CN102659846A - N-substituted phenylbenzimidazole trivalent-iridium organometallic complex and its preparation method and use - Google Patents
N-substituted phenylbenzimidazole trivalent-iridium organometallic complex and its preparation method and use Download PDFInfo
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Abstract
The invention discloses a kind of N- substituted-phenyl benzimidazole trivalent-iridium organometallic complex, preparation method and the application in organic electrophosphorescenpolymer doping type luminescent device. The structural formula of the organometallic complex are as follows:
Or
Wherein, R1, R2 are respectively and independently selected from hydrogen, the alkyl of C1-C4, C1-C4 halogenated alkyl, aromatic radical, condensed ring group, anilino-, carbazyl, any one in fluorenyl. The organometallic complex can be applied to have in the organic electrophosphorescenpolymer doping type luminescent device of stratiform doping type structure, guest materials as luminescent layer, yellow light material of the luminescent spectrum wave band between 560-610nm can be obtained, therefore is had a good application prospect in monochromatic, total colouring and illumination white light parts.
Description
Technical field
The present invention relates to organophosphorus photoelectricity photoluminescence (PhOLED) device technology field, design a kind of N-substituted-phenyl benzimidazoles trivalent-iridium organometallic complex, its preparation method and the application in organic electrophosphorescenpolymer doped luminescent device especially.
Background technology
Electroluminescent organic material and device are current international research hot fields.At present, the commercialization of many electroluminescent organic materials, part organic display spare also is used widely at aspects such as mobile phone, indicating meters.According to the difference of principle of luminosity, electroluminescent organic material can be divided into fluorescent material and phosphor material two big classes.Compare with fluorescent material, phosphor material can make full use of all form of energy that comprise singlet and triplet, can make the internal quantum efficiency of device reach 100% in theory.Therefore, utilize transition metal complex to become a kind of important means that improves device as luminescent material.
At present in the research field of organic electroluminescent phosphorescence luminescent material, the rare earth ion title complex since its luminous wave band narrow with characteristics such as luminous efficiency height, caused the very big research interest of scientists.The compound that wherein has europium (Eu) and the terbium (Tb) of typical triplet state luminescence feature is considered to the candidate material of ruddiness and green glow.But there is the shortcoming of lifetime of excited state oversize (millisecond magnitude) in rare earth compounding, and the self-quenching problem of triplet excitons is not easy to solve, thereby has limited the application of rare earth material.
Small molecules doped cyclic metal complex becomes the emphasis that people pay close attention in recent years, like the title complex of iridium, ruthenium, platinum, copper etc.The advantage of these title complexs is that they can obtain very high emitted energy from the triplet of self.But the photoelectric properties of metal complexess such as ruthenium, platinum, copper are not high, are difficult in industry and go up the big area popularization.And metal iridium complex because the good stability of its compound, reaction conditions is gentle in building-up process, and has very high photoelectric properties, in research process always in occupation of dominant position.
Existing Ir (ppy)
3, phosphor material such as FIrpic obtained certain achievement on photoelectric properties such as brightness, efficient; But because it has the saturated and serious triplet of stronger launching site-triplet quenching phenomenon, so the maximum efficiency of corresponding device appears at (J＜0.1mA/cm under the low current density usually
2), and along with the increase of current density, efficient and brightness meeting decay fast, have limited the application of phosphor material aspect the passive drive organic elctroluminescent device.
For this reason, exploitation has the excited state short life, under HCD high efficiency phosphor material, and be used for yellow, the white organic electroluminescent display device of structure, become a major challenge of academia and industrial community.
Summary of the invention
Technical purpose of the present invention provides a kind of gold-tinted electrophosphoresceniridium iridium complex, its preparation method and application in organic electroluminescence device with bipolarity, high-luminous-efficiency and high brightness.
The present invention realizes that the technical scheme that above-mentioned technical purpose is taked is: a kind of N-substituted-phenyl benzimidazoles trivalent-iridium organometallic complex, and its structural formula is:
Wherein: R
1, R
2Independently be selected from hydrogen, C respectively
1-C
4Alkyl, C
1-C
4In haloalkyl, aromatic base, condensed ring group, anilino, carbazyl, the fluorenyl any one.
The synthetic route of a kind of N-substituted-phenyl of the present invention benzimidazoles trivalent-iridium organometallic complex is as shown in Figure 1, may further comprise the steps:
Step 1: bromine substituted benzene acyl chlorides and 2-amido disubstituted benzenes amine are the synthetic N-substituted-phenyl benzimidizole derivatives of raw material;
Step 2: replacing bromo phenyl imidazo phenyl derivatives with step 1 synthetic N-is the synthetic N-substituted-phenyl benzoglyoxaline boric acid of raw material that ester derivative frequently;
Step 3: step 2 synthetic N-substituted-phenyl benzoglyoxaline boric acid that ester derivative of frequency and various bromo group carry out the SUZUKI reaction, obtain corresponding ligand material;
Step 4: the corresponding chlorine endo compound of preparation of the ligand material that step 3 obtains and iridous chloride reaction;
Step 5: the chlorine endo compound and 2 that step 4 obtains, the reaction of 4-diacetylmethane obtains corresponding phosphor material.
The guest materials that a kind of N-substituted-phenyl of the present invention benzimidazoles trivalent-iridium organometallic complex can be used as luminescent layer in the organophosphorus photodoping type electroluminescent device uses.A kind of structure of this electroluminescent device is a stratiform doped structure; As shown in Figure 2; Being followed successively by substrate (1), nesa coating (2), hole injection layer (3), luminescent layer (4), electron injecting layer (5) and negative electrode (6) by substrate to negative electrode constitutes; Wherein, Luminescent layer (4) is to be dissolved in the thin film layer that the mixture that forms in the chlorobenzene forms on hole injection layer (3) surface altogether by material of main part, guest materials and hole cushioning material, and this guest materials is selected N-substituted-phenyl benzimidazoles trivalent-iridium organometallic complex of the present invention for use.
In the above-mentioned organophosphorus photodoping type electroluminescent device:
Hole injection layer (3) material is preferably and gathers 3,4-enedioxy thiophene and poly styrene sulfonate material (PEDOT:PSS), and its thickness is preferably 30-50nm;
Material of main part is preferably polyvinyl carbazole (PVK) in the luminescent layer (4), and the hole cushioning material is preferably 2-phenyl-5-(4-phenylbenzene)-1,3,4 oxazoles (PBD).
The mass ratio of luminescent layer (4) material of main part, guest materials and PBD is preferably 70: 1-10: 30, and luminescent layer (4) thickness is preferably 40-100nm;
Electron injecting layer (5) material is preferably LiF, MoO
3, WO
3Deng, its thickness is preferably 0.5-2nm; Negative electrode (6) material is preferably aluminium, silver, and calcium, magnesium etc., its thickness is preferably 100-200nm.
In sum; The invention provides a kind of organometallic complex with novel texture; Can be applied to have in the organic electrophosphorescenpolymer doped luminescent device of stratiform doped structure,, can access the gold-tinted material of luminescent spectrum wave band between 560-610nm as the guest materials of luminescent layer; Therefore be a kind of phosphor material simple, that chromaticity coordinates is good for preparing, in monochromatic, panchromatic demonstration and illumination white light parts, have a good application prospect.
Description of drawings
Fig. 1 is the synthetic route chart of N-substituted-phenyl benzimidazoles trivalent-iridium organometallic complex of the present invention;
Fig. 2 is the organophosphorus photodoping type electroluminescent device structural representation that the present invention is based on the trivalent complex of iridium.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing, it is pointed out that the following stated embodiment is intended to be convenient to understanding of the present invention, and it is not played any qualification effect.
Umber related in following examples is molfraction.
Embodiment 1:
In the present embodiment, the structural formula of N-phenyl-2-Phenylbenzimidazole trivalent-iridium organometallic complex is:
The preparation method of above-mentioned N-phenyl-2-Phenylbenzimidazole trivalent-iridium organometallic complex comprises the steps:
Step 1: synthetic intermediate a1:N-phenyl-2-is to bromophenyl benzoglyoxaline (BrPBI)
In the 250mL there-necked flask that stirring, TM, gas access equipment are housed, feed argon gas 10min, add 10 parts of parabromobenzoyl chlorides and 10 parts of reactions of 2-aminodiphenylamine successively; 60 parts of 3 parts of triethylamines and THFs react 24h under the room temperature, in 100 parts of deionized waters of reaction solution impouring; The employing dichloromethane extraction separates, and steams methylene dichloride and obtains crude product, and crude product recrystallization in the mixture solution of methyl alcohol and THF obtains gray solid; This gray solid is dissolved in the 12h that refluxes in 20 parts of acetate; Steam acetate, oven dry obtains pearl midbody a1:N-phenyl-2-to bromophenyl benzoglyoxaline (BrPBI).
Above-mentioned midbody a1 is analyzed: mass spectrum: (M
+): 348.2,350.3; Ultimate analysis: C 65.43, H 4.02, and N 7.95, calculated value: C 65.35, and H 3.75, and N 8.02.
Step 2: synthetic intermediate b1:N-phenyl-2-(4-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) phenyl)-1H-benzoglyoxaline
, the there-necked flask of magnetic stirring apparatus adds 10 parts Potassium ethanoate, 4 parts two glutaryls two boron and 0.2 part of Pd (dppf) Cl in being housed
2Be dissolved in the inferior fen of 200 parts of dimethyl-, under the nitrogen protection, stirring at normal temperature 25min obtains first solution; Then, 2 parts of step 1 synthetic midbody a1:N-phenyl-2-are added in the inferior fen of dimethyl-of 10 deals bromophenyl benzoglyoxaline (BrPBI), obtain second solution; First solution is mixed with second solution, be warming up to 85 ℃, nitrogen protection is reaction 30h down, removes solvent; Cross that post separates, purifying obtains midbody b1:N-benzene, (4-(4,4,5 for base-2-; 5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) phenyl)-the 1H-benzoglyoxaline.
Above-mentioned midbody b1 is analyzed: mass spectrum: (M
+): 396.1; Ultimate analysis: C 75.44, H 6.62, and N 7.27, calculated value: C 75.77, and H 6.36, and N 7.07.
Step 3: synthetic ligands PPBI
In the there-necked flask of magnetic stirring apparatus was housed, (4-(4,4 with 1 part of step 2 synthetic midbody b1:N-phenyl-2-; 5,5-tetramethyl--1,3; 2-dioxy boron penta ring-2-yl) phenyl)-1H-benzoglyoxaline, 1 part of bromobenzene and 0.1 part of four triphenyl phosphorus palladium be dissolved in the toluene of 20 deals; At 105 ℃ of reaction 24h, remove solvent under the nitrogen protection, cross that post separates, purifying obtains part PPBI.
Above-mentioned part PPBI is analyzed: mass spectrum: (M
+): 46.2; Ultimate analysis: C 86.57, H 5.17, and N 8.26, calculated value: C 86.68, and H 5.24, and N 8.09.
Step 4: the chlorine endo compound of synthetic PPBI
2.5 parts PPBI, 1 part of one hydration iridous chloride, 60 parts of EGMEs, 20 parts of deionized waters are placed the there-necked flask of 250mL, and argon atmosphere stirs 30min, heating reflux reaction 10h down.Cooling is filtered, and washing is to neutral, and oven dry obtains yellow powder, is the chlorine endo compound of PPBI;
Step 5: synthetic two (N-phenyl-2-Phenylbenzimidazoles)-2,4-diacetylmethane iridium Ir (PPBI)
2Acac
The chlorine endo compound of the PPBI that step 4 is obtained and 10 part 2, the 4-diacetylmethane, 2 parts KOH, 60 parts EGME places there-necked flask, and argon atmosphere stirs 30min, heating reflux reaction 30h down.Cooling is filtered, and washing is to neutral, and oven dry obtains Ir (PPBI)
2Acac crude product, crude product are purified through column chromatography and are obtained xanchromatic powder Ir (PPBI)
2Acac.
To above-mentioned ligand i r (PPBI)
2Acac analyzes: mass spectrum: (M
+): 982.2; Ultimate analysis: C 67.38, H 4.16, and N 5.81, calculated value: C 67.26, and H 4.21, and N 5.70.
Above-mentioned Ir (PPBI)
2The acac material can be applied in the organophosphorus photodoping type electroluminescent device.This electroluminescent device is stratiform doped structure, and is as shown in Figure 2, comprises that successively substrate is followed successively by substrate 1, nesa coating 2, hole injection layer 3, luminescent layer 4 to negative electrode, electron injecting layer 5 and negative electrode 6.Wherein, substrate 1 is selected glass or transparent plastics for use; It is that the tin indium oxide (ITO) of 20 Ω/sq is as anode that nesa coating 2 is selected face resistance for use; Substrate is cleaned back photoglow under the high purity oxygen atmosphere (plasma) handle 10min, under the ultra-clean condition, the hole injection layer 3 of spin coating 30nm, 40nm, 50nm on nesa coating 2, hole injection layer 3 adopts PEDOT:PSS; Spin coating luminescent layer 4 on hole injection layer 3 prepares complex of iridium Ir (PPBI) in luminescent layer 4 employing PVK, the present embodiment 1 then
2Acac, and the mixing solutions that forms of PBD, its mass ratio is 70: X: 30, X=1 wherein, 2,4,6,8,10, the light emitting layer thickness with different levels of doping is 70nm and 80nm; Afterwards under high vacuum (3～2 * 10
-4Pa) under, electron input horizon 5 on luminescent layer 4, electron injecting layer 5 is selected LiF for use, and its thickness is 0.5nm, 1nm, 1.5nm or 2nm; Deposition cathode 6 on electron injecting layer 5 at last, negative electrode 6 is selected Al for use, and its thickness is 100nm, 150nm or 200nm.
In the preparation process of above-mentioned organophosphorus photodoping type electroluminescent device, the thickness of film adopts the step appearance to measure, and measures luminosity with nitometer, and all organic materialss adopt the mode of spin-coating film, and LiF and metal A l adopt the film forming mode of vacuum evaporation.
When above-mentioned organophosphorus photodoping type electroluminescent device was applied suitable external voltage, the performance that records this electro-phosphorescent luminescent device was as shown in table 1.
Embodiment 2:
In the present embodiment, the structural formula of N-phenyl-2-(1 '-naphthyl) benzoglyoxaline trivalent-iridium organometallic complex is:
The preparation method of above-mentioned N-phenyl-2-(1 '-naphthyl) benzoglyoxaline trivalent-iridium organometallic complex comprises the steps:
Step 1: synthetic ligands NpPBI
In the there-necked flask of magnetic stirring apparatus was housed, (4-(4,4 with step 2 synthetic midbody b1:N-phenyl-2-among 2 parts of embodiment 1; 5,5-tetramethyl--1,3; 2-dioxy boron penta ring-2-yl) phenyl)-1H-benzoglyoxaline, 2 parts of 1-bromonaphthalenes and 0.2 part of four triphenyl phosphorus palladium be dissolved in the toluene of 40 deals; At 105 ℃ of reaction 36h, remove solvent under the nitrogen protection, cross that post separates, purifying obtains part NpPBI.
Above-mentioned part NpPBI is analyzed: mass spectrum: (M
+): 396.2; Ultimate analysis: C 87.59, H 5.18, and N 7.23, calculated value: C 87.85, and H 5.08, and N 7.07.
Step 2: the chlorine endo compound of synthetic NpPBI
5 parts NpPBI, 2 part of one hydration iridous chloride, 120 parts of EGMEs, 40 parts of deionized waters are placed the there-necked flask of 500mL, and argon atmosphere stirs 60min, heating reflux reaction 20h down.Cooling is filtered, and washing is to neutral, and oven dry obtains yellow powder, is the chlorine endo compound of NpPBI;
Step 3: synthetic two (N-phenyl-2-(1 '-naphthyl) benzoglyoxalines)-2,4-diacetylmethane iridium Ir (NpPBI)
2Acac
The chlorine endo compound of the NpPBI that step 2 is obtained and 10 part 2, the 4-diacetylmethane, 2 parts KOH, 60 parts EGME places there-necked flask, and argon atmosphere stirs 30min, heating reflux reaction 30h down.Cooling is filtered, and washing is to neutral, and oven dry obtains Ir (NpPBI)
2Acac crude product, crude product are purified through column chromatography and are obtained xanchromatic powder Ir (NpPBI)
2Acac.
Mass spectrum: (M
+): 1082.1; Ultimate analysis: C 69.81, H 4.08, and N 5.35, calculated value: C 69.92, and H 4.19, and N 5.18.
Luminescent device among luminescent device structure and the embodiment 1 is basic identical, and different is with preparing complex of iridium Ir (NpPBI) in the present embodiment 2
2Acac replaces Ir (PPBI)
2Acac.
Embodiment 3:
In the present embodiment, the structural formula of N-phenyl-2-(9,9-dioctyl-fluorenyl) benzoglyoxaline trivalent-iridium organometallic complex is:
The preparation method of above-mentioned N-substituted-phenyl benzimidazoles trivalent-iridium organometallic complex comprises the steps:
Step 1: synthetic ligands FPBI
In the there-necked flask of magnetic stirring apparatus was housed, (4-(4,4 with step 2 synthetic midbody b1:N-phenyl-2-among 3 parts of embodiment 1; 5,5-tetramethyl--1,3; 2-dioxy boron penta ring-2-yl) phenyl)-1H-benzoglyoxaline, 3 parts of 2-bromo-9,9-dioctyl fluorene and 0.3 part of four triphenyl phosphorus palladium are dissolved in the toluene of 60 deals, under the nitrogen protection at 105 ℃ of reaction 48h; Remove solvent, post separates excessively, purifying obtains part FPBI.
Above-mentioned part FPBI is analyzed: mass spectrum: (M
+): 658.1; Ultimate analysis: C 87.47, H 8.17, and N 4.36, calculated value: C 87.49, and H 8.26, and N 4.25.
Step 2: the chlorine endo compound of synthetic FPBI
7.5 parts FPBI, 3 part of one hydration iridous chloride, 180 parts of EGMEs, 60 parts of deionized waters are placed the there-necked flask of 1000mL, and argon atmosphere stirs 90min, heating reflux reaction 30h down.Cooling is filtered, and washing is to neutral, and oven dry obtains yellow powder, is the chlorine endo compound of FPBI;
Step 3: synthetic two (N-phenyl-2-(9,9-dioctyl-fluorenyl) benzoglyoxalines)-2,4-diacetylmethane iridium Ir (FPBI)
2Acac
The chlorine endo compound of the FPBI that step 2 is obtained and 15 part 2, the 4-diacetylmethane, 3 parts KOH, 90 parts EGME places there-necked flask, and argon atmosphere stirs 45min, heating reflux reaction 45h down.Cooling is filtered, and washing is to neutral, and oven dry obtains Ir (FPBI)
2Acac crude product, crude product are purified through column chromatography and are obtained xanchromatic powder Ir (FPBI)
2Acac.
Mass spectrum: (M
+): 1607.1; Ultimate analysis: C 75.29, H 6.98, and N 3.56, calculated value: C 75.48, and H 7.09, and N 3.49.
Luminescent device among luminescent device structure and the embodiment 1 is basic identical, and different is with preparing complex of iridium Ir (FPBI) in the present embodiment 3
2Acac replaces Ir (PPBI)
2Acac.
Embodiment 4:
In the present embodiment, the structural formula of N-phenyl-2-(N '-octyl group-carbazyl) benzoglyoxaline trivalent-iridium organometallic complex is:
The preparation method of above-mentioned N-phenyl-2-(N '-octyl group-carbazyl) benzoglyoxaline trivalent-iridium organometallic complex comprises the steps:
Step 1: synthetic ligands CzPBI
In the there-necked flask of magnetic stirring apparatus was housed, (4-(4,4 with step 2 synthetic midbody b1:N-phenyl-2-among 1 part of embodiment 1; 5,5-tetramethyl--1,3; 2-dioxy boron penta ring-2-yl) phenyl)-1H-benzoglyoxaline, 1 part of 3-bromo-N-octyl group carbazole and 0.3 part of four triphenyl phosphorus palladium be dissolved in the toluene of 20 deals; At 105 ℃ of reaction 48h, remove solvent under the nitrogen protection, cross that post separates, purifying obtains part CzPBI.
Above-mentioned part CzPBI is analyzed: mass spectrum: (M
+): 547.1; Ultimate analysis: C 85.43, H 6.91, and N 7.66, calculated value: C 85.52, and H 6.81, and N 7.67.
Step 2: the chlorine endo compound of synthetic CzPBI
2.5 parts CzPBI, 1 part of one hydration iridous chloride, 60 parts of EGMEs, 20 parts of deionized waters are placed the there-necked flask of 250mL, and argon atmosphere stirs 30min, heating reflux reaction 10h down.Cooling is filtered, and washing is to neutral, and oven dry obtains yellow powder, is the chlorine endo compound of CzPBI;
Step 3: synthetic N-phenyl-2-(N '-octyl group-carbazyl) benzimidazolyl-2 radicals, 4-diacetylmethane iridium Ir (CzPBI)
2Acac
The chlorine endo compound of the CzPBI that step 2 is obtained and 5 part 2, the 4-diacetylmethane, 1 part KOH, 30 parts EGME places there-necked flask, and argon atmosphere stirs 15min, heating reflux reaction 15h down.Cooling is filtered, and washing is to neutral, and oven dry obtains Ir (CzPBI)
2Acac crude product, crude product are purified through column chromatography and are obtained xanchromatic powder Ir (CzPBI)
2Acac.
Mass spectrum: (M
+): 1383.4; Ultimate analysis: C 72.04, H 5.69, and N 6.13, calculated value: C 71.99, and H 5.75, and N 6.07.
Luminescent device among luminescent device structure and the embodiment 1 is basic identical, and different is with preparing complex of iridium Ir (CzPBI) in the present embodiment 4
2Acac replaces Ir (PPBI)
2Acac.
Embodiment 5:
In the present embodiment, the structural formula of N-phenyl-2-(triphen amido) benzoglyoxaline trivalent-iridium organometallic complex is:
The preparation method of above-mentioned N-phenyl-2-(triphen amido) benzoglyoxaline trivalent-iridium organometallic complex comprises the steps:
Step 1: synthetic ligands TPAPBI
In the there-necked flask of magnetic stirring apparatus was housed, (4-(4,4 with step 2 synthetic midbody b1:N-phenyl-2-among 1 part of embodiment 1; 5,5-tetramethyl--1,3; 2-dioxy boron penta ring-2-yl) phenyl)-1H-benzoglyoxaline, 1 part be dissolved in the toluene of 20 deals bromine triphenylamine and 0.1 part of four triphenyl phosphorus palladium; At 105 ℃ of reaction 48h, remove solvent under the nitrogen protection, cross that post separates, purifying obtains part TPAPBI.
Above-mentioned part TPAPBI is analyzed: mass spectrum: (M
+): 589.1; Ultimate analysis: C 87.57, H5.21, N 7.22, calculated value: C 87.58, and H 5.30, and N 7.13.
Step 2: the chlorine endo compound of synthetic TPAPBI
2.5 parts TPAPBI, 1 part of one hydration iridous chloride, 60 parts of EGMEs, 20 parts of deionized waters are placed the there-necked flask of 250mL, and argon atmosphere stirs 30min, heating reflux reaction 10h down.Cooling is filtered, and washing is to neutral, and oven dry obtains yellow powder, is the chlorine endo compound of TPAPBI;
Step 3: synthetic two (N-phenyl-2-(triphen amido) benzoglyoxalines)-2,4-diacetylmethane iridium Ir (TPAPBI)
2Acac
The chlorine endo compound of the TPAPBI that step 2 is obtained and 5 part 2, the 4-diacetylmethane, 1 part KOH, 30 parts EGME places there-necked flask, and argon atmosphere stirs 15min, heating reflux reaction 15h down.Cooling is filtered, and washing is to neutral, and oven dry obtains Ir (TPAPBI)
2Acac crude product, crude product are purified through column chromatography and are obtained xanchromatic powder Ir (TPAPBI)
2Acac.
Mass spectrum: (M
+): 1315.3; Ultimate analysis: C 72.12, H 4.47, and N 6.44, calculated value: C 72.07, and H 4.52, and N 6.38.
Luminescent device among luminescent device structure and the embodiment 1 is basic identical, and different is with preparing complex of iridium Ir (TPAPBI) in the present embodiment 5
2Acac replaces Ir (PPBI)
2Acac.
Embodiment 6:
In the present embodiment, the structural formula of N-phenyl-2-(3 '-triphen amido) benzoglyoxaline trivalent-iridium organometallic complex is:
The preparation method of above-mentioned N-phenyl-2-(3 '-triphen amido) benzoglyoxaline trivalent-iridium organometallic complex comprises the steps:
Step 1: synthetic ligands 3-TPAPBI
In the there-necked flask of magnetic stirring apparatus was housed, (4-(4,4 with step 2 synthetic midbody b1:N-phenyl-2-among 1 part of embodiment 1; 5,5-tetramethyl--1,3; 2-dioxy boron penta ring-2-yl) phenyl)-the 1H-benzoglyoxaline, bromine triphenylamine and 0.1 part of four triphenyl phosphorus palladium are dissolved in the toluene of 20 deals between 1 part; At 105 ℃ of reaction 48h, remove solvent under the nitrogen protection, cross that post separates, purifying obtains part 3-TPAPBI.
Above-mentioned part 3-TPAPBI is analyzed: mass spectrum: (M
+): 513.2; Ultimate analysis: C 86.48, H 5.34, and N 8.18, calculated value: C 86.52, and H 5.30, and N 8.18.
Step 2: the chlorine endo compound of synthetic 3-TPAPBI
2.5 parts 3-TPAPBI, 1 part of one hydration iridous chloride, 60 parts of EGMEs, 20 parts of deionized waters are placed the there-necked flask of 250mL, and argon atmosphere stirs 30min, heating reflux reaction 10h down.Cooling is filtered, and washing is to neutral, and oven dry obtains yellow powder, is the chlorine endo compound of 3-TPAPBI;
Step 3: synthetic two (N-phenyl-2-(3 '-triphen amido) benzoglyoxalines)-2,4-diacetylmethane iridium Ir (3-TPAPBI)
2Acac
The chlorine endo compound of the TPAPBI that step 2 is obtained and 5 part 2, the 4-diacetylmethane, 1 part KOH, 30 parts EGME places there-necked flask, and argon atmosphere stirs 15min, heating reflux reaction 15h down.Cooling is filtered, and washing is to neutral, and oven dry obtains Ir (3-TPAPBI)
2Acac crude product, crude product are purified through column chromatography and are obtained xanchromatic powder Ir (3-TPAPBI)
2Acac.
Mass spectrum: (M
+): 1315.1; Ultimate analysis: C 72.09, H 4.62, and N 6.19, calculated value: C 72.07, and H 4.52, and N 6.38.
Luminescent device among luminescent device structure and the embodiment 1 is basic identical, and different is with preparing complex of iridium Ir (3-TPAPBI) in the present embodiment 6
2Acac replaces Ir (PPBI)
2Acac.
Embodiment 7:
In the present embodiment, the structural formula of N-phenyl-2-(to the biphenylyl pentanoic) benzoglyoxaline trivalent-iridium organometallic complex is:
The preparation method of above-mentioned N-phenyl-2-(to the biphenylyl pentanoic) benzoglyoxaline trivalent-iridium organometallic complex comprises the steps:
Step 1: synthetic ligands TPAPPBI
In the there-necked flask of magnetic stirring apparatus was housed, (4-(4,4 with step 2 synthetic midbody b1:N-phenyl-2-among 1 part of embodiment 1; 5,5-tetramethyl--1,3; 2-dioxy boron penta ring-2-yl) phenyl)-1H-benzoglyoxaline, 1 part be dissolved in the toluene of 20 deals bromine biphenylyl phenylenediamine and 0.1 part of four triphenyl phosphorus palladium; At 105 ℃ of reaction 48h, remove solvent under the nitrogen protection, cross that post separates, purifying obtains part TPAPPBI.
Above-mentioned part TPAPPBI is analyzed: mass spectrum: (M
+): 589.1; Ultimate analysis: C 87.57, H 5.21, and N 7.22, calculated value: C 87.58, and H 5.30, and N 7.13.
Step 2: the chlorine endo compound of synthetic TPAPPBI
2.5 parts TPAPPBI, 1 part of one hydration iridous chloride, 60 parts of EGMEs, 20 parts of deionized waters are placed the there-necked flask of 250mL, and argon atmosphere stirs 30min, heating reflux reaction 10h down.Cooling is filtered, and washing is to neutral, and oven dry obtains yellow powder, is the chlorine endo compound of TPAPPBI;
Step 3: synthetic two (N-phenyl-2-(to the biphenylyl pentanoic) benzoglyoxalines)-2,4-diacetylmethane iridium Ir (TPAPPBI)
2Acac
The chlorine endo compound of the TPAPPBI that step 2 is obtained and 5 part 2, the 4-diacetylmethane, 1 part KOH, 30 parts EGME places there-necked flask, and argon atmosphere stirs 15min, heating reflux reaction 15h down.Cooling is filtered, and washing is to neutral, and oven dry obtains Ir (TPAPPBI)
2Acac crude product, crude product are purified through column chromatography and are obtained xanchromatic powder Ir (TPAPPBI)
2Acac.
Mass spectrum: (M
++ 1): 1467.9; Ultimate analysis: C 74.27, H 4.46, and N 5.56, calculated value: C 74.41, and H 4.60, and N 5.72.
Luminescent device among luminescent device structure and the embodiment 1 is basic identical, and different is with preparing complex of iridium Ir (TPAPPBI) in the present embodiment 7
2Acac replaces Ir (PPBI)
2Acac.
Embodiment 8:
In the present embodiment, the structural formula of N-p-methylphenyl-2-Phenylbenzimidazole trivalent-iridium organometallic complex is:
The preparation method of above-mentioned N-p-methylphenyl-2-Phenylbenzimidazole trivalent-iridium organometallic complex comprises the steps:
Step 1: synthetic intermediate a2:N-p-methylphenyl-2-is to bromophenyl benzoglyoxaline (N-MBrPBI)
In the 250mL there-necked flask that stirring, TM, gas access equipment are housed, feed argon gas 10min, add 10 parts of parabromobenzoyl chlorides and N-p-methylphenyl-1 successively; 10 parts of reactions of 2-phenylenediamine, 60 parts of 3 parts of triethylamines and THFs react 24h under the room temperature; In 100 parts of deionized waters of reaction solution impouring, adopt dichloromethane extraction to separate, steam methylene dichloride and obtain crude product; Crude product recrystallization in the mixture solution of methyl alcohol and THF obtains gray solid, and this gray solid is dissolved in the 12h that refluxes in 20 parts of acetate, steams acetate; Oven dry obtains pearl midbody a2:N-p-methylphenyl-2-to bromophenyl benzoglyoxaline (N-MBrPBI).
Above-mentioned midbody a2 is analyzed: mass spectrum: (M
+): 362.1,364.3; Ultimate analysis: C 65.93, H 4.07, and N 7.92, calculated value: C 66.13, and H 4.16, and N 7.71.
Step 2: synthetic intermediate b2:N-p-methylphenyl-2-(4-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) phenyl)-1H-benzoglyoxaline
, the there-necked flask of magnetic stirring apparatus adds 10 parts Potassium ethanoate, 4 parts two glutaryls two boron and 0.2 part of Pd (dppf) Cl in being housed
2Be dissolved in the inferior fen of 200 parts of dimethyl-, under the nitrogen protection, stirring at normal temperature 25min obtains first solution; Then, 2 parts of step 1 synthetic midbody a2:N-p-methylphenyl-2-are added in the inferior fen of dimethyl-of 10 deals bromophenyl benzoglyoxaline (N-MBrPBI), obtain second solution; First solution is mixed with second solution, be warming up to 85 ℃, nitrogen protection is reaction 30h down, removes solvent; Cross that post separates, purifying obtains midbody b2:N-p-methylphenyl-2-(4-(4,4,5; 5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) phenyl)-the 1H-benzoglyoxaline.
Above-mentioned midbody b2 is analyzed: mass spectrum: (M
+): 410.2; Ultimate analysis: C 76.45, H 6.68, and N 6.88, calculated value: C 76.11, and H 6.63, and N 6.83.
Step 3: synthetic ligands N-MPPBI
In the there-necked flask of magnetic stirring apparatus was housed, (4-(4,4 with 1 part of step 2 synthetic midbody b2:N-p-methylphenyl-2-; 5,5-tetramethyl--1,3; 2-dioxy boron penta ring-2-yl) phenyl)-1H-benzoglyoxaline, 1 part of bromobenzene and 0.1 part of four triphenyl phosphorus palladium be dissolved in the toluene of 20 deals; At 105 ℃ of reaction 24h, remove solvent under the nitrogen protection, cross that post separates, purifying obtains part N-MPPBI.
Above-mentioned part N-MPPBI is analyzed: mass spectrum: (M
+): 360.1; Ultimate analysis: C 86.69, H 5.47, and N 7.84, calculated value: C 86.64, and H 5.59, and N 7.77.
Step 4: the chlorine endo compound of synthetic N-MPPBI
2.5 parts N-MPPBI, 1 part of one hydration iridous chloride, 60 parts of EGMEs, 20 parts of deionized waters are placed the there-necked flask of 250mL, and argon atmosphere stirs 30min, heating reflux reaction 10h down.Cooling is filtered, and washing is to neutral, and oven dry obtains yellow powder, is the chlorine endo compound of N-MPPBI;
Step 5: synthetic two (N-p-methylphenyl-2-Phenylbenzimidazoles)-2,4-diacetylmethane iridium Ir (N-MPPBI)
2Acac
The chlorine endo compound of the N-MPPBI that step 4 is obtained and 10 part 2, the 4-diacetylmethane, 2 parts KOH, 60 parts EGME places there-necked flask, and argon atmosphere stirs 30min, heating reflux reaction 30h down.Cooling is filtered, and washing is to neutral, and oven dry obtains Ir (N-MPPBI)
2Acac crude product, crude product are purified through column chromatography and are obtained xanchromatic powder Ir (N-MPPBI)
2Acac.
Mass spectrum: (M
++ 1): 1010.1; Ultimate analysis: C 67.58, H 4.67, and N 5.51, calculated value: C 67.77, and H 4.49, and N 5.55.
Luminescent device among luminescent device structure and the embodiment 1 is basic identical, and different is with preparing complex of iridium Ir (N-MPPBI) in the present embodiment 8
2Acac replaces Ir (PPBI)
2Acac.
Embodiment 9:
In the present embodiment, the structural formula of N-p-methylphenyl-2-(9,9-dioctyl-fluorenyl) benzoglyoxaline trivalent-iridium organometallic complex is:
The preparation method of above-mentioned N-p-methylphenyl-2-(9,9-dioctyl-fluorenyl) benzoglyoxaline trivalent-iridium organometallic complex comprises the steps:
Step 1: synthetic ligands N-MFPBI
In the there-necked flask of magnetic stirring apparatus was housed, (4-(4,4 with step 2 synthetic midbody b2:N-p-methylphenyl-2-among 1 part of embodiment 8; 5,5-tetramethyl--1,3; 2-dioxy boron penta ring-2-yl) phenyl)-1H-benzoglyoxaline, 1 part of 2-bromo-9,9-dioctyl fluorene and 0.1 part of four triphenyl phosphorus palladium are dissolved in the toluene of 20 deals, under the nitrogen protection at 105 ℃ of reaction 48h; Remove solvent, post separates excessively, purifying obtains part N-MFPBI.
Above-mentioned part N-MFPBI is analyzed: mass spectrum: (M
+): 672.4; Ultimate analysis: C 87.56, H 8.47, and N 3.97, calculated value: C 87.45, and H 8.39, and N 4.16.
Step 2: the chlorine endo compound of synthetic N-MFPBI
2.5 parts N-MFPBI, 1 part of one hydration iridous chloride, 60 parts of EGMEs, 20 parts of deionized waters are placed the there-necked flask of 250mL, and argon atmosphere stirs 30min, heating reflux reaction 10h down.Cooling is filtered, and washing is to neutral, and oven dry obtains yellow powder, is the chlorine endo compound of N-MFPBI;
Step 3: synthetic two (N-p-methylphenyl-2-(to the biphenylyl pentanoic) benzoglyoxalines)-2,4-diacetylmethane iridium Ir (N-MFPBI)
2Acac
The chlorine endo compound of the N-MFPBI that step 2 is obtained and 5 part 2, the 4-diacetylmethane, 1 part KOH, 30 parts EGME places there-necked flask, and argon atmosphere stirs 15min, heating reflux reaction 15h down.Cooling is filtered, and washing is to neutral, and oven dry obtains Ir (N-MFPBI)
2Acac crude product, crude product are purified through column chromatography and are obtained xanchromatic powder Ir (N-MFPBI)
2Acac.
Mass spectrum: (M
++ 1): 1634.9; Ultimate analysis: C 75.58, H 7.33, and N 3.29, calculated value: C75.65, H 7.21, and N 3.43.
Luminescent device among luminescent device structure and the embodiment 1 is basic identical, and different is with preparing complex of iridium Ir (N-MFPBI) in the present embodiment 9
2Acac replaces Ir (PPBI)
2Acac.
Embodiment 10:
In the present embodiment, the structural formula of N-p-methylphenyl-2-(N '-octyl group-carbazyl) benzoglyoxaline trivalent-iridium organometallic complex is:
The preparation method of above-mentioned N-p-methylphenyl-2-(N '-octyl group-carbazyl) benzoglyoxaline trivalent-iridium organometallic complex comprises the steps:
Step 1: synthetic ligands N-MCzPBI
In the there-necked flask of magnetic stirring apparatus was housed, (4-(4,4 with step 2 synthetic midbody b2:N-p-methylphenyl-2-among 1 part of embodiment 8; 5,5-tetramethyl--1,3; 2-dioxy boron penta ring-2-yl) phenyl)-1H-benzoglyoxaline, 1 part of 3-bromo-N-octyl group carbazole and 0.1 part of four triphenyl phosphorus palladium be dissolved in the toluene of 20 deals; At 105 ℃ of reaction 48h, remove solvent under the nitrogen protection, cross that post separates, purifying obtains part N-MCzPBI.
Above-mentioned part N-MFPBI is analyzed: mass spectrum: (M
+): 561.3; Ultimate analysis: C 85.57, H 6.94, and N 7.49, calculated value: C 85.52, and H 7.00, and N 7.48.
Step 2: the chlorine endo compound of synthetic N-MCzPBI
2.5 parts N-MCzPBI, 1 part of one hydration iridous chloride, 60 parts of EGMEs, 20 parts of deionized waters are placed the there-necked flask of 250mL, and argon atmosphere stirs 30min, heating reflux reaction 10h down.Cooling is filtered, and washing is to neutral, and oven dry obtains yellow powder, is the chlorine endo compound of N-MFPBI;
Step 3: synthetic pair (N-p-methylphenyl-2-(N '-octyl group-carbazyl) benzoglyoxaline)-2,4-diacetylmethane iridium Ir (N-MCzPBI)
2Acac
The chlorine endo compound of the N-MCzPBI that step 2 is obtained and 5 part 2, the 4-diacetylmethane, 1 part KOH, 30 parts EGME places there-necked flask, and argon atmosphere stirs 15min, heating reflux reaction 15h down.Cooling is filtered, and washing is to neutral, and oven dry obtains Ir (N-MCzPBI)
2Acac crude product, crude product are purified through column chromatography and are obtained xanchromatic powder Ir (N-MFPBI)
2Acac.
Mass spectrum: (M
++ 1): 1412.3; Ultimate analysis: C 72.36, H 6.01, and N 5.73, calculated value: C 72.26, and H 5.92, and N 5.95.
Luminescent device among luminescent device structure and the embodiment 1 is basic identical, and different is with preparing complex of iridium Ir (N-MCzPBI) in the present embodiment 10
2Acac replaces Ir (PPBI)
2Acac.
Embodiment 11:
In the present embodiment, the structural formula of N-naphthyl-2-triphen amido benzoglyoxaline trivalent-iridium organometallic complex is:
The preparation method of above-mentioned N-naphthyl-2-triphen amido benzoglyoxaline trivalent-iridium organometallic complex comprises the steps:
Step 1: synthetic intermediate a3:N-naphthyl-2-is to bromophenyl benzoglyoxaline (N-NpBrPBI)
In the 250mL there-necked flask that stirring, TM, gas access equipment are housed, feed argon gas 10min, add 10 parts of parabromobenzoyl chlorides and N-naphthyl-1 successively; 10 parts of reactions of 2-phenylenediamine, 60 parts of 3 parts of triethylamines and THFs react 24h under the room temperature; In 100 parts of deionized waters of reaction solution impouring, adopt dichloromethane extraction to separate, steam methylene dichloride and obtain crude product; Crude product recrystallization in the mixture solution of methyl alcohol and THF obtains gray solid, and this gray solid is dissolved in the 12h that refluxes in 20 parts of acetate, steams acetate; Oven dry obtains pearl midbody a3:N-naphthyl-2-to bromophenyl benzoglyoxaline (N-NpBrPBI).
Above-mentioned midbody a3 is analyzed: mass spectrum: (M
+): 398.2,399.8; Ultimate analysis: C 69.26, H 3.72, and N 7.13, calculated value: C 69.19, and H 3.79, and N 7.02.
Step 2: synthetic intermediate b3:N-naphthyl-2-(4-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) phenyl)-1H-benzoglyoxaline
, the there-necked flask of magnetic stirring apparatus adds 10 parts Potassium ethanoate, 4 parts two glutaryls two boron and 0.2 part of Pd (dppf) Cl in being housed
2Be dissolved in the inferior fen of 200 parts of dimethyl-, under the nitrogen protection, stirring at normal temperature 25min obtains first solution; Then, 2 parts of step 1 synthetic midbody a3:N-naphthyl-2-are added in the inferior fen of dimethyl-of 10 deals bromophenyl benzoglyoxaline (NpBrPBI), obtain second solution; First solution is mixed with second solution, be warming up to 85 ℃, nitrogen protection is reaction 30h down, removes solvent; Cross that post separates, purifying obtains midbody b3:N-naphthyl-2-(4-(4,4,5; 5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) phenyl)-the 1H-benzoglyoxaline.
Above-mentioned midbody b3 is analyzed: mass spectrum: (M
+): 446.1; Ultimate analysis: C 78.09, H 6.11, and N 6.14, calculated value: C 78.04, and H 6.10, and N 6.28.
Step 3: synthetic ligands N-NpTPAPBI
In the there-necked flask of magnetic stirring apparatus was housed, (4-(4,4 with 1 part of step 2 synthetic midbody b3:N-naphthyl-2-; 5,5-tetramethyl--1,3; 2-dioxy boron penta ring-2-yl) phenyl)-the 1H-benzoglyoxaline, bromine triphen benzene and 0.1 part of four triphenyl phosphorus palladium are dissolved in the toluene of 20 deals; At 105 ℃ of reaction 24h, remove solvent under the nitrogen protection, cross that post separates, purifying obtains part N-NpTPAPBI.
Above-mentioned part N-NpTPAPBI is analyzed: mass spectrum: (M
+): 563.1; Ultimate analysis: C 86.15, H 5.12, and N 8.73, calculated value: C 87.36, and H 5.19, and N 7.45.
Step 4: the chlorine endo compound of synthetic N-NpTPAPBI
2.5 parts PPBI, 1 part of one hydration iridous chloride, 60 parts of EGMEs, 20 parts of deionized waters are placed the there-necked flask of 250mL, and argon atmosphere stirs 30min, heating reflux reaction 10h down.Cooling is filtered, and washing is to neutral, and oven dry obtains yellow powder, is the chlorine endo compound of N-NpTPAPBI;
Step 5: synthetic two (N-naphthyls-2-triphen amido benzoglyoxaline)-2,4-diacetylmethane iridium Ir (N-NpTPAPBI)
2Acac
The chlorine endo compound of the N-NpTPAPBI that step 4 is obtained and 10 part 2, the 4-diacetylmethane, 2 parts KOH, 60 parts EGME places there-necked flask, and argon atmosphere stirs 30min, heating reflux reaction 30h down.Cooling is filtered, and washing is to neutral, and oven dry obtains Ir (N-NpTPAPBI)
2Acac crude product, crude product are purified through column chromatography and are obtained xanchromatic powder Ir (N-NpTPAPBI)
2Acac.
Mass spectrum: (M
++ 1): 1416.1; Ultimate analysis: C 73.92, H 4.24, and N 5.88, calculated value: C 73.76, and H 4.48, and N 5.93.
Luminescent device among luminescent device structure and the embodiment 1 is basic identical, and different is with preparing complex of iridium Ir (N-NpTPAPBI) in the present embodiment 11
2Acac replaces Ir (PPBI)
2Acac.
Embodiment 12:
In the present embodiment, the structural formula of the basic benzoglyoxaline trivalent-iridium organometallic complex of N-fluorenyl-2-(3 '-triphenylamine) is:
The preparation method of the basic benzoglyoxaline trivalent-iridium organometallic complex of above-mentioned N-fluorenyl-2-(3 '-triphenylamine) comprises the steps:
Step 1: synthetic intermediate a4:N-(3 '-triphenylamine) base-2-is to bromophenyl benzoglyoxaline (N-FBrPBI)
In the 250mL there-necked flask that stirring, TM, gas access equipment are housed, feed argon gas 10min, add 10 parts of parabromobenzoyl chlorides and N-(9 successively; 9 ' dibutyl) fluorenyl-1,10 parts of reactions of 2-phenylenediamine, 60 parts of 3 parts of triethylamines and THFs; React 24h under the room temperature, in 100 parts of deionized waters of reaction solution impouring, adopt dichloromethane extraction to separate; Steam methylene dichloride and obtain crude product, crude product recrystallization in the mixture solution of methyl alcohol and THF obtains gray solid, and this gray solid is dissolved in the 12h that refluxes in 20 parts of acetate; Steam acetate; Oven dry obtains pearl midbody a4:N-(9,9 ' dibutyl) fluorenyl-2-to bromophenyl benzoglyoxaline (N-FBrPBI).
Above-mentioned midbody a4 is analyzed: mass spectrum: (M
+): 548.3,550.1; Ultimate analysis: C 74.23, H 5.97, and N 5.21, calculated value: C 74.31, and H 6.05, and N 5.10.
Step 2: synthetic intermediate b4:N-(3 '-triphenylamine) base-2-(4-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) phenyl)-1H-benzoglyoxaline
, the there-necked flask of magnetic stirring apparatus adds 5 parts Potassium ethanoate, 2 parts two glutaryls two boron and 0.1 part of Pd (dppf) Cl in being housed
2Be dissolved in the inferior fen of 200 parts of dimethyl-, under the nitrogen protection, stirring at normal temperature 25min obtains first solution; Then, 2 parts of step 1 synthetic midbody a4:N-(3 '-triphenylamine) base-2-is added in the inferior fen of dimethyl-of 5 deals bromophenyl benzoglyoxaline (N-FBrPBI), obtain second solution; First solution is mixed with second solution, be warming up to 85 ℃, nitrogen protection is reaction 15h down, removes solvent; Cross that post separates, purifying obtains midbody b4:N-(3 '-triphen amido)-2-(4-(4,4,5; 5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) phenyl)-the 1H-benzoglyoxaline.
Above-mentioned midbody b4 is analyzed: mass spectrum: (M
+): 596.1; Ultimate analysis: C 80.17, H 7.33, and N 4.84, calculated value: C 80.53, and H 7.60, and N 4.70.
Step 3: synthetic ligands N-F-3-TPAPBI
In the there-necked flask of magnetic stirring apparatus was housed, (4-(4,4 with 1 part of step 2 synthetic midbody b4:N-(3 '-triphenylamine) base-2-; 5,5-tetramethyl--1,3; 2-dioxy boron penta ring-2-yl) phenyl)-1H-benzoglyoxaline, 1 part of bromobenzene and 0.1 part of four triphenyl phosphorus palladium be dissolved in the toluene of 10 deals; At 105 ℃ of reaction 12h, remove solvent under the nitrogen protection, cross that post separates, purifying obtains part N-F-3-TPAPBI.
Above-mentioned part N-F-3-TPAPBI is analyzed: mass spectrum: (M
+): 713.2; Ultimate analysis: C 87.58, H 6.67, and N 5.75, calculated value: C 87.48, and H 6.64, N5.89.
Step 4: the chlorine endo compound of synthetic N-F-3-TPAPBI
2.5 parts N-F-3-TPAPBI, 1 part of one hydration iridous chloride, 60 parts of EGMEs, 20 parts of deionized waters are placed the there-necked flask of 250mL, and argon atmosphere stirs 30min, heating reflux reaction 10h down.Cooling is filtered, and washing is to neutral, and oven dry obtains yellow powder, is the chlorine endo compound of N-F-3-TPAPBI;
Step 5: synthetic two (N-(3 '-triphenylamine) base-2-Phenylbenzimidazoles)-2,4-diacetylmethane iridium Ir (N-F-3-TPAPBI)
2Acac
The chlorine endo compound of the N-F-3-TPAPBI that step 4 is obtained and 5 part 2, the 4-diacetylmethane, 1 part KOH, 30 parts EGME places there-necked flask, and argon atmosphere stirs 15min, heating reflux reaction 15h down.Cooling is filtered, and washing is to neutral, and oven dry obtains Ir (N-F-3-TPAPBI)
2Acac crude product, crude product are purified through column chromatography and are obtained xanchromatic powder Ir (N-F-3-TPAPBI)
2Acac.
Mass spectrum: (M
++ 1): 1717.1; Ultimate analysis: C 76.11, H 5.74, and N 4.39, calculated value: C 76.24, and H 5.81, and N 4.89.
Luminescent device among luminescent device structure and the embodiment 1 is basic identical, and different is with preparing complex of iridium Ir (N-F-3-TPAPBI) in the present embodiment 12
2Acac replaces Ir (PPBI)
2Acac.
Among the foregoing description 1-12, the performance of organophosphorus photodoping type electroluminescent device is as shown in table 1 below:
Table 1: the performance table of organophosphorus photodoping type electroluminescent device among the embodiment 1-12
From above-mentioned table 1, can find out; Through changing the doping guest materials in the electroluminescent device luminescent layer; Control the thickness of its concentration and each functional layer, can access the higher electro-phosphorescent luminescent device of performance, realize that the electroluminescent spectrum peak value is the yellow emission of 560-610nm.Therefore, N-substituted-phenyl imidazoles acene class trivalent-iridium organometallic complex of the present invention can be applied in monochrome, panchromatic demonstration and illumination white light parts.
Above-described embodiment specifies technical scheme of the present invention; Be understood that the above is merely specific embodiment of the present invention; Be not limited to the present invention; All any modifications of in principle scope of the present invention, being made, replenish or similar fashion substitutes etc., all should be included within protection scope of the present invention.
Claims (9)
1. N-substituted-phenyl benzimidazoles trivalent-iridium organometallic complex, it is characterized in that: its structural formula is:
Wherein: R
1, R
2Independently be selected from hydrogen, C respectively
1-C
4Alkyl, C
1-C
4In haloalkyl, aromatic base, condensed ring group, anilino, carbazyl, the fluorenyl any one.
2. the preparation method of N-substituted-phenyl benzimidazoles trivalent-iridium organometallic complex as claimed in claim 1 is characterized in that: comprise the steps:
Step 1: substituted benzene acyl chlorides and 2-amido disubstituted benzenes amine are the synthetic N-substituted-phenyl benzimidizole derivatives of raw material;
Step 2: replacing bromo phenyl benzimidizole derivatives with step 1 synthetic N-is the synthetic N-substituted-phenyl benzoglyoxaline boric acid of raw material that ester derivative frequently;
Step 3: step 2 synthetic N-substituted-phenyl benzoglyoxaline boric acid that ester derivative of frequency and various bromo group carry out the SUZUKI reaction, obtain corresponding ligand material;
Step 4: the corresponding chlorine endo compound of preparation of the ligand material that step 3 obtains and iridous chloride reaction;
Step 5: the chlorine endo compound and 2 that step 4 obtains, the reaction of 4-diacetylmethane obtains corresponding phosphor material.
3. organophosphorus photodoping electroluminescent device; Constitute laminate structure by substrate (1), nesa coating (2), hole injection layer (3), luminescent layer (4), electron injecting layer (5) and negative electrode (6) successively, it is characterized in that: described luminescent layer (4) is to be dissolved in the mixture that forms in the chlorobenzene altogether by material of main part PVK, guest materials and PBD to be spin-coated on the thin film layer that hole injection layer (3) surface forms; Described guest materials is the described N-substituted-phenyl of claim 1 an imidazoles acene class trivalent-iridium organometallic complex.
4. organophosphorus photodoping electroluminescent device as claimed in claim 3 is characterized in that: the mass ratio of material of main part, guest materials and PBD is 70 in the described luminescent layer (4): 1-10: 30.
5. like claim 3 or 4 described organophosphorus photodoping electroluminescent devices, it is characterized in that: described hole injection layer (3) is for gathering 3,4-enedioxy thiophene and poly styrene sulfonate material.
6. like claim 3 or 4 described organophosphorus photodoping electroluminescent devices, it is characterized in that: the thickness of described hole injection layer (3) is 30-50nm.
7. like claim 3 or 4 described organophosphorus photodoping electroluminescent devices, it is characterized in that: described luminescent layer (4) thickness is 70-80nm.
8. like claim 3 or 4 described organophosphorus photodoping electroluminescent devices, it is characterized in that: the material of described electron injecting layer (5) is LiF, MoO
3, WO
3
9. organophosphorus photodoping electroluminescent device as claimed in claim 8 is characterized in that: the thickness of described electron injecting layer (5) is 0.5-2nm.
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| CN102863391A (en) * | 2012-09-21 | 2013-01-09 | 浙江欧普光电科技有限公司 | Compound containing 4-N-substituted phenyl-benzimidazole and preparation method thereof |
| CN102863391B (en) * | 2012-09-21 | 2015-04-15 | 浙江欧普光电科技有限公司 | Compound containing 4-N-substituted phenyl-benzimidazole and preparation method thereof |
| CN103666460A (en) * | 2013-12-27 | 2014-03-26 | 武汉大学 | Low-triplet-state-energy-level blue-light phosphorescent main body material and application thereof |
| JP2015199685A (en) * | 2014-04-08 | 2015-11-12 | 住友化学株式会社 | Metal complex and light emitting element made using the metal complex |
| CN106146568A (en) * | 2015-04-23 | 2016-11-23 | 上海和辉光电有限公司 | A kind of compound and its preparation method and application |
| CN108641707A (en) * | 2018-05-30 | 2018-10-12 | 武汉华星光电半导体显示技术有限公司 | The preparation method of OLED luminescent materials |
| US10868259B2 (en) | 2018-05-30 | 2020-12-15 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Method for manufacturing OLED light-emitting material |
| CN113105510A (en) * | 2021-04-16 | 2021-07-13 | 吉林省元合电子材料有限公司 | Metal iridium complex and organic electroluminescent device with complex as light-emitting layer |
| CN113105510B (en) * | 2021-04-16 | 2022-07-08 | 吉林省元合电子材料有限公司 | Metal iridium complex and organic electroluminescent device with complex as luminescent layer |
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