an orange solid suspended in the water phase. -40- The standard of this paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1238819 A7 _ B7 __ V. Invention Explanation (38) liquid. The orange solid was separated by filtration, washed thoroughly with water, and dried in vacuo, yielding 0.94 g (95%) of an iridium hydroxyl dimer (spectrum-grade purity). 4 NMR (CD2C12 )--1.0 (s, 1H, IrOH), 5.5 (dd, 2H), 6.6 (dt, 2H), 7.7 (dd, 2H), 7.9 (dd, 2H), 8.0 (d, 2H), 9.1 (d, 2H). 19F NMR (CD2C12): -62.5 (s5 3F), 109.0 (ddd, IF). Example 5 This example illustrates the preparation of a bicyclic metal from an iridium dimer. Chemical complex.

Compound 1-P A mixture of the iridium hydroxy dimer (1000 mg), ethyl acetate (0.075 ml; 4-fold excess), and dioxane (4 ml) of Example 4 at room temperature Stir overnight. The solution was filtered through a plug of short silica and evaporated to give an orange-yellow solid, which was washed with hexane and dried. The yield of the complex was 109 mg (94%). 4 NMR (CD2C12): 1.1 (t, CH3), 3.9 (dm, CH2), 4.8 (s, CH3COC / 〇, 5.9 (m), 6.7 (m), 7.7 (m), 8 · 0 (m), 8.8 (d). 19F NMR (CD2C12): -63.1 (s, 3F), -63.2 (s, 3F), -109.1 (ddd, 1F), -109.5 (ddd). Analysis: Calculated: C, 44 · 9; H, 2 · 6; N, 3.5. Found: C, 44.4; H, 2.6; N, 3.3. Compound 1-w The hydroxyiridium dimer of Example 4 (0 20 g) was dissolved in The THF (6 ml) solution was treated with 50 mg of trifluoroacetic acid, filtered through a short silica plug, evaporated to about 0.5 ml, treated with hexane (8 ml), and left overnight. The yellow crystalline solid was separated and separated with hexane. Wash with alkane and dry in vacuum. Yield (1: 1 THF-41-wood paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 mm) 1238819 A7 B7 V. Description of the invention (39) Compound): 0.24 g (96%). 19F NMR (CD2C12, 20.0, (5: -63.2 (s, 3F), -76.4 (s, 3F), -107.3 (ddd, IF). 4 NMR ( CD2C12 5 20 ° C) 5 δ · 9.2 (br s? 1H), 8.2 (dd, 1H), 8.1 · (d, 1H), 7.7 (m, 1H), 6.7 (m, 1H), 5.8 (dd , 1H), 3.7 (m, 2H, THF), 1.8 (m, 2H, THF). Compound 1 x x the digas acetate intermediates-compound 1w (75 mg), and 2- (4-bromophenyl) _5_bromo.pyridine ( 130 mg) of the mixture was stirred in N2 at 150-155 ° C for 30 minutes. The resulting solid was cooled to room temperature and dissolved in <: ΓΙ2 <: 12. The resulting solution was filtered through Shijiao And evaporated ^ The residue was washed several times with warm hexane and dried in vacuum, leaving a yellow, yellow photoluminescent solid. Yield: 74 mg (86%). 19F NMR (CD2C12, 20 ° C) Ά: -63 · 1 (s, 3F), -63.3 (s, 3F), -108.8 (ddd, 1F), -109.1 (ddd, IF). 4 NMR (CD2C12, 20.0, 5: 8.2 ( s), 7.9 (m), 7.7 (m), 7.0 (d), 6.7 (m), 6.2 (dd), 6.0 (dd). As confirmed by X-ray analysis, this complex is meridian and the nitrogen of the fluorinated ligand is trans. Example 6 This example illustrates the preparation of the silver compound of the fifth chemical formula f-Ir (La) 3 above. Compound 1-s This complex is synthesized in a similar manner to the compound. Based on NMR, TLC, and TGA data, the result was an approximately 1: 1 mixture of noodle and meridional isomers. -42- This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 public love) 1238819 A7 B7 V. Description of the invention (4〇) Compound 1-t makes IrCl3.nH20 (54% Ir; 0.40 g), 2 A mixture of-(3,5-difluorophenyl) -5-trifluoromethylpyridine (1.40 g), AgOCOCF3 (0.81 g), and water (0.5 ml) was vigorously stirred in a N2 stream, and simultaneously Slowly increase the temperature (ρο-βο minutes) to 165. (: (Oil bath). After 40 minutes at 165 ° C, the mixture solidified. The mixture was allowed to cool to room temperature. The solid was extracted with digas methane until the extract was discolored. The combined dichloromethane solution was filtered through a short Silica column and evaporation. The residue was washed thoroughly with hexane and dried in vacuum. Yield: 0.53 g (49%). 19F NMR (CD2C12, 20 ° C), 5: -63.55 (s, 3F) , -63.57 (s, 3F), -63.67 (s, 3F), -89 · 1 (t, 1F), -100.6 (t, 1F), -102.8 (dd, 1F), -118.6 (ddd, 1F) , -119.3 (ddd, 1F), .123.3 (ddd, IF). 4 NMR (CD2C12, 20 ° c), 5: 8.4 (s), 8.1 (m), 7.9 (m), 7.6 ( s), 7.5 (m), 6.6 (m), 6.4 vm). Also as confirmed by X-ray analysis, this complex is a meridian. Compound 1-u This complex was prepared and isolated similarly to compound 1 -q, and then purified by crystallization from 1,2-digasethane-hexane. The yield of the purified product was 53%. According to the NMR data, the complex was meridian. 19f (CD2C12, 20.0, 5: -63.48 (s, 3F), -63.52 (s, 6F) -105.5 (ddd, 1F), -105.9 (ddd, IF), -106.1 (ddd, 1F)

-107.4 (t, 1F), -107.9 (t, 1F), -109.3 (t, IF). NMR (CD2C12 '20 .〇 '5: 8.6 (m), 8.3 (s), 8.2 (s), 8.1 (m) 7.9 (m), 7.6 (m), 6.6 ( m), 6.4 (m), 6.0 · (m), 5.8 (m). -43- This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 1238819 A7 B7 V. Description of the invention ( 41)

Compounds 1 to V were prepared in a similar manner to compound 1-w using the trifluoroacetic acid bicyclic metallization intermediates, compound 1-x, and 2- (4-fluorophenyl) -5-trifluoromethylpyridine. This meridian-complex. 19f NMR (CD2C12, 20.0, 5: -63.30 (s, 3F), -63.34 (s, 3F), -63.37 (s, 3F), -108.9 (ddd, 1F), -109.0 (ddd, 1F) -109.7 (ddd, 1F). 4 NMR (CD2C12, 20 ° C), 5: 8.3-7.6 (m), 6.7 (m), 6.6 (dd), 6.3 (dd), 6.0 (dd). When sublimed at 1 atmosphere, this yellow luminescent meridium complex isomerizes to a green luminescent surface isomer, Compound 1-b. Example 7 This example illustrates the formation of an OLED using the iridium complex of the present invention. A thin film including a hole transporting layer (HT layer), an electroluminescent layer (EL layer), and at least one electron transporting layer (E Ding layer) was fabricated by thermal evaporation technology. An Edward Auto 306 with an oil diffusion pump was used for evaporation. The basic vacuum for all thin film deposition is in the range of ton (ton *). The deposition chamber can deposit five different films without interrupting the vacuum. Indium tin oxide (ITO) with an ITO layer of about 10 ⑻ to 2000 angstroms ( ITO) coated glass substrate. First use unnecessary IN HC1 solution to cut away unnecessary ITO area and pattern the substrate to form the first electrode pattern. Use polyimide tape as Then, the patterned ITO substrate was ultrasonically cleaned in a detergent aqueous solution. Then the substrate was first washed with distilled water, then with isopropyl alcohol, and then degreased in toluene vapor for ~ 3 hours. The clean patterned ITO substrate is loaded into a vacuum chamber, and the chamber is evacuated to 10.6 Torr. Then the substrate is further cleaned using an oxygen plasma about 5- -44- This paper is applicable to Chinese national standards (CNS) A4 specification (21〇x 297 mm) 1238819 A7 _____ B7___ V. Description of the invention (42) Min. After cleaning, the multilayer film is then continuously deposited on the substrate by evaporation. Finally, through the photomask The patterned metal electrode was deposited on the eighth. The thickness of the film was measured using a quartz crystal monitor (SycoI1 STC-200) during the deposition process. All film thicknesses described in the examples were calculated assuming the density of the deposited material was 1. The nominal thickness obtained is then taken out of the completed OLED device from the vacuum chamber and immediately characterized without encapsulation. Table 6 shows the overview and thickness of the device layers. In all cases, the anode system is IT as discussed above. , And the cathode system has A1 having a thickness in the range of 700-76 Angstroms. In some samples, a double-layer electron transport layer is used. The layer indicated first is adjacent to the EL layer. Table 6 Alq3 = ref (8- Hydroxypyridinium) hydrazine = 2,9-difluorenyl-4,7-diphenyl-1,10_morpholine fr (ppy) 3 = noodles_seng (2 · phenylpyridine iridium MPMP = Bis [4 < N, N-diethylamino) -2-tolyl] (4-tolyl) pinane sample HT layer (thickness, A) EL layer (thickness, A) ET layer (thickness, A) Compare MPMP (528) Ir (ppy> 3 (408) DDPA (106) + Alq3 (320) 1 MPMP (520) compound izfe (499) DDPA (125) + Alq3 (365) MPMP (541) compound 1-b ( 580) DDPA (407) 3 — MPMP (540) Compound 1-e (499) DDPA (112) + Alq3 (340) 4 ^ MPMP (525) Compound 1-k (406) DDPA (106) Alq3 (341) 5 ^^ MPMP (570) compound Izi (441) DDPA (107) + Alq3 (339) -45- This paper size is applicable to China National Standard (CNS) A4 specification (21〇X 297 mm) 1238819 A7 ^^ _-_ -V. Description of the invention (43) 6 MPMP (545) compound lii (462) — DDPA (111) + Alq3 (319) 7 MPMP (643) compound l_q (409) DDPA (112) + Alq3 (361) 8 MPMP ( 539) Compound M (430) DDPA (109) + Alq3 (318) 9 MPMP (547) Compound U (412) DDPA (105) + Alq3 (300) 10 MPMP (532) Compound 1-h (457) DDPA (108) + Alq3 (306) 11 MPMP (603) Compound 1-d (415) DDPA (111) + Alq3 (303) 12 MPMP (551) Compound (465) DDPA (106) + Alq3 (313) 13 MPMP (520) Compound 1: 1 (405) DDPA (410) 14 MPMP (504) Compound JL ^ (400) DDPA (393) 15 MPMP (518) Compound ϋ (153) DDPA (418) 16 MPMP (556) Compound 1-m (416) DDPA (430) 17 MPMP (520) Compound IrS (419) DDPA (420) 18 MPMP (511) Compound 1-0 (412) DDPA (413) 19 MPMP (527) Compound 1-p (425) DDPA (412) 20 MPMP (504) Compound 1-b (417) DPA (407) 2T ^ MPMP (525) Compound Ιζί (419) DPA (416) 22 ^ MPMP (520) Compound 1-u (421) DPA (405) -46 -This paper size is in accordance with Chinese National Standard (CNS) A4 (210 x 297 mm) 1238819 A7 B7 V. Description of the invention (44 OLED samples are measured by (1) the current-voltage (IV) curve, (2) Electroluminescence photometric vs. voltage, and (3) Electroluminescence spectrum vs. voltage. Figure 2 shows the device 200 used. The Keithley Source-Measurement Unit 23 7 and 280 were used to measure the I-V curve of the OLED sample 220. While scanning voltage with Kesley SMU, use Minolta LS-110 luminance meter 210 to measure the electroluminescence luminosity (unit candle light (Cd) / m 2) versus voltage. The electroluminescence spectrum is obtained by using a pair of lenses 230 through an electronic shutter 240 to disperse the light scattered through the spectrograph 250 and then measure it with a diode array detector 260. All three measurements are performed simultaneously and controlled using a computer 270. The efficiency of a device at a particular voltage is measured by dividing the electroluminescence of the LED by the current density required to operate the device. The unit is candlelight / amp. The results are shown in Table 7 below: Table 7 Electroluminescence properties of iridium compounds Sample peak photometric efficiency Cd / m2 Peak photometric efficiency Cd / A Peak efficiency Cd / A Approximate peak wavelength mn Comparison 540 at 22 V 0.39 0.48 522 1 1400 at 21 V 3.4 11 525 2 1900 at 25 V 5.9 13 525 3 830 at 18 V 1.7 13.5 525 4 7.6 at 27 V 0.005 0.13 521 -47- This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1238819 A7 B7 V. Description of the invention (45 Table 7 Electroluminescence properties of iridium compounds Sample peak luminosity Cd / m2 Peak efficiency Cd / A Peak efficiency Cd / A Approximate peak wavelength nm 5 175 at 25 V 0.27 1.8 530, 563 6 514 at 20 V 1.5 2.2 560 7 800 at 26 V 0.57 1.9 514 8 1200 at 28 V 0.61 2 517 9 400 at 18 V 1.1 4 545 10 190 at 16 V 2.3 3.3 575 11 1150 at 25 V 1.2 3.8 506, 526 12 340 at 20 V 0.49 2.1 525 13 400 at 21 V 3 5 520 14 1900 5 9 525 15 2500 6 11 525 16 100 at 27 V 0.17 0.2 560 17 3.5 at 28 V 0.005 0.014 575 18 30 at 26 V 0.08 0.16 590 19 2000 at 21V 6 8 532 -48- This paper size applies to China Standard (CNS) A4 specification (210 X 297 mm) 1238819 A7 B7 V. Description of invention (46 Table 7 Electroluminescence properties of iridium compounds Sample peak photometric Cd / m2 Peak photometric efficiency Cd / A Peak photometric efficiency Cd / A Approximate The peak wavelength of nm 20 350 at 26 V 0.60 1.6 595 21 1200 at 22 V 5 545 22 80 at 19 V 1 540 The peak efficiency is the best indication of the value of the electroluminescent compound in the device. Its instruction needs to be entered into the device, This is a measure of the number of electrons that a particular number of photons leave (photometric). It is a fundamentally important value that reflects the inherent efficiency of a light-emitting material. It is also important for practical applications, because higher efficiency means less electrons are needed to reach the same luminosity, which in turn means lower power consumption. Higher efficiency devices also tend to have longer lifetimes because a higher percentage of injected electrons are converted into photons rather than generating heat or causing unwanted chemical side reactions. Most of the iridium complexes of the present invention have much higher peak efficiencies than the mother-faced-ginseng (2-phenylpyridine) iridium complex. As discussed above, these less efficient complexes can also be useful as phosphorescent or photoluminescent materials, or as catalysts. Example 8 This example illustrates the preparation of the ligand parent compound of formula XI-1- (2,4-difluorobenzyl) isoxoline. Use 2,4-difluorophenylboronic acid (Aldrich Chemical Co., 13.8 g, -49-) This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) 1238819 A7 ______ B7 V. Description of the invention ( 47 ~) '' ~ 87 4 Moore) ,! -Gas iso 4-leaching (Aldrich Chemical Co., 13 g 79.4 Emole), triphenylphosphine 1 bar (〇) (Aidrich, 3.0 g, 2.59¾ mole), carbonic acid bell (em Science, 24 · 2 g, 175 mmol), water (300 ml), and dimethoxyethane (Aldrich, 300 ml) were stirred under reflux in N 2 for 20 hours, after which the mixture was cooled to room temperature, and the organic The layers are separated from the water layer. The aqueous layer was extracted with 3 x 150 ml of ether, and the combined organic portions were dried over sodium sulfate, filtered, and the filtrate was evaporated to dryness. The crude material was chromatographed on a silica gel column. The catalyst by-products were first dissolved in 4: 1 hexane / CHAl2, and finally the products were dissolved in CH2Cl2 / MeOH (9.5: 0.5, product Rf = 0.7). The pure product fraction was collected and dried in vacuo to give 177 g (92% isolated yield) of a pale yellow solid with > 95% NMR spectral purity. 1H NMR (CDC13, 296 K, 300 ΜΗζ), (58.61 (1Η, d, J = 5 · 7 Ηζ), 7.89 (1Η, d, J = 8.2 Ηζ), 7.67-7.85 (3Η, m), 7. · 52-7.63 (2H, m), 6.95-7 · 12 (2H, m) ppm. 19F NMR (CDC13, 296 K, 282 MHz) 5 -109.01 (1F, brs), -109.87 (1F, d, JF_F = 8.5 Hz). Example 9 This example illustrates the preparation of a bridged digas dimer- [IrCl {2- (2,4-difluorophenyl) isoquinoline} 2] 2. Let Example 8-1 -(2,4-difluorophenyl) isoxoline (1.00 g, 4.15 mmol), IrCl3 (H2O) 3 (Strem Chemicals, 703 mg, 1.98 mmol), and 2-ethoxyethanol ( Aldrich Chemical Co. (25 ml) was stirred under reflux for 15 hours, and then the precipitate was separated by filtration, and the methanol was -50. This paper size is applicable to China National Standard (CNS) A4 (210X 297 mm) 1238819 A7 B7 5 2. Description of the invention (48 washings and drying in vacuum to obtain 104 g (74/0) of orange-red solid product, > 95% NMR spectral purity. 1H NMR (CD2C12, 296 K , 300 MHz): 5 8 · 85 (2H, d, J = 6 · 4 Ηζ), 8 · 38 (2H, dd, J = 8.8 & 9.5Hz), 7.82-7.97 (m, 4H), 7.67-7.78 (2H, m), 6.81 (2H, d, J: 6.4 Hz), 6.42 (2H, ddd, J = 2.4, 3.3, and 11. · 4 Hz), 5.25 (2H, dd, J = 2.4 and 8.8 Hz) ppm. I9F NMr (CE) Cl3, 296K, 282 MHz) (5-95.7 (2F, d, JF-F = 12 Hz), -108.03 (2F, d, JF_F = 12 Hz). Example 10 This example illustrates the bicyclic metallized iridium complex- [Ir (acac) {l_ (2,4-difluorophenyl)) in Table 8. Preparation of quinoline} 2] -complex 8-! *. [IrCl {l- (2,4-difluorophenyl) isoxoline} 2] 2 (300 mg '0.212 mmol Ear), sodium acetoacetone (Aldrich chemical Co., 78 g, 0.636 mmol), and 2-ethoxyethanol (1 (ml)) were stirred at 120 ° F for 0.5 hour. The volatile components were then removed in a vacuum. The residue was dissolved in digas methane, and the solution was passed through a pad of silica gel, and digas firing was used as a dissolution solvent. The resulting orange-red filtrate was evaporated to dryness and then suspended in methanol. The precipitated product was separated by filtration and dried in vacuo. Isolated yield = 230 mg (70%). 4 NMR (CD2C12, 296 K '300 MHz) · 5 8 · 40 (2Η, dd, J = 8.8 and 9 Hz), 7.97 (2H, d, J = 8.1 Hz), 7.78 (2H, ddd, J = 0.7, 6.6, and 7.8 Hz), 7.70 (2H, dd, J = 1.3 and 8.4 Hz), 7.66 (2H, d, J = 6.4 Hz), 6.44 (2H, ddd, J = 2.4, 5.9, and, 1〇 · 8 ppm), -51-This paper size is in accordance with Chinese National Standard (CNS) A4 specification (21〇x 297 mm) 1238819 A7 B7 V. Description of the invention (49) 5.68 (2H, dd, J = 2.4 & amp 8.5 Hz), 5.30 (lH, s), 1.78 (6H, s). 19F NMR (CDC13, 296K, 282 MΗζ) 5. " 96 · 15 (2F, d, JF_F = 11.3 Ηζ), -109.13 (2F, d, JF-F = 11.3 Hz). Compounds 8-a to 8-k and 8-s in Table 8 were prepared using similar procedures. Compounds 8-1 to 8-q in Table 8 were prepared using the procedure of Example 2. Example 11 A thin film OLED device was manufactured using the procedure according to Example 7. Table 10 shows the overview and thickness of the device layers. In all cases, the anode system is ITO as discussed above, and the cathode system is A1 having a thickness in the range of 700-760 Angstroms. MPMP = bis [4- (N, N_diethylamine | DPA = 4, 7-di $ 10 I0-2-tolyl] (4-fluorenyl) pyranyl-1,10-morpholine sample HT layer EL layer ET layer (thickness, A) (thickness, person) (thickness, person ) 11-1 MPMP compound 8-a DPA (572) (419) (400) 11-2 MPMP compound 8-b DPA (512) (407) (394) 11-3 MPMP compound 8-c DPA (548) ( 441) (408) -52- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Binding

1238819 A7 B7 V. Description of the invention (50.11-4 MPMP compound 8-d DPA (508) (410) (408) 11-5 MPMP compound 8-e DPA (560) (421) (407) 11-6 MPMP Compound 8-f DPA (526) (409) (405) 11-7 MPMP Compound 8-g DPA (890) (408) (402) 11-8 MPMP Compound 8-h DPA (514) (465) (403) 11-9 MPMP compound 8-i DPA (564) (418) (413) 11-10 MPMP compound 8-j DPA (564) (405) (407) 11-11 MPMP compound 8-k DPA (522) (400 ) (408) 11-12 MPMP compound 8-1 DPA (529) (421) (408) 11-13 MPMP compound 8-m DPA (530) (411) (411) 11-14 MPMP compound 8-0 DPA ( 537) (412) (409) -53- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 1238819

A7 B7 V. Description of the invention (51) 11-15 MPMP (509) compound 8-p (405) DPA (405) 11-16 MPMP (512) compound 8-q (414) DPA (402) 11-17 MPMP (529) Compound 8-r (442) DPA (412) 11-18 102961-31 MPMP (524) Compound 8-s (407) DPA (408) The OLED samples were characterized as in Example 7, and the results are shown in Table 11 below. Table 11 Electroluminescence properties of iridium compounds Sample peak photometric Cd / m2 Peak efficiency Cd / A Approximate peak wavelength, nm 11-1 45 at 22V 0.13 628 11-2 32 at 20V 0.12 > 600 11-3 340 at 24 2.5 590 11-4 350 at 22V 1.7 625 -54- This paper size applies Chinese National Standard (CNS) A4 size (210 x 297 mm) 1238819 A7 B7 V. Description of invention (52 11-5 300 at 21V 1.5 > 600 11-6 200 at 20V 1.1 605, 650 11-7 300 at 23V 5 605 11-8 280 at 21V 2.9 590 11-9 1000 at 20V 3.5 592 1M0 380 at 21V 2.3 610, 650 11-11 8 at 23V 0.25 624 11-12 800 at 20V 2.3 610, 650 11-13 360 at 22V 1.5 590 11-14 160 at 24V 1.2 590 11-15 80 at 21V 1.1 597 -55- This paper size applies to China National Standard (CNS) A4 specifications ( 210 X 297 mm) 1238819 A7 B7 V. Description of the invention (53)

11-16 170 at 21V 0.8 615 11-17 1300 4 600 at 22V 11-18 540 1.6 622 at 20V Example 12 This example illustrates the preparation of other phenylpyridine ligands. The phenylpyridine compounds 12-a to 12-j shown in Table 12 below were prepared as described in Example 1.

Table 12 Compound A Ri r2 Rs R4 Rs FU r7 Rs r9 12-a CH ch3 HHFHFHH 12-b CH ch3 HHH cf3 H cf3 H 12-cc HH ch3 HFHFHH 12-dc H ch3 HHH cf3 HHH 12-ec HH ch3 HH cf3 H cf3 H 12-fc HHHHH cf3 HHH 12-gc HHHHFHFHH 12-hc H t-Bu HHHHFHH 12-ic H t-Bu HHH cf3 H cf3 H 12-ic H ch3 HHHH cf3 HH -56- This paper is applicable to China Standard (CNS) A4 specification (210 X 297 mm) 1238819 A7 B7 V. Description of the invention (54 Analysis and NMR data are shown in Table 13 below. Table 13 Compound yield (%) Bp / ιηπι Hg (mp) ° C NB No 1hnmr 19FNMR 12-a 61.5 70-72 / 0.03 101394-104 2.39 (3H), 6'99 (2H), 7.02 (1 H), 7.57 (1 H), 7.99 (1 H) 8JS6 (1H) -102.96 (IF, m), -113,18 〇F, m) 12-b 39 66-68 / 0.01 101394-115 ^ 2.47 (3 H), 7.I7 (1H), 7.63 (1¾ 7.91 (1¾ S.4 `` (2H), 8.60 (111), 9.D0 (1H) -63.23 (s) 1Z-C 76 75-76 / 0.01 (54-56) 101394-12J 2.25 (3 »), 6.90 (2H), 7.55 (2H), S.50 (1H), 8.35 (1 H), 10.37 (IF, m) -113.50 (lF.m) 12-d 76 69 ^ 70 / 0.06 (44-46) 101394-129 2.35 (3H ), 7.05 (1H), 7-55 (210, S.010H), 8.18 (1H), 8.50 (IH) -63.03 (s) -57- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1238819 A7 B7 V. Description of the invention (55 Compound yield (%) Β.ρ7 mm Hg (mp) ° C ND No ^ NMR J9F nmr 12- «84 (83-85) 102960-48 2.43 (3H) 7.66 (1 H) 7 7.87 (1¾ S * 47 (2H), S.59 (1H) -63.IS (s) I2-f 72 64-65 / 0.026 99344-Π 7.20 (1 H), 7.65 (3H) S 8.10 (1 HX Sn (lH), S .65 (1H), 9.43 (1 H) -63.05 (s) 12-g 3d 62 / 0.01 101394-93 6.90 (1 H), 7.1S (2HX 7.6S (2H), 7.95 (1 H), S. 65 (IH), -109.70 〇F, m) -113.35 (IF, m) 12-h 49 99-101 / 0.26 102960-Π7--.12-i 58 108-109 / CJ 103555-3 1.35 (9 H ) 7.34 (1 H) 7.72 (1 H) 7. $ S (1H) 8.44 (2H) 8.6K1H) -63.29 12-j 46 76-77 / 01 (52-54) 1 102960-143 2.46 (3H) 7.15 (1H) 7.60 () H) 7.73 (2H) 8.11 (2H) 8-59 (iH) -62.86 -58- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 1238819 A7 B7 5 2. Description of the invention (56 in the presence of [(dppb) PdCl2] catalyst (dppb = 1,4-bis (diphenylphosphino) butane)), via 2-gas-5-trifluorofluorinylpyridine and bromide 2 , 4-two Kuma Da magnesium oxide stupid group (the Kumada) the conjugation was prepared to give 2- (2,, 4, - dimethoxybenzene-yl) -5 - difluoromethyl ° instigate ratio. Example 13 This example illustrates the formation of a bigas bridged dinuclear bicyclic metallization IΓ complex.

The Ir complex is prepared by reacting IrCl3.nH2O with the corresponding 2-arylpyridine in an aqueous solution of 2-ethoxyethanol. This method is similar to the literature procedure of phenylpyridine (Sprouse, S .; King, KA; Spellane, P. Watts, R.J., J. Am. Chem. Soc., 1984, 106, 6647-53; Garces King, KA; Wans, R. J., Inorg. Chem., 1988, 27, 3464-71). Make irCl3nH20, 2-arylpyridine (2.2-2.8 equivalents per Ir), 2-ethoxyethanol (approximately 30 ml per 1 g of IrCl3.nH20), and water (approximately 5 per 30 ml of 2-ethoxyethanol) The mixture was stirred vigorously under reflux (N2) for 4 to 10 hours. After cooling to room temperature, concentrated HC1 (3 ml of IrCh.ni ^ O per 1 g) was added, and the mixture was stirred for 30 minutes. The mixture was diluted with water, stirred for 1-2 hours, and filtered. The solid product was washed with water, methanol and dried in vacuo. Yields are from 65 to 99%. Example 14 This example illustrates the formation of an Ir. Complex of the invention having a sixth chemical formula (where L "is cl). Contains a monodentate graph-phosphine, co, a Or isonitrile ligand bicyclic metallized arylpyridine iridium ΠΙΙ) plutonium complex-59- This paper size applies to Chinese National Standard (CNS) A4 specification (210 X 297 mm) A7 B7 1238819 V. Invention Explanation (57) The two gas-bridged dinuclear bicyclic metallized lr complexes, monodentate ligand L ', and 1,2-digas ethane (DCE) or toluene were prepared as in Example 13. The mixture was stirred under reflux (N2 or C0 (when L is C0)) until all solids were dissolved, and then stirred for an additional 3 minutes. The product was isolated and purified by evaporation and crystallization in air. Selected The detailed steps of the complex are described below. All the complexes were characterized using NMR spectral data (31p NMR = hp-yHJNMR). Due to the insufficient thermal stability of the complexes, no satisfactory results were obtained. Combustion analysis. Using single crystal 1-ray diffraction to separate two isomers of compound 9-k- Major isomers and minor isomers with nitrogen cis-qualitative. Complex 9-d (袅 9. Dichloro-bridged dinuclear bicyclic ring prepared using the phenylpyridine compound 12-f of Example 12 Metallized Ir complex (100 mg), as ligand 1, the ligand NC-1 (which is 2,6- (CH3) 2C6H3NC) (26 mg) (purchased from Fluka line of chemicals, The mixture of Sigma-Aldrich) and DCE (1.5 ml) was stirred under reflux for 5 minutes. When cooled to room temperature, the photoluminescence solution with a strong turquoise color was treated with hexane (丄 5 ml in portions). Yellow crystals were isolated ', washed with hexane (3x3 ml), and dried in vacuo. Yield:

0.115 g (96%). 4 NMR (CD2C12, 20.0, 5: 2.2 (s, 6H, CH3), 6.35 (d, 1H, aromatic ring H), 6.65 (d, 1H, aromatic ring H), 7.1 (m, 4H, aromatic ring H), 7.3 (m, 1H, aromatic ring H), 7.5 (m, 1H, aromatic ring H), 7.9 (d, 2H, aromatic ring H), 8.1 (m, 5H, aromatic ring H), 9.4 (d, 1H, aromatic ring H), 10.0 (d, 1H, aromatic ring H). 19F NMR (CD2C12, 20 ° C), δ · -62 · 7 (s, 3F, CF3),- 62.8 (s, 3F, -60- This paper size applies to China National Standard (CNS) A4 (210 x 297 mm)

Binding

1238819 A7 B7 V. Description of the invention (58) cf3). 9-g complex (Table 9V: the digas-bridged binuclear bicyclic metallized Ir complex (120 mg) prepared using the phenylpyridine compound 2-y of Example 1 as the ligand L, A mixture of the ligand NC-1 (which is 2,6- (CH3) 2C6H3NC) (26 mg) (purchased from Fluka line of chemicals, Sigma-Aldrich), and DCE (2 ml) was stirred under reflux for 10 minutes. When cooled to room temperature, the photoluminescence solution with a strong turquoise color was treated with hexane (4 ml in portions). The yellow crystals were separated and washed with hexane (3 x 3 ml) and dried in vacuum. Rate: 0.13 g (93%). 4 NMR (CD2C12, 20.0, (5: 2.2 (s, 6H, CH3), 6.35 (d, 1H, aromatic ring H), 6.65 (d, 1H, aromatic ring) ), 7.1 (m, 5Η, aromatic ring Η), 8.0 (d, 2Η, aromatic ring Η), 8.25 (m, 4Η, aromatic ring H), 9.6 (s, 1H, aromatic ring H), 10.4 ( s, 1H, aromatic ring H). 19F NMR (CD2C12, 20t), 5 ·· -62.8 (s, 6F, CF3), -62.9 (s, 3F, CF3), -63.0 (s, 3F, CF3 ). Complex 9-K-Bom 9, the bi-gas-bridged binuclear bicyclic metallization Ir obtained using the 2-phenylpyridine compound 2-k of Example 1 A mixture of the compound (300 mg), triphenylphosphine (120 mg), and toluene (6 ml) as the ligand L was stirred under reflux for 10 minutes. When cooled to room temperature, the photoluminescence from green The solution precipitated yellow crystals. After 2 days at room temperature, hexane (8 mL) was added. After 1 day, the yellow crystals were separated, the strip was washed with hexane (3 X 3 mL), and dried in vacuum Yield: 0.41 g (97%). 4 NMR (CD2C12, 20.0, 5: 5.5 (m, 2H, aromatic ring H), 6.7 (m, 2H, aromatic ring H), 7.2-7.9 (m, -61-

This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 1238819 A7 B7 V. Description of the invention (59) 21H, aromatic ring H), 8.05 (s, 2H, aromatic ring H), 9.15 (s , 1H, aromatic ring H), 9.65 (s, 1H, aromatic ring H). 19f NMR (CD2C12, 20.0, 5: -62.9 (s, 3F, CF3), -63 · 0 (s, 3F, CF3), -107.9 (m, 1F, aromatic ring F), -108.3 (m, 1F , Aromatic ring F). 31P NMR (CD2C12, 20 ° C), 5 ... 3.2 (d, JP_F = 59 Hz). The product contains minor isomers with the following NMR parameters (about 10%) : 19f NMR (CD2CI2, 20.0, 6: _63 · 5 (s, 3F, Cf3), _63 9 (s, 3F, cf3), -107.4 (m, 1F, aromatic ring f), _108.9 (m , 1F, aromatic ring F). 31P NMR (CD2C12, 20.0, 6 ·· _ΐ〇 · 8 (d, JP_F = 6.3 Hz). Complex 9-k (Table 9) The benzene of Example 1 was used Dichloro-bridged dinuclear bicyclic metallized Ir complex (102 mg) prepared as a ligand α to bite compound 2-k, and as a ligand L, a triarylphosphine compound (Arf) 3P (where Arf = 3 The mixture of 5- (CF3) 2C6H3) (102 mg) and toluene (8 ml) was stirred at reflux for 10 minutes until all solids were dissolved. After cooling to room temperature, hexane (1 () Ml) The mixture was treated 'and maintained at about +10 ° C for 3 hours. The yellow crystalline solid was separated, washed with hexane' and dried in vacuo. The product exhibited sky blue photoluminescence. 19F NMR analysis of this product indicated about 10% unreacted digas bridged complex. The solid was heated in boiling toluene in the presence of 1 ^ (30 mg) , And then again at about +10. (: After cooling for 12 hours, the complex 9-k without any dichlorobridged complex was isolated. It was washed with hexane and dried in vacuum. Product Rate: 0.17 g (86%). 4 NMR (CD2C12, 20 C), 5: 5.4 (m, 1H, aromatic ring H), 5.9 (m, 1H, aromatic ring H), 0.75 (m, 2H, aromatic ring) H), 7.2 (m, 2H, aromatic ring H), 7.75 (m, 2H, aromatic ring -62-) The paper size is applicable to the Chinese National Standard (CNS) A4 specification (21〇x 297 mm) '1238819 A7- --- Ί V. Description of the invention (60) H), 7.9 (m, 7H, aromatic ring H), 8.05 (s, 2H, aromatic ring H), 8.15, 2H, aromatic ring H), 8.85 (s, 1H, aromatic ring H), 9.4 (s, 1H, aromatic ring H). 19F NMR (CD2C12, 20 ° C), 6: -63.2 (s, 3F, CF3), -63.9 (s, 3F, CF3), 64.0 (s, 18F, L5 CF3), -105.4 0, iF, aromatic ring F), -106.1 (m, if, aromatic ring F). 31P NMR (CD2C12 ′ 20 ° C), δ: _2 · 2 (d, JP-F = 5.9 Hz). This complex has nitrogen atom rays that are trans to each other). Some crystals of different shapes were also found in single crystals subjected to x-ray analysis. X-ray diffraction is also used to analyze one of them, which determines the ordinal arrangement of the N atoms of the minor isomers around Ir. The complex blew carbon oxide as one of L ′ through a bi-gas-bridged dinuclear bicyclic metallized Ir complex (18 mg) in DCE (8 ml) prepared from phenylpyridine compound 2-k of Example 1. In boiling solution. The heater was turned off and the solution was allowed to slowly cool to room temperature under CO foaming through the mixture. When the pale yellow crystals started to precipitate, hexane (10 ml) was slowly added in 2 ml portions. After 30 minutes at room temperature, the crystals (whiteish blue photoluminescence) were separated, washed with hexane, and dried under vacuum for 15 minutes. Yield: 0.145 g (78%). 4 NMR (CD2C12, 20.0, 5: 5.6 (m, 1H, aromatic ring H), 6.15 (m, 1H, aromatic ring H), 6.8 (m, 2H, aromatic ring H), 7.8 (m, 2H, Aromatic ring H), 8.1 (m, 2H, aromatic ring H), 8.25 (m, 2H, aromatic ring H), 9.2 (s, 1H, aromatic ring H), 10.15 (s, 1H, aromatic ring H). 19F NMH (CD2C12, 20 ° C), 5: _62 · 8 (s, 3F, CF3), · 62 · 9 (s, 3F, CF3), _106.5 (m, 1F, aromatic ring F), -106.7 ( m, 1F, aromatic ring F). -63- This paper size applies to China National Standard (CNS) A4 (210X 297 public directors) 1238819 A7 B7 ____ 5. Description of the invention (61) Use the same as the complex 9-d In the step, phenylpyridine compounds 12-a, 12-c, 12-g, 12-d, 2-k, 12-f, and 2-k are used to prepare complexes 9-a and 9-b, respectively. , 9-c, 9-e, 9-f, 9-h, and 9-i. Example 15 A thin-film OLED device was manufactured using the procedure according to Example 7. Table 14 shows the overview and thickness of the device layers. In all cases The anode system is ITO as discussed above, and the cathode system is A1 with a thickness in the range of 700-760 Angstroms. MPMP = bis [4- (N, N-diethylamine; 1 DPA = 4,7d 14 10-2-Tolyl) (4-Tolyl) methane -1,10-morpholine sample HT layer EL layer ET layer (thickness, A) (thickness, A) (thickness, A) 15-1 MPMP compound 9-a DPA (516) (408) (413) 15- 2 MPMP compound 9-c DPA (518) (404) (402) 15-3 MPMP compound 9-d DPA (508) (354) (421) 15-4 MPMP compound 9-e DPA (504) (403) ( 410) 15-5 MPMP compound 9-f DPA 102924-5 (501) (407) (415) -64- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 1238819 A7 B7 V. DESCRIPTION OF THE INVENTION (62) The OLED samples were characterized as in Example 7, and the results are shown in Table 15 below. Table 15 Electroluminescence properties of iridium compounds Sample peak photometric peak efficiency Approximate Cd / m2 Cd / A peak wavelength, nm 15-1 6 at 16V 0.7 450 + 500 15-2 1 at 21V 0.25 510 15-3 60 at 22V 0.8 464 + 493 15-4 25 at 23V 1.2 460 + 512 15-5 320 at 22V 2.4 538 15-6 350 at 23V 1.5 484 + 509

Binding

15-6 MPMP compound 9-g DPA 102924-40 (518) (404) (405) -65- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 mm)

Claims (1)

123 881ane 090133244 Patent Application_Chinese Patent Application Replacement (June 1993g VI. Application Patent Scope 1. A compound selected from the compounds 8-a to 8-5 listed below ... La, Lb, Lc y ζ R substituents L, L ,, 8-3. IrLaLbL, yL ,, z Structure (I) 1 0 r3 = cf3 R7 = F (a) Me-8hq 8-b IrLaLbL'yL, , Z structure (I) 1 0 R3 = CF3 R7 = F (a) 8hq 8-c IrLaLbL, yLnz structure (XI) 1 0 Rl8 = CF3 (a) acac-8-d IrLaLbL, yL''z structure (XΠ ) 1 0 R29 = CF3 (a) acac-8-e IrLaLbL'yL " z structure (χπ) 1 0 R28 = CF3 (a) acac-8-f IrLaLbL, yL "z structure (χΠ) 1 0 R29 = F (a) acac-8-g IrLaLbL, yL, 'z structure (χπ) 1 0 R27 = F R29 = F (a) acac 8-h IrLaLbL'yL ”z structure (χπ) 1 0 R27 = F R29 = F R30 = F (a) acac 8-i IrLaLbL'yL ', z structure (χπ) 1 0 R28 = F R-29 = F R30 = F (a) acac 8-j IrLaLbL, yL "z structure (χπ) 1 0 R28 = F R30 = F (a) acac 8-k IrLaLbL, yL ,, z structure (χπ) 1 0 R29 = CgFi7 (a) acac-8-1 IrLaLbLc structure (χπ)--R29 = CF3 (a)--This paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) 1238819 έ β8 C8 D8 VI. Application scope of patent 8-m IrLaLbLc Structure (XΠ) R28 = F R29 = F R30 = F ( a) 8-n IrLaLbLc structure (XΠ) R27 = F R29 = F R30 = F (a) 8-0 IrLaLbLc structure (XΠ) R27 = F R29 = F (a) 8-p IrLaLbLc structure (XΠ)--R28 = CF3 (a)--8-q IrLaLbLc structure (XΠ) R28 = F R3〇 = F (a) 8-r IrLaLbL, yL ,, z structure (XΠ) 1 0 R27 = F R29 = F ⑻ acac 8- s IrLaLbL'yL ,, z structure (χΠ) 1 0 R29 = OCF3 (a) acac-where: Structure (I) represents Among them, A series C: Structure (XI) representative -2-This paper size is applicable to Chinese National Standard (CNS) A4 specification (210 X 297 mm) 1238819 A8 B8 C8 D8 6. Scope of patent application (X0 (a) represents the remaining R substituents are hydrogen; 8hq represents 8-Cycloline; Me-8hq represents 2-methyl-8-hydroxyquinoline; and acac represents 2,4-pentanedione. 2. An organic electronic device comprising at least one active layer between two electrical contact layers, wherein the at least one active layer includes a compound selected from the group consisting of the first item of the patent application. 3. The device according to item 2 of the scope of patent application, wherein the active layer is a light emitting layer. 4. The device according to item 2 of the scope of patent application, wherein the active layer is a charge transport layer. 5. An organic electronic device comprising an emission layer having an emission maximum in a range of 570 to 700 nm, wherein at least 20% by weight of the emission layer includes at least one compound having the following second chemical formula: IrLaLbL'yL " z (Second Chemical Formula) -3- This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) A8 B8 C8 D8 1238819 6. Scope of patent application Among them: y is 1; z is 0; L 'is double Pellet ligand, and not phenylpyridine, phenylpyrimidine, or phenyl p-quinine; L " is a single-group ligand, and not phenylpyridine, phenylpyrimidine, or phenyl p-quinine La & Lb is similar or different from each other, and each La & Lb has a structure selected from the following structure (XI) and structure (XΠ): At least one of R10 to R19 is selected from the group consisting of F, 〇CnF2n + 1, and OCF2X, where n is an integer from X, and X is Η, Cl, or Br; At least one of R21 to R30 is selected from the group consisting of ρ, c ρ2 〇CnF2n + 1, and OCFJ, where n is the integer since -4- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ) 8 8 8 8 ABCD 1238819 Number of patent applications, and X is Η, Cl, or Br. 6. An organic electronic device comprising an emission layer having an emission maximum in a range of 57 to 700 nanometers, wherein at least 20 weight percent of the emission layer includes at least a compound having a third chemical formula: (Third Chemical Formula) IrLaLbLc wherein: ab, L, and L are similar or different from each other, and each, Lb, and L have a structure selected from the following structures: wherein Han 17, Rl6 Ri04 (χτ) at least one of R10 to Ri9 is selected from F, CnF2n + i, 0CnF2n + 1, and 0CF2X 'where n is an integer from and X is Η, Cl, or Br; (ΧΠ) Among them: At least one of 2n + 1 R21 to R3〇 is selected from F, c F -5-This paper size is applicable to China National Standard (CNS) A4 specification (210x 297 mm) 1238819 172 88 C8 D8 VI. Application The patent scope is 0CnF2n + 1, and OCF2X, where η is an integer from 1 to 6, and X is Η, C1, or Br. 7. A compound having a sixth chemical formula, which is selected from the following compounds 9-a to 9-1: IrLaLbLfLM (sixth chemical formula) compounds La and Lb L, L "Ri r2 R3 R4 r5 r6 Rt r8 9- a Structure (I) NC-1 chloride Η ch3 Η HFHFH 9-b Structure ① NC-1 chloride Η ch3 HFHFH 9-c Structure (I) NC-1 chloride Η Η HFHFH 9-d Structure (I ) NC-1 chloride Η Η Η HH cf3 HH 9-e structure (I) NC-1 chloride Η ch3 Η HH cf3 HH 9-f structure (I) NC-1 chloride Η Η cf3 HHHFH 9-g structure (I) NC-1 chloride Η cf cf3 HH cf3 HH 9-h structure (I) NC-2 chloride Η Η Η HH cf3 HH 9-i structure (I) NC-3 chloride Η Η cf3 HHHFH 9- j Structure (I) PPh3 chloride Η cf3 HHHFH 9-k Structure (I) PtmPh3 chloride Η Η cf3 HHHFH 9-1 Structure (I) CO chloride Η Η cf3 HHHFH where: Structure (I) represents This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) 1238819 Patent application park, where A is C; NC-1 is 2,6- (CH3) 2C6H3NC, · NC-2 is 3- CF3C6H4NC; NC-3 is 4-CH3C6H4S02CH2NC; PPh3 is P (C6H5) 3; and 8. PtmPh3 is (Arf) 3p, of which Arf H (CF3) 2C6H3. -An organic electronic device comprising an emission layer having an emission maximum in a range of 45 (5) to 5 μm, wherein at least 20 weight percent of the emission layer includes at least one compound having the sixth chemical formula: IrLaLbL, L, (sixth chemical formula) wherein: LW is selected from the group consisting of phosphine, isonitrile, and carbon monoxide; L "is selected from the group consisting of F, cn, Br, and I; 1 / and 1 ^ have the following structures, 0) R4 where 1 To 1 series are selected from the group consisting of alkyl, alkoxy, halogen, nitro, cyano, fluoro, fluorinated alkyl and fluorinated alkoxy, respectively. ^ This paper size applies to Chinese National Standards (CNS) A4 specifications (210X297 mm) 1238819 A8 B8 C8 D8 At least one of the patent application scopes is selected from F, CnF2n + i, OCnF2n + i, and OCF2X, where n is an integer from 1 to 6, and X is Η, Cl, or Br, and A are C. 9. The device according to item 8 of the scope of the patent application, wherein L "is C1, and L is selected from triphenylphosphine, ginseng [3,5-bis (trifluoromethyl) ) Phenyl] phosphine, isocyanate 2,6-xylene, isocyanate 3-trifluorotoluene, and isocyanate 4-toluenesulfonylmethane. 10. The device according to item 8 of the scope of patent application, wherein the compound is selected from the compounds according to item 7 of the scope of patent application. H. A compound of structure (II), which is selected from the following compounds to 12j: Compound A Ri r2 Rs R4 Rs Λβ__ r7 R〇Rn 12-a CH ch3 HHHHF '" 〇 HH 12-b CH ch3 HHHH cf3 XI H 12-cc HH ch3 HFHFHH 12-dc H ch3 HHHHHH 12-ec HH ch3 HHHH cf3 Hi H _J2-f c HHHHHHHHXXH c HHHHFHFHXXH This paper size is applicable to national national standards (CNS) M specifications (other 297 public love) 1238819 A8 B8 C8 D8 VI. Application scope 12-h CH t-Bu HHHHFHH 12 -i CH t-Bu HHH cf3 H cf3 H 12-jc H ch3 HHHH cf3 HH -9-This paper size applies to China National Standard (CNS) A4 (210X 297 mm)