TW201127933A - Phosphorescent transition metal complex having a facially arranged carbon-phosphorus-carbon (C-P-C) tridentate chelate and organic light emitting diode containing the same - Google Patents

Abstract

The present invention provides a series of phosphorescent transition metal complexes having a facially arranged, carbon-phosphorus-carbon (C-P-C) tridentate chelate, alone with one monoanionic bidentate chromophoric chelate (either C-N or A-N) and one arbitrary charge neutral chelate (L), or with one charge neutral bidentate chromophoric chelate (N-N) and one arbitrary anionic ligand (X); all of them can be used to generate high efficiency photo-induced phosphorescence at room temperature, as well as bright electroluminescence upon employment of these materials in the fabrication of organic light-emitting devices.

Description

201127933 VI. Description of the Invention: [Technical Field] The present invention relates to a transition metal-based high-efficiency luminescent material, and more particularly to a phosphorescent flaw with a surface-structured carbon-phosphorus-carbon (CAPAC) chelating body. Compound, its synthesis method and its phosphorescent organic light-emitting diode. [Prior Art] Phosphorescent organic light-emitting diodes (OLEDS) are intensively researched because of their potential to achieve improved device brightness and performance. The electroluminescence of the 'heavy transition metal complex of the fluorescein (4) eetn) phQsphQrescent) is easily generated by the single and triplet excited states, and thus, the internal quantum efficiency will reach the theoretical energy level of homogeneity, rather than The 25% inherent upper limit given by the single excitation of the fluorescent counterpart. Therefore, great efforts have been made for the second and third columns of transition metal complexes to develop very effective phosphors that emit all three primary colors. US-〇1(10)8 A1 discloses a phosphorescent roll-meal transition metal complex comprising i) two identical non-conjugated ring metallated ligands (cydomeUUted coordination + s) combined with a transition metal to form the error The coordination layer of the complex' and the chelating luminescent group (or luminescent chelating body) is bonded to the (iv) coordination layer; or the Π)-non-co-light ring metallized ligand is combined with a transition metal form. The coordination layer of the substance 'and the two integrated luminophores are bound to the coordination layer" in which the metal is 铱, Ming, 锇 or ordered. The chelated luminophore has a lower energy gap than the energy gap of the non-conjugated ring metal compound ligand. Inhibition of the ligand carrier coordination charge transfer process 201127933 can provide effective resistance Barriers, w, ▲ ^ 浑 So the thought of the transitional complex of the excited state will be limited to the whole person, / crab mouth first group. The structure and energy gap of the coupled luminophore are suitable for generating high; ^. Xuan. # Between the living room efficiency blue light 'green light or even red light radiation. However, it has not been proposed to disclose a carbon-phosphorus-carbon (c PC) cleavage body, or a cyclo-type bisphosphonite phosphinite cheiate. , a transition metal complex. SUMMARY OF THE INVENTION A primary object of the present invention is to provide a phosphorescent transition metal complex as an electrophosphorescent material in a light-emitting layer of an organic electroluminescence device. This complex can also act as a catalyst. Another object of the present invention is to provide a transition metal complex as an electrophosphorescent material in an emissive layer of an electroluminescent device capable of emitting blue light. The phosphorescent transition metal complex according to the present invention has carbon-phosphorus- A transition metal complex of a carbon (C^PAC) tridentate chelate, that is, a transition metal complex of a bimorphized bicyclic metalized chelate chelating chelate. The structures summarized by them are represented by the following structural diagrams la, Ib, Ic or their stereoisomers, which comprise a one-sided configuration of carbon-phosphorus-carbon ((: 卟 〇 〇 牙 牙 ,, and a pair a carbon-nitrogen (CAN) or azole-nitrogen (ΑΛΝ) anionic luminophore chelate, either in the same neutral neutral donor ligand (L) as shown in la or lb; or a one-sided carbon-scale - Carbon (CapaC) tridentate chelate and a neutral diimine nitrogen-nitrogen (ΝΛΝ) luminophore chelate, with the same arbitrary anion donor ligand, as shown in Ic, 201127933:

Ic where Μ is the transition metal and is 铱, 锇 or 钌; carbon atoms (C) and nitrogen atoms (Ν) linked by a bow (CAN), bowed $

LO' J 5 201127933 (ΑΛΝ) The nitrogen atom (A) of the linked azole has a general expression with a nitrogen atom (N) or a neutral diimine having a dinitrogen atom (ΝΛΝ). Ar _Ar2, where Ari is The aryl 'substituted aryl or polyaromatic moiety' in the ON chelate of la is in the alpha lambda chelate of lb. Pyrolpyiide, functionalized pyrrolyl, pyrazolyl, functionalized pyrazolyl, triazolyl, functionalized oxazolyl or tetrazolyl; or at 1 (; a heterocyclic nitrogen donor group in the diimine ΝλΝ chelate, and Ar2 in each of the ruthenium, osmium and νλν chelates of the formulae Ia, Ib and Ic is a neutral heteroaromatic nitrogen-containing donor group;

The carbon atom (c) and the phosphorus atom (p) and the carbon atom (C) linked by a double arc (CAP%) have the formula PR4(OAr5)2, wherein R4 is an alkyl group, an aryl group, a substituted aryl group, An aryloxy group or a substituted aryloxy group; and A〆 is an inclusion of rS

(ortho-cyclometalated carbon atom) 较佳 preferably

Preferably, M is deuterium and Ar5 is phenyl or substituted phenyl. Preferably, the complex of the present invention is represented by the formula la or Π), wherein

Independently represented by leukoxyl, methoxy, aryl, lan or lb, wherein r2r3, and R1, R2 and substituted aryl, aryloxy 201127933 or substituted aryloxy; or any nitrogen Donor pyridine. Preferably, the complex of the present invention is represented by the formula Ic, wherein X in the formula Ic is selected from the group consisting of acetate, a amide, a cyanide, a cyanate, a thiocyanate and a quasi-compound. a group of inorganic anions; or selected from the group consisting of aryl, alkoxy, phenoxide, substituted phenoxide, azolyl' thiolate, substituted oxazolyl, acetylide, and substituted acetylide Group of organic anions. Preferably, R4 is methoxy, phenyloxy or phenyl. More preferably, R4 is a phenoxy group. Preferably, the carbon-nitrogen (CAN) chelate is

Wherein BV is a third butyl group. Preferably, the azole-nitrogen (ΑΛΝ) chelate is 201127933

Phenyl or by wherein R is hydrogen, CF3, decyl, tert-butyl, small alkyl, substituted phenyl, and wherein Bu1 is a third butyl group. Preferably, the diimine nitrogen nitrogen (ruthenium) chelate is

Wherein R is hydrogen, methyl, tert-butyl, small alkyl, phenyl aryl, fluoride, halide, pseudohalide, methoxy, phenyl or diphenylamine. Preferably, the diimine nitrogen-nitrogen (ruthenium) chelate is a substituted monomethylamine

Aryl. Wherein R is methyl, B*, small alkyl, phenyl or substituted. Preferably, the complex of the present invention is represented by the formula: 201127933

PhO

Wherein Ph is a phenyl group. Preferably, the complex of the present invention is represented by the following formula:

Wherein Ph is a phenyl group and Bu1 is a third butyl group. Preferably, the complex of the present invention is represented by the following formula:

Wherein Ph is a phenyl group and Bu1 is a third butyl group. Preferably, the complex of the present invention is represented by the following formula:

201127933 wherein Ph is a phenyl group and Bul A is a third butyl group. Preferably, the faulty private sigma of the present invention is represented by the following formula

PhO

Wherein Ph is a phenyl group, and But is a second butyl group. Preferably, the complex of the present invention is represented by the following formula:

Wherein Ph is a phenyl group, and χ = chloride and thionate. Preferably, the complex of the present invention is represented by the following formula:

Wherein Ph is phenyl and χ = vapor and thiocyanate. The present invention also provides an organic light emitting diode comprising: a positive electrode formed on a substrate; - negative and - a light emitting layer disposed between the positive electrode and the negative electrode, wherein the light emitting layer comprises the mismatch of the present invention Things. Selecting the twinning sites, the carbon atoms (C) and the phosphorus atoms (p) and carbon atoms (c) linked by the two arcuate forms (c^pAc) of the formulas la, lb and Ic have the formula 10 201127933 PR4(CH2Ar5)2 That is, the methyl substituted oxygen is used as a linker. [Embodiment] The present invention provides a bicyclic metallated sulphate chelating body having a carbon-phosphorus-carbon (CaPa〇 dentate chelating body, that is, having the above structures la, lb, Ic or a stereoisomer thereof) Transition metal complex. The chelating ligand coordinated to the _ heart metal atom includes a carbon-fill-carbon (CAp^c) tridentate chelate, a carbon-nitrogen (CAN) or an azole-nitrogen (ΑΛΝ) a monoanionic bidentate ligand, and an arbitrary charge-neutral donor group (L), while the second arrangement comprises a carbon-phosphorus-carbon (CAPAC) tridentate chelate, a neutral diam Amine type (ΝΛΝ) luminophore chelators and an arbitrary anion donor complex (the definition of X luminophore chelator follows the traditional concept, in other words: part of the metal-chelate fragment, which is responsible for its visible color and / Or separate luminescence. Furthermore, when there is a metal complex with at least one hair color chelating body, you #, :/§忐φ a ω Μ .,丄& _

Two. The first type of surface segments, such as pyridine, isoquinoline, and quinone functionalized aromatic moieties, can be reacted with a reagent to provide the so-called ring gold ~ 201127933 genus chelate. The second type is referred to hereinafter as the (ΑΛΝ) chelating neutral Ν-donor segment plus the second segment of the Ν-Η functional group having an azole from a chelating agent similar to the (C^N)H chelating agent. CH activation is carried out by reacting with a metal ion to form an anion (A/sN) chelate. An example of a ligand of the luminophore located in the entire genus: (0ΛΝ> chelate] which has the latter Way 'below column

(ΑΛΝ) chelating body

Ν=μ

NT Ν The preferred silver (ΠΙ) complex of the invention is synthesized: according to the procedure of Process 1 of 3 12 201127933

lrCI3(THT)3 + L + NaOAc + (CAPAC) L = phosphine with formula PR1R2R3 (CAPAC) = phosphinate with formula PR4(〇Ar)2 1. R1=R2=R3=phenoxy or A Oxygen-designated Example 2. R1=R2=R3=Alkyl, aryl 1. R4=Ph, OPh, OMe 3. R1=R2=Alkyl, while R3=Aryl 2.Ar=Benzene with R5 substituent Base 4. R1 = alkyl, while R2 = R3 = aryl 3. R5 = H, alkyl, halide, cyano 5. 4-ethyl-1-phosphorus-2,6,7-trioxane [2.2.2] Octane designation Example 1. Rl=R2=R3=OPh 2. Rl=R2=R3=OMe 3. Rl=R2=R3=Ph 4. Rl=R2=Ph > R3=Me 5. Rl=Ph - R2=R3=Me Scheme 1 In Scheme 1, the silver reagent IrCl3(THT)3, THT=1 tetrahydroquinone' is improved in solubility due to its high boiling hydrocarbon solvent such as decalin. Selected. Thus, one equivalent of (CAPAC) (i.e., a three-dentate phosphinate having the formula PR4(OAr)2) and another equivalent of L (i.e., a phosphine or phosphinate having a formula PR1R2R3) Treatment of IrCl3(THT)3 in the presence of excess sodium acetate will result in a high yield of intermediate [11' (1〇((:/^/^(:))). An equivalent amount of ((^:^)11 chelating or (ΑΛΝ)Η chelate treatment [Ir(L)(CAPAC)(OAc)] yields the expected distribution of i «di-i 13 201127933 position exchange and medium yield [Ir(L)(CAPAC)(CAN)] [Ir(L)(CAPAC)(AAN)] is formed. Alternatively, this reaction can skip the separation of the product [Ir(L)(CApAC)(OAc)] in the reaction. And simplified; therefore, the single-pot procedure can be achieved by further reducing its production cost. Another preferred ruthenium (III) complex of the present invention can be synthesized according to the method shown in Scheme 2:

lrCI3(THT)3 + ΝΛΝ + NaOAc + (CAPAC) (CAPAC)=phosphinate X with formula PR4(OAr)2 = anion ligand designation example designation example 1. R4 = Ph ' OPh, OMe 1· X = SCN, OPh, OMe, CCPh 2. Ar = with R5 substituent phenyl 2. azole 3. R5 = H, alkyl, fluoride, cyano 2 In Scheme 2, the hydrazine reagent IrCl3 (THT 3) was again selected for its improved solubility in high boiling hydrocarbon solvents such as decylene. Thus, one equivalent of the (CAPAC) phosphinate of the formula PR4(OAr)2 and one equivalent of the electrically neutral diimine oxime chelate in the presence of excess sodium acetate. Jrb Heli 14 201127933

IrCldTHT) 3 and the mixture was heated at 180 ° C for 8 hours. After cooling to room temperature, the solvent was removed and the residue was purified by silica gel column chromatography. The product in the form of [(N^N)Ir(C^PAC)Cl] can be obtained in a moderate yield. Further, [(NAN)Ir(C^PAC)Cl] and 10 equivalents of X- (i.e., inorganic or organic anion) were added to DMF (15 mL) and the mixture was refluxed for 32 hours. After cooling to room temperature, the solvent was removed and the residue was purified by silica gel column chromatography. A product of [(ΝλΝ)Ιγ((:λ;Ρλ〇Χ] can be obtained in a medium yield. The synthesis and spectral data of the phosphorescent Ir complex according to the present invention will be described in detail later, and this type of error will be described in detail. The composition is a photoluminescent material of an organic light-emitting diode (OLED).Example: General experimental procedure. All reactions are carried out under a nitrogen atmosphere using an anhydrous solvent or a solvent treated with a suitable desiccant. Obtained by the je〇l SX-102A instrument operating in electron impact (EI) mode or fast atomic bombardment (FAB) mode. The 丨η and NMR spectra were recorded on a Varian Mercury-400 or INOVA-500 instrument. Ray diffraction studies. Single crystal X-ray diffraction data is utilized

(Μο-Κα) Radiation (λ = 0.71073 A) was measured with a Bruker SMART Apex CCD diffractometer. Receipt collection is performed using the SMART program. Cell refinement and receipt conversion are performed using the SAINT program. These structures are measured using the SHELXTL/PC program and refined using the full matrix ς ^ ί > i 15 201127933 array least squares method. Spectral and dynamic measurements. Steady state absorption and emission spectroscopy

Hitachi (U-3310) spectrometer and Edinburgh (FS920) fluorometer are recorded. The quantum yield of radiation was measured at room temperature in CH2C12 at excitation wavelength = 350 nm. In this method, quinine sulfate having a radiation yield of φ 0.54 ± 0.2 in a 1 〇 N sulfuric acid solution was used as a standard for calculating the radio quantum yield. Lifetime studies were performed using the hydrogen fluoride or nitrogen lamp as the excitation source by the Edinburgh FL 900 photon counting system. The data was analyzed using a nonlinear least squares program combined with an iterative convolution method. Radiation decay is analyzed by the sum of the exponential functions, which allows the instrument to be partially widened and thus provides an instantaneous resolution of ~200 ps. Example 1

[Ir(tpp)(tpit)(OAc)] (1) Synthesis: IrCl3(THT)3 (11〇mg '0.20 mmol), triphenyl phosphinate (tpit, 62 mg, 0.20 mmol), II Phenylphosphine (tpp, 53 mg, 0.20 mmol) and sodium acetate (82 mg, 1.00 mm 〇1) were added to decahydronaphthalene (15 mL). At 190. (: heating the mixture for a few hours. After cooling to room temperature and removing the solvent, a 1:1 mixture of ethyl acetate and hexane is used as an eluent by cartridge column chromatography. 16 201127933 Residue Purification. Light yellow crystals of [Ir(tpp)(tpit)(OAc)] (131 mg, 0.16 mmol, 80%) were obtained by slowly diffusing hexane to a saturated ch2ci2 solution at room temperature [Ir] Spectral data of (tpp)(tpit)(OAc)]: MS (FAB, 193Ir): m/z 763 (M-OAc)+; towel NMR (500 MHz, CDC13, 294K): d 7.40 to 7.37 (m, 1H), 7.36 to 7.33 (m, 3H), 7.30 to 7.16 (m, 15H), 7.07 (d, ·/= 8.0 Hz, 1H), 6.95 to 6.89 (m, 5H), 6.58 (td, J= 7.5 , 1.0 Hz, 1H), 5.52 (d, /= 8.0 Hz, 1H), 6.43 (td, 7.0, 1.0 Hz, 1H), 1.45 (s, 3H). NMR (202 MHz, CDC13, 294K) : d 111.66 (¢1, /=9.7 Hz, 1P), 12.37 (4 9.7 Hz, IP). Example 2

Synthesis of [Ir(tpp)(tpit)(pptz)] (2): IrCl3(THT)3 (110 mg, 0.20 mmol), triphenyl phosphinate (62 mg, 0.20 mmol), triphenylphosphine (53 mg, 0.20 mmol) and sodium acetate (82 mg, 1·mmol) were added to decahydronaphthalene (15 mL) and the mixture was heated at 190 °C for 6 hours. After cooling to room temperature, 3-phenyl-5-pyridyl-i,2,4-triazole (pptzH) (48 mg, 0.22 mmol) was added and taken to 190. (The mixture was heated for 12 hours. Finally, the solvent was removed and the residue was purified by gel column chromatography using ethyl acetate and a hexane mixture of 3:1 as an eluent. The alkane was slowly diffused to a solution of CH2C12 at room temperature to obtain colorless crystals (97 mg, 0.11 mmo, 48%) of iyvi 17 201127933 [Ir(tpp)(tpit)(pptz)] [Ir(tpp)(tpit) Spectral data for (pptz)]: MS (FAB, 193Ir): m/z 985 (M+l)+ ; ]H NMR (500 MHz, CDC13, 294K): d 9.02 (d, 7 = 6.0 Hz, 1H) , 8.41 (d, /= 6.5 Hz, 1H), 7.86 (br, 1H), 7.54 to 7.49 (m, 3H), 7.43 to 7.37 (m, 3H), 7.28 (t, = 7.5 Hz, 1H), 7.19 ~7.17 (m,3H), 7.10 to 7.01 (m, 16H), 6.87, 6.83 (m, 2H), 6.76 to 6.71 (m,3H), 6.62 (t, 7.5 Hz, 1H), 6.34 (t, J = 7.5 Hz, 2H), 6.01 (t, J = 6.0 Hz, 2H). 31?-{^} NMR (202 MHz, CDC13, 294K): d 123.38 (br, IP), -11.15 (d, J= 12.9 Hz, IP). Example 3

Synthesis of [Ir(tpp)(tpit)(bptz)] (3): IrCl3(THT)3 (110 mg '0.20 mmol), triphenyl phosphinate (62 mg, 0.20 mmol), triphenyl scale (53 mg, 0.20 mmol) and sodium acetate (164 mg, 2.00 mmo.l) - and added to decahydronaphthalene (15 mL) at 190. (: The mixture was heated for 6 hours. After cooling to room temperature, 3-tert-butyl-5-(2-pyridyl)-1,2,4-tris-sodium (bptzH) (45 mg, 0.22 mmol) was added. The mixture was heated for 5 hours at 190 ° C. Finally, the solvent was removed and the residue was purified by hard-column column chromatography using a 3:1 mixture of ethyl acetate and hexanes as eluent. A colorless crystal of [Ir(tpp)(tpit)(bptz)] (97 mg, 〇.1〇18 201127933 mmol, 51%) was obtained by slowly diffusing hexane to a CH2C12 solution at room temperature. [Ir( Spectral data of tpp)(tpit)(bptz)]: MS (FAB, 193Ir): m/z 965 (M+l)+ ; !H NMR (500 MHz, CDC13, 294K): d 9.12 (d, /= 7.0 Hz, 1H), 8.25 (d, ·/= 5.5 Hz, 1H), 7.79 (d, /= 7.0 Hz, 1H), 7.43 ~ 7.37 (m, 3H), 7.27 (t, ·/= 7.5 Hz, 1H), 7.21 to 7.18 (m, 3H), 7.13 to 7.08 (m, 13H), 7.03 (d, J = 9.0 Hz, 2H), 6.83 to 6.78 (m, 2H), 6.71 to 6.66 (m, 2H) , 6.61 (t,= 7.0 Hz, 1H), 6.36 (t,/= 7.0 Hz, 1H), 5.76 (t, 7=6.5 Hz, 1H), 1.62 (s, 9H). ^Ρ-Ι'Η} NMR (202 MHz, CDC13, 294K): d 124.17 (d, J = 12.5 Hz, IP), -11.79 (d, "/= 12.5 Hz, IP). Example 4

Synthesis of [Ir(tpit)2(bptz)](4): irci3(THT)3(ll〇mg, 0.20 mmol), triphenyl phosphinate (tppH, 186 mg, 0.60 mmol) and sodium acetate ( 164 mg '2.000 mmol) - and added to degassed decalin (15 mL) and the mixture was heated at 190 °C for 6 hours. After cooling to room temperature, 3-t-butyl-5-(2-pyridyl)-, 2,4-triazole (bptzH) (45 mg, 0.22 mmol) was added, (: The mixture is heated for η hours. After cooling to room temperature and removing the solvent, the residue is pure by using a mixture of acetic acid and a mixture of hexane and hexane as a eluent.

Chemical. Light yellow crystals (101 mg, 0·10 mmol, 50%) of L \ 201127933 [Ir(tpit) 2 (bptz)] were obtained by slowly diffusing hexane to a solution at room temperature. Spectral data of [Ir(tpit) 2 (bptz)]: MS (FAB, i93Ir): m/zl013 (M+l) +; ]H NMR (500 MHz, CDC13, 294K): d 9.10 (d, J= 5.5 Hz, 1H), 8.24 (d, J = 5.5 Hz, 1H), 8.12 (br, lH), 7.56 to 7.51 (m, 3H), 7.48 (t, 8.0 Hz, 2H), 7.33 (t,·/ = 7.5 Hz, 1H), 7.03 to 6.96 (m, 9H), 6.91 to 6.86 (m, 2H), 6.82 to 6.80 (m, 1H), 6.73 (dd, J = 8.0, 4.0 Hz, 1H), 7.06 ( t, 7= 7.5 Hz, 1H), 6.57 (t,··= 6.0 Hz, 1H), 6.44 to 6.34 (m,7H), 5.73 (t, ·/= 8.0 Hz, 1H), 1.59 (s, 9H) 31Ρ—{!Η} NMR (202 MHz, CDC13, 294K): d 125.02 (br,1P), 76.13 (4, J= 23.4 Hz, IP) 〇Example 5

[Ir(mdpp)(tpit)(bptz)](5) Synthesis: IrCl3(THT)3 (110 mg '0,20 mmol), triphenyl phosphinate (62 mg, 0.20 mmol), sulfhydryl Diphenylphosphine (mdpp, 40 mg, 0.20 mmol) and sodium acetate (164 mg, 2.00 mmol) were added to decahydronaphthalene (15 mL) at 19 〇. The mixture was heated under c for 6 hours. After cooling to room temperature, 3_t-butyl_5_(2-11-pyridyl)-1,2,4-triazole (bptzH) (45 mg, 0.22 mmol) was added and heated at 190 °C. The mixture was allowed to stand for 12 hours. After cooling to room temperature and removing the solvent, the residue was purified by a ruthenium column chromatography using a 1:3 mixture of ethyl acetate and hexane as the eluent "by slowly diffusing hexane to 201127933 A light yellow crystal of [Ir(mdpp)(tpit)(bptz)] (98 mg, 0.11 mmol '54%) was obtained from CH2C12 solution at room temperature. Spectral data of [Ir(mdpp)(tpit)(bptz)]: MS (FAB, 193Ir): m/z 903 (M+l)+ ; !H NMR (500 MHz, CDC13, 294K) : d 9.14 (t , 7.0 Hz, 1H), 8.23 (d, 5.5 Hz, 1H), 7.83 (d, 7.5 Hz, 1H), 7.48 to 7.43 (m, 3H), 7.34 to 7.30 (m, 3H), 7.21 (td, /= 6.5, 1.0 Hz, 1H), 7.17 to 7.05 (m, 7H), 6.97 (t, 9.0 Hz, 2H), 6.89 (t, /= 7.5 Hz, 1H), 6.84 (t, /= 7.5 Hz, 1H), 6.73 (d,··= 8·5 Hz, 2H), 6.65 to 6.62 (m, 2H), 6.40 (t, ··= 7.5 Hz, 1H), 5.94 (t, J= 6·5 Hz ,1H),1.62 (s,9H),1.61 (d,/= 9.0 Hz,3H). 31P—{!H} NMR (202 MHz, CDC13, 294K): d 126.46 (d, J= 11.9 Hz, IP ), -21.67 (d, «/= 11·9Ηζ, IP). Example 6

[Ir(dmpp)(tpit)(bptz)](6) Synthesis: IrCl3(THT)3(ll〇mg, 0,20 mmol), phosphinic acid triphenyl sulfonate (62 mg, 0.20 mmol) Di-nonylphenylphosphine (dmpp, 28 mg, 0.20 mmol) and sodium acetate (164 mg, 2.00 mmol) were added to decahydronaphthalene (15 mL) and the mixture was heated at 190 °C for 6 hours. After cooling to room temperature, 3-tert-butyl-5-(2-° ratio thiol)-1,2,4-tris(bptzH) (45 mg, 0.22 mmol) was added, and at 19 0 The mixture was heated at ° C for 12 hours. After cooling to room temperature and removal of the solution, the residue was purified by silica gel column chromatography using a mixture of ethyl acetate and hexanes as a mixture. The pale yellow crystals (76 mg, 〇.〇9 mmol, 45%) of [ir(dmpp)(tpit)(bptz)] were obtained by slowly diffusing hexane to a CH2C12 solution at room temperature. Spectral data of [Ir(dmpp)(tpit)(bptz)]: MS (FAB, 193Ir): m/z 841 (M+l)+ ; *Η NMR (500 MHz, CDC13, 294K) : d 9.05 (t , /= 6.0 Hz, 1H), 8.23 (d, "/= 5.5 Hz, 1H), 7.94 (d, 8.5 Hz, 1H), 7.53 to 7.46 (m, 5H), 7.36 to 7.32 (m, 1H) ), 7.10 (td, /= 7.5, 1.0 Hz, 1H), 7.02 (td, ·/= 7.5, 1.0 Hz, 2H), 6.90 to 6.86 (m, 2H), 6.83 to 6.81 (m, 1H), 6.73 ~6.70 (m,3H), 6.67 ~ 6.62 (m,2H),6.42 (t,··= 7.5 Hz, 1H), 6.07 (td, J= 7.0, 1.0 Hz, 1H), 1.62 (s, 9H) , 1.40 (d,7= 9.0 Hz, 3H), 1.12 (d, /= 10.5 Hz, 3H). 31?-{^} NMR (202 MHz, CDC13, 294K): d 127.79 (d, /= 14.1 Hz , IP), -29.10 (d, 14.1 Hz, IP). Example 7

Synthesis of [Ir(tpit)2(fptz)] (7): IrCl3(THT)3 (110 mg, 0.20 mmol), triphenyl phosphinate (tppH, 136 mg, 0.44 mm〇i) and acetic acid Nano (164 mg '2.000 mmol) - and added to degassed decalin (i5 mL) and the mixture was heated at 190 °C for 6 hours. After cooling to room temperature, 3-trifluoromethyl-5-(2-pyridyl)-1,2,4-triazole (fptzH) (47 22 201127933 mg '0.22 mmol) was added and heated at i90oC. The mixture was 12 hours. After cooling to room temperature and removing the solvent, the residue was purified by silica gel column chromatography using a 3:1 mixture of ethyl acetate and hexane as an eluent. Light yellow crystals of [Ir(tpit) 2 (fptz)] (92 mg '〇·〇 9 mmol, 45 °/〇) were obtained by slowly diffusing hexane to a CH2C12 solution at room temperature. Spectral data of [Ir(tpit) 2 (bptz)]: MS (FAB, 193Ir): w/z 1025 (M+l)+; *H NMR (500 MHz, CDC13, 294K): d 8.83 (d, J = 7.0 Hz, 1H), 8.46 (d, J = 5.5 Hz, 1H), 8.04 (d, 8.0 Hz, 1H), 7.64 (t, /= 7.0 Hz, 1H), 7.55 (d, J = 9.0 Hz, 2H), 7.49 (t, "/= 8.0 Hz, 2H), 7.35 (t, /= 7.0 Hz, 1H), 7.04 to 6.97 (m, 9H), 6.94 to 6.89 (m, 2H), 6·82 ~ 6.80 (m, 2H), 6.75 (dd, /= 7.5, 4.0 Hz, 1H), 6.69 (t, 7.0 Hz, 1H), 6.46 (t, 7= 8.0 Hz, 6H), 6.42 (t, J= 8.0

Hz, 1H), 5.72 (t, / = 8.0 Hz, 1H). 19F-{lH} NMR (470 MHz, CDC13, 294K): d -63.71(s,3F). 31P-(3⁄4 NMR (202 MHz, CDC13, 294K): d 122.66 (d, 25.8 Hz, 1P), 75.45 (d, 25.8 Hz, IP).

Synthesis of [Ir(bpy)(tpit)Cl](8): IrCl3(THT)3 (ll〇mg, 0.20 mmol), triphenyl phosphinate (tpit '62 mg, 0.20 mmol), 2, 2 '-Bipyridine (bpy, 3 1 mg' 0.20 mmol) and sodium acetate (82 mg, 1.0 mmol) were added to decalin (15 mL) and the mixture was heated at 18 ° C. 8 hours. After cooling to room temperature, the solvent was removed and the residue was purified using a mixture of CH2C12 and ethyl acetate (3:1) as the eluent by silica gel i w t ό 1 23 201127933 column chromatography. Green crystals (88 mg, 0.13 mmol, 64%) of [Ir(bpy)(tpit)Cl] were obtained by slowly diffusing hexane to a CH2C12 solution at room temperature. Spectral data of [Ir(bpy)(tpit)Cl]: MS (FAB, 193Ir): m/z 657 (M-Cl)+; !H NMR (500 MHz, CDC13, 294K): d 8.18 (d, 7 = 7.0 Hz, 2H), 8.00 (d, / = 5.0 Hz, 2H), 7.86 to 7.80 (m, 4H), 7.24 (t, "/= 6.0 Hz, 2H), 6.98 to 6.96 (m, 4H), 6.90 to 6.87 (m, 2H), 6.78 (t, 7.5 Hz, 1H), 6.61 (t, ·/= 8.0 Hz, 1H), 6.51 (d, J = 8.0 Hz, 1H). 31?-{^} NMR (202 MHz, CDC13, 294K): d 118.95 (s, IP) 〇Example 9

〇·20 mmol), triphenyl phosphinate (tpit, 62 mg, 0.20 mmol), 2,2, · bismuth (bpy, 52 mg, 0.20 mmol) and sodium acetate (82 mg, 1.00 mmo 〇 And adding decalin (15 mL), and heating the mixture at 180 ° C for 8 hours, etc. After cooling to room temperature, the solvent was removed, and CH2C12 and acetic acid B were utilized by Shixi rubber column chromatography. The residue was purified as an eluent 3:1 mixture. The green crystals of [Ir(bq)(tpit)C1] were obtained by slowly diffusing hexane to a CH2C12 solution at room temperature (μ mg, 〇 〇8 [^(bqKtpiGCl] (9) Synthesis: IrCl3(THT)3 (110 mg, 24 201127933 mmol, 42%). Spectral data of [Ir(bq)(tpit)Cl]: MS (FAB, 193Ir ) : m/z 664 (M-C1)+ ; !H NMR (500 MHz, CDC13, 294K) : d 8.49 (d, J= 9.5 Hz, 2H), 8.25 (d, J = 5.0 Hz, 1H), 8.23 (d, y = 9.5 Hz, 3H), 7.97 (d, J = 8.5 Hz, 2H), 7.70 (d, / = 8.0 Hz, 2H), 7.46 (t, J = 7.5 Hz, 2H), 7.27 ( t, /= 8.0 Hz, 2H), 6.84 to 6.83 (m, 4H), 6.76 to 6.74 (m, 2H), 6.71 (t, /= 7·5 Hz, 1H), 6.32 (t, */= 8.0 Hz, 2H), 6.51 (d, /=8.0 Hz, 2H 31?-{^} NMR (202 MHz, CDC13, 294K): d 113.43 (s, IP) 实施 Example 10

Synthesis of [Ir(bpym)(tpit)Cl] (10): IrCl3(THT)3 (110 mg, 0.20 mmol), triphenyl phosphinate (tpit, 62 mg, 0.20 mmol), 2, 2' - conjugated hydrazine (bpym, 32 mg, 0.20 mmol) and sodium acetate (82 mg, 1.00 mmol) - and added to decahydronaphthalene (15 mL), and the mixture was heated at 180 ° C for 8 hours. After cooling to room temperature, the solvent was removed and a 3:1 mixture of CH2C12 and ethyl acetate was used by cartridge column chromatography. The residue was purified as an eluent. Yellow crystals (19 mg, 0.03 mmol, 16%) of [Ir(bpym)(tpit)Cl] were obtained by slowly diffusing hexane to a CH2C12 solution at room temperature.

Spectral data of [Ir(bpym)(tpit)Cl]: MS (FAB, 193Ir): m/z 566 (M-C1)+ ; *H NMR (500 MHz, CDC13, 294K): d 9.00 (dd, J = 4.5, 2.0 Hz/c S i Or 25 201127933 2H),8·15 ～8·13 (m,4H),7.35 (t,/= 5.5 Hz, 2H), 7.02 ～6.98 (m,4H), 6.91 ~6.88 (m, 2H), 6.85 to 6.81 (m, 3H), 6.52 (d, */= 8.0 Hz, 2H)· 4-(3⁄4 NMR (202 MHz, CDC13, 294K): d 119.16 (s, IP Example 11

Synthesis of [Ir(bpy)(tpit)SCN] (11): Ir(bpy)(tpit)Cl (50 mg, 0.07 mmol) and KSCN (70 mg, 0.7 mmol) - added to DMF (15 mL) And the mixture was refluxed for 32 hours. After cooling to room temperature, the solvent was removed, and the residue was purified by hexane column chromatography using a mixture of CH2C12 and ethyl acetate as an eluent. The pale yellow crystals (22 mg, 0.03 mmol, 42%) of [Ir(bpy)(tpit)SCN] were obtained by slowly diffusing hexane to CH2C12 solution at room temperature. Spectral data of [Ir(bpy)(tpit)SCN]: MS (FAB, 193Ir): m/z 715 M+ ; NMR (500 MHz, CDC13, 294K): d 7.94 (d, 5.5 Hz, 2H), 7.90 ~ 7.85 (m, 4H), 7.78 (d, 8.0 Hz, 2H), 7.29 (td, «/= 5.5, 2.5 Hz, 2H), 7.00 to 6.97 (m, 4H), 6.92 (td? /= 7.0, 2.0 Hz, 2H), 6.78 (t, /= 7.5 Hz, 1H), 6.72 (t, J= 7.5 Hz, 2H), 6.46 (d, J = 8.0 Hz, 2H). 31Ρ-{!Η} NMR (202 MHz, CDC13, 294K) : d 121.58 (s, IP) ° Example 12 26 201127933

Synthesis of [Ir(tpp)(tpit)(dfppy)](12): IrCl3(THT)3 (110 mg, 0.20 mmol), triphenyl phosphinate (tpit, 62 mg, 0.20 mmol), three stupid The phosphine (53 mg, 0.20 mmol) and sodium acetate (164 mg, 2.00 mmol) were added to decahydronaphthalene (15 mL), and the mixture was heated at 190 ° C for 6 hours. After cooling to room temperature, 4,6-difluorophenylpyridine (dfppy) (42 mg, 0.22 mmol) was added, and the mixture was heated at 190 °C for 12 hours. Finally, the solvent was removed and the residue was purified by hydrazine column chromatography using a 3:1 mixture of ethyl acetate and hexane as eluent. Colorless crystals of [Ir(tpp)(tpit)(bptz)] (23 mg, 0.02 mmol, 12%) were obtained by slowly diffusing hexane to a CH2C12 solution at room temperature. Spectral data of [Ir(tpp)(tpit)(dfppy)]: MS (FAB, 193Ir): m/z 954 (M+l)+ ; ]H NMR (500 MHz, CDC13, 294K): d 9.43 (d , J = 5.5 Hz, 1H), 7.70 (d, /= 10.5 Hz, 1H), 7.39 to 7.33 (m, 3H), 7.30 to 7.26 (m, 5H), 7.21 (d, */= 7.5 Hz, 1H ), 7.13 ~ 7.09 (m, 6H), 7.06 ~ 6.98 (m, 9H), 6, 92 (d, / = 7.5 Hz, 1H), 6.84 ~ 6.78 (m, 2H), 6.48 (t, "/= 7.5 Hz, 1H), 6.44 to 6.39 (m, 3H), 6.20 (td, J = 7.5, 1.5 Hz, 1H). NMR (376 MHz, CDC13, 294K): d -110.39 (dd, / = 14.7, 9.4 Hz, IF), -110.73(t, J = 9.4 Hz, IF) ·31Ρ—{4} NMR (202 MHz, CDC13, 294K): d 124.91 to 124.57 (m,1P), 11.72 19.0, 10.9 Hz, IP ). 27 201127933 Figures 1, 2 and 3 show the single crystal ray diffraction structures of the complexes 丨, 7 and 8, respectively. The photophysical properties of the compounds (2) to (9) are listed in Table 1. The absorption and normalized emission spectra of the complexes 2 to 7 and 8 to 9 recorded in the degassing solution at room temperature are shown in Figs. 4 and 5. Table 1 Alignment of complex Xmax (nm) QE t〇bs kr(1/s) knr (1/S) 2 462 , 486 , 509 0.22 5.5 μβ 4.00 xl〇4 1.40 X l〇5 3 450 , 475 , 492 0.07 2.5 μβ 2.80 xl〇4 3.72 x 105 4 447 , 472 , 492 0.87 44.5 μβ 1.95 x 104 3.00 xl〇3 5 450 , 473 , 498 0.34 11.1 μβ 3.06 xl〇4 5.95 x 104 6 One 45 473 , 498 0.45 14.3 μβ 3.15 xl〇4 3.85 x 104 7 416 , 442 , 458 0.012 243 ns 4.89 x 104 4.09 x 106 8 574 0.48 839 ns 5.77 x 105 6.15 x 105 9 646 0.11 325 ns 3.39 xl〇5 2.74 x 106 Example 13 : General Manufacturing Method of OLEDs According to the disclosure of the specification, the compound synthesized by the temperature gradient is increased by 28 201127933

The south China vacuum was applied for purification prior to subsequent device studies. OLEDs were fabricated on an IT〇_coated glass substrate with multiple organic layers sandwiched between a transparent bottom indium tin oxide (ITO) anode and a top metal cathode. The material layer was deposited by vacuum evaporation in a vacuum with a base pressure of <1〇6 Torr. The deposition system allows the entire unit structure to be fabricated in a single vacuum pumping without damaging the vacuum. The deposition rate of the organic layer was maintained at about nm 2 nm/s ^ The active area of the device was 2 x 2 mm 2 ' as defined by the shadow mask for cathodic deposition. The structure and material of the device used are IT0/a_NPD (30 nm)/TCTA (20 nm)/CzSi (3 nm)/CzSi: (4) 8.0 wt% (35 nm)/UGH2: (4) 8.0 wt% (3) Nm) / UGH2 (2 nm) / BCP (50 nm) / Cs2C03 (2 nm) / Al. α-NPD, TCTA, CzSi, UGH2 and BCP represent α_naphthylphenylbiphenyldiamine, 4,4',4',_volume (N_decidyl)triphenylamine, 9_(4· Second·butyl-based)-3,6-bis-(triphenyl-6)-9H-flavored odor, ρ-bis(triphenyl-phosphonium) benzene and 2,9-dimethyl-4,7-di Phenyl-1,1 fluorene-phenanthroline. The naphthylphenylbiphenyldiamine (a_NPD) and 4,4,4'-indole (indole-carbazolyl)triphenylamine (TCTA) are used as a hole transfer layer (HTL). Czsi (30 A) acts as both a hole transfer layer and a buffer layer for blocking high-energy triple-excitation (on (4)) migration to TCTA (with lower triplet energy). The weight % of (4) CzSi and UGH2) are used to achieve a better balance between the hole and the electron injection/transport, thereby moving the excitation formation band away from the quenching interface containing the carrier transport layer to obtain CzSi. The nature of the hole transport and the nature of the electron transport of UGH2. The thin UGH2 (20 A) acts as both an electron transport/hole-blocking layer and a high-energy triple-excitation migration to Β〇ρ (with Lower triplet energy) buffer layer. Finally 'BCP is used as electron transport [Gua 29 201127933 layer, and A1 or Cs2C03 is used as an electron injection layer. Using source measurement unit (SMU) and containing Photo Research PR650 The calibrated Si photodiode performs current-voltage (IV) characterization of the illuminating device. The EL spectroscopy of the device is via Corrected CCD spectrogram collection. Figure 6 shows the structure of the blue-emitting OLED fabricated using the ruthenium complex (4) of the present invention, and the structure of the compound used together, and the energy level diagram. Figure 7 and Table 2 show this example. The efficacy of the manufactured blue OLEDs. Table 2 External quantum efficiency of the device (%) Luminous efficiency (cd/A) Power efficiency (lm/W) Blue OLED peak 10.13 17.60 10.43 100 cd/m2 6.80 11.69 4.71 The structure of a white LED The material is ITO/a-NPD (30 nm)/TCTA (20 nm)/CzSi: (4) 8.0 wt% (15 nm) / UGH2: (13) 8.0 wt% (5 nm) / BCP (45 nm) / Cs2C03 (2 nm) / Al (150 nm). The α-naphthylphenylbiphenyldiamine (α-NPD) and 4,4',4"-fluorene (bromazolyl)triphenylamine ( TCTA) is used as a hole transfer layer (HTL). Two radiation layers (doped with 8.0% by weight of (4) CzSi and 8.0% by weight of (13) UGH2) are used to achieve a better balance between hole and electron injection/transportation. The excitation formation band is removed from the quenching interface containing the carrier transport layer, and the advantages of the hole transporting nature of CzSi and the electron transporting nature of UGH2 are obtained. 30 201127933 Finally, BCP is used as an electron transport layer, and A1 or Cs2C03 is used as an electron injection layer. Current-voltage (I-V) characterization of the illumination device was performed using a source measurement unit (SMU) and a calibrated Si photodiode containing Photo Research PR650. The EL spectrum of the device was collected via a calibrated CCD spectrogram. Fig. 8 is a view showing the structure and energy level diagram of the structure of the white-emitting OLED produced by using the ruthenium complexes (4) and (13) of the present invention. Figures 9 and 3 show the efficacy of white OLEDs fabricated using ruthenium complexes (4) and (13). Table 3 Device External Quantum Efficiency (%) Luminous Efficiency (cd/A) Power Efficiency (lm/W) White OLED 10.93 28.70 24.70 100 cd/m2 7.20 18.22 10.60 [Simplified Schematic] FIG. 1 shows an embodiment in accordance with the present invention. The X-ray structure of the ruthenium complex (1) synthesized in 1 is a 0RTEP pattern of (1) showing a thermal ellipsoid at a 30% probability level; key length: Ir-C(l) = 2.016 (3) ), Ir-C(7) = 2.074(3), Ir-O(l) = 2.137(2), Ir-P(2) = 2..1421(8), Ir-0(2) = 2.236( 2) &Ir-P(l) = 2.3775(8)A. 2 shows an X-ray structure of a ruthenium complex synthesized in Example 7 according to the present invention (7\31 201127933, which is an ORTEP pattern of (7) showing a thermal ellipsoid at a 30% probability level; :ir_c(1〇) = 2 〇62(5), Ir_N(2)= 2.093(5), Ir-C(16) = 2.094(5), Ir-N(l) = 2.145(5), Ir- P(l) = 2.1708(14) and Ir-P(2) = 2.2695(15). Figure 3 shows the X-ray structure of the ruthenium complex (8) synthesized in Example 8 according to the present invention, The ORTEP pattern of (8) showing the thermal ellipsoid at 30% probability; key length: Ir_c(7) = 2 〇51(4) ' Ir C(1) =2.054(4) Ίγ-Ν(1) = 2.134(3). Ir-P(l) = 2.1441(10) > Ir-N(2) = 2.145(3) and Ir-Cl(l) = 2.4455(9) A. Figure 4 shows the complex (2) to (7) a structural diagram in the CH2Cl2 solution and UV/visible absorption and emission spectra, which were prepared in accordance with Examples 2 to 7 of the present invention. Fig. 5 shows complexes (8), (9). And (11) a structural diagram in solution and UV/visible absorption and emission spectra, which were prepared in accordance with Examples 8 to 9 of the present invention. Figure 6 shows the use of the ruthenium complex of the present invention (4) The structure of the blue-emitting OLED produced and the structure of the compound used together, and the energy level diagram. Figure 7 shows the performance data of the blue OLED fabricated using the ruthenium complex (4) of the present invention, wherein (a) current Density versus drive voltage mapping, (匕) external quantum efficiency versus luminance mapping, (c) power efficiency versus luminance mapping, and (sentence luminous efficiency versus luminance mapping. Figure 8 shows the use of erbium complexes (4) and (13) The structure of the manufactured white light and the structure of the compound used together, and the energy level diagram. Figure 9 shows the performance data of 32 201127933 white OLEDs fabricated using erbium complexes (4) and (13) as phosphors. (a) Current density versus drive voltage mapping, (b) external quantum efficiency versus luminance mapping, (c) power efficiency versus luminance mapping, and (d) luminous efficiency versus luminance mapping.

33

Claims (1)

201127933 VII. Patent application scope: 1. A phosphorescent transition metal complex represented by the formula la, lb, Ic or a stereoisomer thereof, which comprises a one-sided carbon-phosphorus-carbon (CAPAC) three a dental chelate, and a pair of carbon-nitrogen (CAN) or azole-nitrogen (anthracene) anionic luminophore chelators, together with any neutral donor ligand (L), as shown in la or lb; Containing a one-sided carbon-phosphorus-carbon (CAPAC) tridentate chelate and a neutral diimine nitrogen-nitrogen (ΝΛΝ) luminophore chelate, with the same arbitrary anion donor ligand (X), such as Ic Shown in: 34 201127933 Ic wherein M is the transition metal and is silver, iron or ruthenium; the carbon atom (C) linked by the arc (CAN) and the nitrogen atom (Ν) of the nitrogen atom (Ν), the azole of the oxazole (弓λΝ) and the nitrogen The atom (ν) or the neutral diimine having a dinitrogen atom (ΝλΝ) has the general formula Ai^-Ar2, wherein Αγ1 is an aryl group, a substituted aryl group or a polyaromatic group in the CAN chelate of la Fragment; pyrrolyl (ie), functionalized pyrhadyl, π-saltyl, functionalized η-saltyl, tri-beta, functionalized in lb ΑΛΝ chelate Triazolyl or tetrazolyl; or a heterocyclic nitrogen donor group in the diimine oxime of Ic' and Ar2 in each of the CAN, ruthenium and iridium complexes of formulas la, lb and Ic a neutral heteroaromatic nitrogen-containing donor group; the carbon atom (C) and the phosphorus atom (p) and the carbon atom (C) linked by a double arcuate (CAPAC) have the formula PR4(〇Ar5)2 'where R4 is An alkyl group, an aryl group, a substituted aryl group, an aryloxy group or a substituted aryloxy group; and Ar5 is an aryl group or a substituted aryl group containing an R5 substituent, wherein R5 is an alkyl group, an alkoxy group a dentate or pseudohalide; and the two carbon atoms in the CAPAC of the equation represent the aryl ring, ortho_cycl〇metaUted carbon atom 〇35 201127933 2. The complex of the first aspect of the patent, wherein Μ is silver, and Αγ5 is a stupid or substituted phenyl group. 3. As in the second aspect of the patent application, wherein the complex is by the formula la Or lb to indicate that in the formula & τ, h and lb are phosphorus donors PR R R3, and R2 and r3 are independently alkyl, alkoxy, aryl, substituted aryl, aryloxy A substituted or substituted aryloxy group. 4. The complex according to claim 3, wherein R1, Ri^ are independently methyl, phenyl or phenoxy. a complex, wherein the complex is represented by the formula la or lb, wherein l in the formulas 1 & and Ib is a non-phosphorus donor AsR1^, and Ri, R2 and r3 are independently alkyl, alkane An oxy group, an aryl group, a substituted aryl group, an aryloxy group or a substituted aryloxy group; or an arbitrary nitrogen donor pyridine. The complex of item 2, wherein the complex is represented by the formula Ic, wherein X in the formula ic is selected from the group consisting of acetate, halide, chaotic compound, disorganized acid radical, sulfur chaos and _ An inorganic anion of the group consisting of: or an aryl group, an alkoxy group, a phenoxide, a substituted phenoxide, a sulfhydryl group, a thiolate, a substituted fluorenyl group, an acetylate, and a substituted An organic anion of the group consisting of acetylides. & Si I j 36 201127933 7. The complex according to claim 2, oxy or phenyl. ^ + R4 is 8. The complex as in the seventh aspect of the patent application. 9. The complex of the first aspect of the patent application is a compound wherein R4 i wherein the carbon methoxy group and the benzene phenyl group are oxy. - nitrogen (0: ΛΝ) chelate Where But is a third butyl group. Nitrogen (ΑΛΝ) meal 10. As in the patent scope, the complex of the compound, wherein the azole is 37 201127933 \ / l· h >=n Wherein R is hydrogen, CF3, methyl, tert-butyl, small alkyl, phenyl or substituted base ' and wherein Bul is a third butyl group. 11. The complex of claim i, wherein the diimine nitrogen (N) chelating agent is Wherein R is hydrogen 'methyl, tert-butyl, small alkyl, phenyl, substituted aryl, fluoride, halide, pseudohalide, methoxy 'dimethylamino or diphenyl Amine. 12. The complex of claim 1, wherein the diimine nitrogen-nitrogen (ΝΛΝ) chelate is 38 201127933 R wherein R is methyl, ethyl, small alkyl, phenyl or substituted aryl. 13. The complex of claim 1 of the patent application is represented by the following formula: PhO Wherein Ph is a phenyl group. 14. The complex of claim 1 of the patent application is represented by the following formula: PhO _ Wherein Ph is a phenyl group and Bu1 is a third butyl group. 15. The complex of claim 1 of the patent application is represented by the following formula: 39 201127933 PhO Wherein Ph is a phenyl group, and Bu1 is a third butyl group. 16. The complex of claim 1 is represented by the following formula: Wherein Ph is a phenyl group, and Βι1 is a third butyl group. 17. The complex of the first aspect of the patent application is represented by the following formula: Wherein Ph is a phenyl group and is a third butyl group. 18. The complex of the first aspect of the patent application is represented by the following formula: 丨D C ^ J 40 201127933 Chaos and sulphate 19. As described in the patent application, the complex is represented by the following formula Wherein Ph is a phenyl group, and X = chloride and thiocyanate are formed on the substrate. An organic light-emitting diode comprises: a negative electrode, and a disposed between the positive electrode and the negative electrode The light-emitting layer VIII light-emitting layer contains the complex compound as described in Patent Application No. 1 as an electro-fill material. 21. The light-emitting diode of claim 2, wherein the metal is silver' and Ar5 is phenyl or substituted phenyl. 22. The light-emitting diode according to claim 21, wherein the complex is represented by the formula la or lb, wherein L is pr and W, and ri, R and R are independently burned and burned. An oxy group, an aryl group, a substituted aryl group, a stupid oxide or a substituted phenoxide. 201127933 23. The light-emitting diode of claim 21, wherein R4 is methoxy, phenyl or phenoxy. 24. The light-emitting diode of claim 22, wherein r1, R2 and R3 are independently fluorenyl, stupid or phenoxy. % 25. The light-emitting diode of claim 21, wherein the complex is represented by the formula Ic, wherein the oxime in the formula Ic is selected from the group consisting of acetate, halide cyanide, isocyanate, An inorganic anion of a group consisting of thiocyanate and a pseudo-form; or an aryl group, an alkoxy group, a phenoxide, a substituted phenoxide, an azole group, a thiolate, a substituted azole group, An organic anion of the group consisting of an acetylide and a substituted acetylide. 26. A phosphorescent transition metal complex represented by Formula Ia, Ib, Ic or a stereoisomer thereof comprising a one-sided carbon-璘 carbon (ς;ΛρΛς;) three-dentate chelate, And a pair of carbon-nitrogen (CAN) or azole-nitrogen (ΑΛΝ) anionic luminophore chelators, coordinated with any neutral donor. The sub-(L), as shown in Ia or Ib; a carbon-phosphorus-carbon (CaP/sC) tridentate chelate and a neutral diimine nitrogen-nitrogen (ΝΛΝ) luminophore chelate, with the same arbitrary anion donor ligand (X), as in Ic Show: 42 201127933 Ic wherein M is the transition metal and is ruthenium, hungry or ruthenium; the carbon atom (C) linked by the arc (CAN) and the nitrogen atom (Ν) of the nitrogen atom (Ν), the azole of the oxazole (Α) and the nitrogen Atom (Ν) or a neutral diimine having a dinitrogen atom (ΝΛΝ) 43 201127933 has the general formula Ar^-Ar2, wherein Ar1 is an aryl group, a substituted aryl group or a polyaryl group in the CAN chelate body. Family fragment; pyrrolyl (pyrr〇nde), functionalized pyridyl, pipityl, functionalized 嗤 嗤 、, tridecyl, functionalized in lb ΑΛΝ chelate a oxadiazolyl or a tetradecyl group; or a heterocyclic nitrogen donor group in the diimine oxime of Ic, and in each of the formulas la, lb, and Ic (: ΛΝ, ΑΛΝ, and νλΝ Ar2 is a neutral heteroaromatic nitrogen-containing donor group; the carbon atom (〇 and phosphorus atom (p) and carbon atom (C)) linked by a double arcuate (CAPAC) has the formula PR4(CH2Ar5)2, wherein R4 Is an alkyl group, an aryl group, a substituted aryl group, an aryloxy group or a substituted aryloxy group; and Ar5 is an aryl group or a substituted aryl group containing a stilbene 5 substituent. Wherein R5 is an alkyl group, an alkoxy group, a functional group or a pseudohalide; and the two carbon atoms in the CAPAC of the equation represent the ortho-cyclometalated carbon of the aryl ring, Ar5, Atom) ° [tSS]] 44