CN103666450A

CN103666450A - Blue-light organic electrophosphorescence material, and preparation method and application thereof

Info

Publication number: CN103666450A
Application number: CN201210363797.2A
Authority: CN
Inventors: 周明杰; 王平; 张娟娟; 张振华
Original assignee: Oceans King Lighting Science and Technology Co Ltd; Shenzhen Oceans King Lighting Engineering Co Ltd
Current assignee: Oceans King Lighting Science and Technology Co Ltd; Shenzhen Oceans King Lighting Science and Technology Co Ltd; Shenzhen Oceans King Lighting Engineering Co Ltd
Priority date: 2012-09-26
Filing date: 2012-09-26
Publication date: 2014-03-26

Abstract

The invention belongs to the field of organic semiconductor materials, and discloses a blue-light organic electrophosphorescence material, and a preparation method and application thereof. The material has the following structural formula, wherein R is a hydrogen atom, C1-C6 alkyl group or C1-C6 alkoxy group; and LK is an auxiliary ligand contained by an iridium metal complex. The blue-light organic electrophosphorescence material disclosed by the invention uses 2,3'-dipyridine as a major structure of the ring metal ligand, and the introduction of the alkyl and alkoxy groups can obtain satisfactory energy transfer efficiency and blue-light emitting wavelength and can a certain steric hindrance effect, thereby reducing the direct actions among metal atoms, reducing the self-quenching phenomenon of triplet-state excitons and greatly enhancing the light conversion efficiency of the material; and meanwhile, the Cl substitution on the ring metal ligand can improve the luminescence property, facilitate vapor deposition, improve the film-forming property, enhance the stability of the device and enhance the color purity.

Description

Blue light organic phosphorescent electroluminescent materials and its preparation method and application

Technical field

The present invention relates to organic semiconductor material, relate in particular to a kind of blue light organic phosphorescent electroluminescent materials and its preparation method and application.

Background technology

Organic electroluminescent refers to that organic materials is under electric field action, electric energy is converted into a kind of luminescence phenomenon of luminous energy.In early days former because the driving voltage of organic electroluminescence device is too high, luminous efficiency is very low etc. thereby make the research of organic electroluminescent stay cool.Until 1987, the human hairs such as the Tang of Kodak understand with oxine aluminium (Alq ₃) be luminescent material, make the high-quality thin film of even compact with aromatic diamine, made low-work voltage, high brightness, high efficiency organic electroluminescence device, opened the new prelude to electroluminescent organic material research.But due to the restriction of the statistical theory that is subject to spinning, the theoretical internal quantum efficiency limit of fluorescent material is only 25%, how makes full use of all the other phosphorescence of 75% and realize higher luminous efficiency and become the hot research direction in this field after this.1997, Forrest etc. found electrophosphorescence phenomenon, and the internal quantum efficiency of electroluminescent organic material has been broken through 25% restriction, makes the research of electroluminescent organic material enter another new period.

In research subsequently, the title complex of small molecules doping type transition metal has become people's research emphasis, as the title complex of iridium, ruthenium, platinum etc.The advantage of this class title complex is that they can obtain very high emitted energy from the triplet state of self, and metal iridium (III) compound wherein, due to good stability, in building-up process, reaction conditions is gentle, and there is very high electroluminescent properties, in research process subsequently, accounting for dominant position always.And in order to make device obtain full-color demonstration, generally must obtain ruddiness, green glow and the blue light material of excellent performance simultaneously.Compare with green light material with ruddiness, the development of blue light material lags behind comparatively speaking, and the light conversion efficiency that improves blue light material has just become the breakthrough point of people's researchs with purity of color.

Summary of the invention

Problem to be solved by this invention is to provide a kind of light conversion efficiency the higher and higher blue light organic phosphorescent electroluminescent materials of purity of color.

The present invention also provides the preparation method of this blue light organic phosphorescent electroluminescent materials.

The present invention also provides the application as luminescent material in organic electroluminescence device of this blue light organic phosphorescent electroluminescent materials.

Technical scheme of the present invention is as follows:

A blue light organic phosphorescent electroluminescent materials, is characterized in that, this material has following structural formula:

In formula, R is hydrogen atom, C ₁~ C ₆alkyl or C ₁~ C ₆alkoxyl group; LK is the contained assistant ligand of iridium metal complex, and LK is respectively the assistant ligand with following structural formula:

Described blue light organic phosphorescent electroluminescent materials, wherein, R is C ₁~ C ₆straight chained alkyl or C ₁~ C ₆branched-chain alkyl; Or R is C ₁~ C ₆straight chain alkoxyl group or C ₁~ C ₆branched alkoxy.

The preparation method of above-mentioned blue light organic phosphorescent electroluminescent materials, comprises the steps:

Under protection of inert gas, by structural formula, be

compound D and structural formula be

compd A according to 1: 1.2 ratio of mol ratio, join in the first solvent that contains alkali and catalyzer, obtain mixing solutions, then mixing solutions is heated to 100 ℃, stirring reaction 20h, is chilled to after room temperature, obtains structural formula to be

compd B;

Under protection of inert gas, it is in the cellosolvo of 3:1 and the mixed solvent of water that the compd B that is 2.2:1 by mol ratio and three hydration iridous chlorides are dissolved in volume ratio, and stirring reaction 24h under reflux state is chilled to and obtains structural formula after room temperature and be

compound C;

Under protection of inert gas; the represented contained assistant ligand of iridium metal complex of the Compound C that is 1:2.2 ~ 3:1 by mol ratio and LK is dissolved in cellosolvo, and heated solution is warming up to reflux state, stirring reaction 24h; naturally be chilled to after room temperature, obtain structural formula and be

described blue light organic phosphorescent electroluminescent materials;

Above-mentioned various in, R is hydrogen atom, C ₁~ C ₆alkyl or C ₁~ C ₆alkoxyl group; What X and Y were separate is halogen atom; LK is the contained assistant ligand of iridium metal complex, and LK is respectively the assistant ligand with following structural formula:

The preparation method of described blue light organic phosphorescent electroluminescent materials, wherein, R is C ₁~ C ₆straight chained alkyl or C ₁~ C ₆branched-chain alkyl; Or R is C ₁~ C ₆straight chain alkoxyl group or C ₁~ C ₆branched alkoxy.

The preparation method of described blue light organic phosphorescent electroluminescent materials, wherein, described alkali is K ₂cO ₃or Na ₂cO ₃; The molar weight of described alkali is 2 ~ 5 times of Compound D molar weight.

The preparation method of described blue light organic phosphorescent electroluminescent materials, wherein, described catalyzer is tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride, the molar weight of catalyzer is 0.05 times of Compound D molar weight.

The preparation method of described blue light organic phosphorescent electroluminescent materials, wherein, described the first solvent is that volume ratio is the toluene of 6:1 and the mixed solvent of water or DMF and water.

Blue light organic phosphorescent electroluminescent materials provided by the invention, it is with 2,3 '-dipyridyl is cyclic metal complexes agent structure, the introducing of alkyl, alkoxyl group can obtain satisfied energy transmission efficiency and blue light emitting wavelength, and can produce certain space steric effect, thereby the direct effect between minimizing atoms metal, reduces the self-quenching phenomenon of triplet exciton, has greatly improved the light conversion efficiency of material; Meanwhile, the Cl that carries out on cyclic metal complexes replaces, and can improve luminescent properties, is beneficial to evaporation, increases film-forming type and improves the stability of device, has improved purity of color.

Synthesizing of blue light organic phosphorescent electroluminescent materials provided by the invention, what adopt is Suzuki coupling method, allow with the bromo on the boric acid base group on the pyridine ring of halogenic substituent and another pyridine ring in suitable solvent, under the effect of alkali and palladium catalyst, linked reaction occur, this coupling method technology maturation, raw material are easy to get, reaction conditions gentle, and reaction yield is more high; Cyclic metal complexes generates corresponding containing iridium dichloro dimer with three hydration iridous chlorides reactions in the cellosolvo solvent refluxing, the dimer crude product making can drop in next step reaction without further purification, reaction unit is simple, and synthetic operation is easy; In suitable solvent, there is ligand exchange reaction with corresponding assistant ligand raw material and generate corresponding ultimate aim title complex in dipolymer.

Accompanying drawing explanation

Fig. 1 is the utilizing emitted light spectrogram of the blue light organic phosphorescent electroluminescent materials that makes of embodiment 1;

Fig. 2 is the organic electroluminescence device structural representation of embodiment 29; Wherein:

101 glass substrate 102 anode 103 hole injection layers

104 hole transmission layer 105 electronic barrier layer 106 luminescent layers

107 hole blocking layer 108 electron transfer layer 109 electronic injection buffer layers

110 negative electrodes.

Embodiment

The invention reside in and select with 2,3 '-dipyridyl or derivatives thereof is cyclic metal complexes, with 2-pyridine formyl, four pyrazoles boron, 3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole or 5-(2 '-pyridyl)-1,2,3,4-tetrazolium is wherein a kind of is assistant ligand, synthetic a kind of iridium metal complexes of blue light organic phosphorescent electroluminescent materials, and pass through cyclic metal complexes 2, the chemically modified of 3 '-dipyridyl realizes the adjusting to material glow color, thereby obtains the more blue phosphorescent emissions of emission wavelength.The object of the present invention is to provide a kind of like this blue light organic phosphorescent material iridium metal complex and preparation thereof.

Blue light organic phosphorescent electroluminescent materials of the present invention, its structural formula is as follows:

In formula, R is hydrogen atom, C ₁~ C ₆alkyl or C ₁~ C ₆alkoxyl group;

represent assistant ligand, it is in same assistant ligand structure with two haptos of iridium (Ir) coordination that semicircle represents on assistant ligand;

Preferably R is C ₁~ C ₆straight chained alkyl or C ₁~ C ₆branched-chain alkyl or R can be C ₁~ C ₆straight chain alkoxyl group or C ₁~ C ₆branched alkoxy;

That X and Y are separate is Cl;

LK is the contained assistant ligand of iridium metal complex, and LK is respectively the assistant ligand with following structural formula:

(being 2-pyridine formyl),

(i.e. four pyrazoles boron),

(being 3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) or

(being 5-(2 '-pyridyl)-pyrrotriazole).

Blue light organic phosphorescent electroluminescent materials provided by the invention, it is with 2,3 '-dipyridyl is cyclic metal complexes agent structure, the introducing of alkyl, alkoxyl group can obtain satisfied energy transmission efficiency and blue light emitting wavelength, and can produce certain space steric effect, thereby the direct effect between minimizing atoms metal, reduces the self-quenching phenomenon of triplet exciton, has greatly improved the light conversion efficiency of material; Meanwhile, meanwhile, the F carrying out on cyclic metal complexes, Cl replace, and can improve luminescent properties, are beneficial to evaporation, increase film-forming type and improve the stability of device, have improved purity of color.

The synthetic route of blue light organic phosphorescent electroluminescent materials provided by the invention is:

With Cl pyridine ring and another pyridine ring or its with alkyl, alkoxyl group substitutive derivative by the synthetic cyclic metal complexes of Suzuki coupling, then with IrCl ₃3H ₂o reaction generates chlorine bridge dipolymer, finally reacts with 2-pyridine carboxylic acid, or at NaOCH ₃and AgOCOCF ₃act on lower and four pyrazoles boronation nak responses, or at alkali (NaOCH ₃) under effect respectively with 3-trifluoromethyl-5-(pyridine-2 '-yl)-1,2,4-triazole and 5-(pyridine-2 '-yl)-pyrrotriazole reaction makes the iridium metal complex of blue light organic phosphorescent electroluminescent materials.

S1, under rare gas element (rare gas element of the present invention comprises nitrogen, argon gas or nitrogen and argon gas mixed gas, following similar) protection, by structural formula, be

compound D (when R is H, name 2-bromopyridine; When R is alkyl, called after 4-alkyl-2-bromopyridine; When R is alkoxyl group, called after 4-alkoxyl group-2-bromopyridine) with structural formula be

compd A (2,6-, bis-halogens-3-pyridine boric acid) according to mol ratio 1:1.2 ratio, join in the first solvent that contains alkali and catalyzer, obtain mixing solutions, then mixing solutions is heated to 100 ℃, stirring reaction 20h, is chilled to after room temperature, obtains structural formula to be compd B (when R is H, called after 2 ', 6 '-bis-is chloro-2,3 '-dipyridyl; When R is alkyl, called after 2, chloro-4 '-alkyl-4 of 6-bis-, 2 '-dipyridyl; When R is alkoxyl group, called after 2, chloro-4 '-alkoxyl group-4 of 6-bis-, 2 '-dipyridyl); Reaction formula is as follows:

Preferably, after reaction finishes, compd B is carried out to purification process:

After reaction finishes, by the aqueous phase separation in reaction mixture, and with the extraction of 100mL ethyl acetate repeatedly, then merge organic phase, then the organic phase merging with salt water washing, anhydrous magnesium sulfate drying, filtration, rotation is steamed and is desolventized to obtain crude product; The trichloromethane that the volume ratio of take is subsequently 1:3 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain the white solid product of purification process, i.e. compd B;

S2, under protection of inert gas, the compd B that is 2.2:1 by mol ratio and three hydration iridous chloride (IrCl ₃3H ₂o) being dissolved in volume ratio is in the cellosolvo of 3:1 and the mixed solvent of water, under reflux state (in view of the boiling point of cellosolvo is 135 ℃, the boiling point of water is 100 ℃, the boiling point of mixed solvent is 100 ~ 135 ℃ between the two, therefore, reflux temperature is 100 ~ 135 ℃) stirring reaction 24h, be chilled to and obtain structural formula after room temperature and be

compound C (when R is H, called after cyclic metal complexes is that 2,6-bis-is chloro-4,2 '-dipyridyl containing iridium dichloro dimer; When R is alkyl, name cyclic metal complexes is chloro-4 '-alkyl-4 of 2,6-bis-, 2 '-dipyridyl containing iridium dichloro dimer; When R is alkoxyl group, name cyclic metal complexes is chloro-4 '-alkoxyl group-4 of 2,6-bis-, 2 '-dipyridyl containing iridium dichloro dimer); Reaction formula is as follows:

Preferably, after reaction finishes, Compound C is carried out to purification process:

Question response liquid cooling, to room temperature, has Precipitation in mixed solution, rotate and steam except partial solvent, adds distilled water, filters, and solid with distilled water, methyl alcohol, washing with acetone, obtains white solid thing, i.e. Compound C with this after vacuum-drying;

S3, under protection of inert gas; (cyclic metal complexes is 2 ' to the Compound C that is 1:2.2 ~ 3:1 by mol ratio; 6 '-bis-halogen-2; 3 '-dipyridyl containing iridium dichloro dimer) be dissolved in cellosolvo with the contained assistant ligand of the represented iridium metal complex of LK; heated solution is warming up to 135 ℃ of reflux states; stirring reaction 24h, is chilled to after room temperature naturally, obtains structural formula to be

described blue light organic phosphorescent electroluminescent materials; Reaction formula is:

(being 2-pyridine formyl),

(i.e. four pyrazoles boron),

(being 3-trifluoromethyl-5-(2 '-pyridyl)-1,2,4-triazole) or

(being 5-(2 '-pyridyl)-pyrrotriazole).

The preparation method of described blue light organic phosphorescent electroluminescent materials, wherein, preferably R is C ₁~ C ₆straight chained alkyl or C ₁~ C ₆branched-chain alkyl or R be C ₁~ C ₆straight chain alkoxyl group or C ₁~ C ₆branched alkoxy.

The preparation method of described blue light organic phosphorescent electroluminescent materials, wherein, alkali described in step S1 is K ₂cO ₃or Na ₂cO ₃; The molar weight of described alkali is 2 ~ 5 times of Compound D molar weight.

The preparation method of described blue light organic phosphorescent electroluminescent materials, wherein, catalyzer described in step S1 is tetrakis triphenylphosphine palladium (Pd (PPh ₃) ₄) or two (triphenylphosphine) palladium chloride (Pd (PPh ₃) ₂cl ₂), the molar weight of catalyzer is 0.05 times of Compound D molar weight.

The preparation method of described blue light organic phosphorescent electroluminescent materials, wherein, the first solvent described in step S1 is that volume ratio is the mixed solvent of 6:1 toluene and water or DMF (DMF) and water.

Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.

Embodiment 1

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (2-pyridine formyl) close iridium

(1) 2,6-bis-is chloro-4,2 '-dipyridyl synthetic

Under nitrogen protection, (0.95g, 6.00mmol) 2-bromopyridine, (1.38g, 7.20mmol) 2, the chloro-4-pyridine of 6-bis-boric acid, (0.276g, 20mmol) K ₂cO ₃and (0.2311g, 0.20mmol) Pd (PPh ₃) ₄be dissolved in the mixing solutions of 30mL toluene and 5mL water, be heated to 100 ℃, stirring reaction 24h.Be chilled to after room temperature, by the aqueous phase separation in reaction mixture, and with ethyl acetate 100mL extraction three times, merge organic phase.The organic phase merging with salt water washing, anhydrous magnesium sulfate drying.Filter, rotation is steamed and is desolventized to obtain crude product.The trichloromethane that the volume ratio of take is 1:1 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain white solid thing 0.85g, and yield is 62.9%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 224.0 (M ⁺+ 1)

Ultimate analysis (%) C10H6Cl2N2: theoretical value C.53.36; H.2.69; Cl.31.50; N.12.45; Measured value: C.53.31; H.2.72; Cl.31.55; N.12.42.

(2) part is that 2,6-bis-is chloro-4,2 '-dipyridyl dimeric synthetic containing iridium dichloro

Under nitrogen protection, 0.99g (4.4mmol) 2,6-bis-is chloro-4, and 2 '-dipyridyl and 0.63g (2mmol) three hydration iridous chlorides are dissolved in 30mL cellosolvo/water (3/1) mixed solution, stirring reaction 24h under reflux state.Liquid cooling to be mixed, to room temperature, has Precipitation in mixed solution.Rotation is steamed except partial solvent, adds appropriate distilled water, filters.Solid with distilled water, methyl alcohol, washing with acetone, obtains white solid thing 0.82g with this after vacuum-drying, yield is 60.7%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 1349.8 (M ⁺+ 1)

Ultimate analysis (%) C40H20Cl10Ir2N8: theoretical value C, 35.55; H, 1.49; Cl, 26.23; Ir, 28.44; N, 8.29; Measured value: C, 35.50; H, 1.47; Cl, 26.29; Ir, 28.40; N, 8.34.

(3) two (2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C for title complex ²') (2-pyridine formyl) close the synthetic of iridium

Under nitrogen protection; 1.35g (1mmol) part is that 2,6-bis-is chloro-4, being dissolved in 30mL2-ethoxy ethanol containing iridium dichloro dimer and 0.27g (2.20mmol) 2-pyridine carboxylic acid of 2 '-dipyridyl; be heated to reflux state, stirring reaction 24h.Naturally be chilled to after room temperature, progressively drip the 1N HCl aqueous solution, in reaction solution, have Precipitation.Filter, solid is used a small amount of normal hexane, the ultrasonic lower washing of ether successively.Methylene dichloride/sherwood oil mixed solution that the volume ratio of take is 1: 1, as elutriant carries out silica gel column chromatography separation, obtains final title complex 0.64g, and yield is 42.0%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 761.0 (M ⁺+ 1)

Ultimate analysis (%C26H14Cl4IrN5O2 theoretical value: C, 40.96; H, 1.85; Cl, 18.60; Ir, 25.21; N, 9.19; O, 4.20; Measured value: C, 40.90; H, 1.88; Cl, 18.63; Ir, 25.14; N, 9.18; O, 4.28.

As shown in Figure 2, transverse axis is wavelength (Wavelength, the nm of unit), and the longitudinal axis is standardized photoluminescence intensity (Normalized PL intensity), and end product is CH at 298K temperature ₂cl ₂solution (~ 10 ^-5the maximum emission peak of middle emmission spectrum M), at 453nm place, has an acromion at 478nm place simultaneously, can be used as the preparation field that blue light electroluminescent material is widely used in organic electroluminescence device.

Embodiment 2

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (four pyrazoles boron) close iridium

(1) 2,6-bis-is chloro-4, the synthesis step of 2 '-dipyridyl

The step (1) of this step embodiment 1 is identical;

(2) part is that 2,6-bis-is chloro-4,2 '-dipyridyl containing the dimeric synthesis step of iridium dichloro

This step is identical with the step (2) of embodiment 1;

(3) title complex two (2 ', 6 '-bis-chloro-2,4 '-dipyridyl-N, C2 ') (four pyrazoles boron) closes the synthetic of iridium

Under nitrogen protection; it is 2 containing 1.35g (1mmol) part that 50mL is slowly added drop-wise to 60mL containing the methanol solution of 0.54g (2.1mmol) AgOTf; 6-bis-is chloro-4,2 '-dipyridyl containing in the dimeric dichloromethane solution of iridium dichloro, stirring reaction 2h under room temperature.Whizzer separation obtains settled solution after removing AgCl, and rotary evaporation desolventizes.Under nitrogen protection, residue and 0.95 (3mmol) KBpz ₄be dissolved in 50mL acetonitrile back flow reaction 24h.Be chilled to room temperature, filter, the appropriate washed with dichloromethane of filter residue, merging filtrate, rotation is steamed and is desolventized, and obtains crude product.Crude product is used methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization obtains pure products 0.55g, and productive rate is 30.0%.

Mass spectrum (m/z): 920.1 (M ⁺+ 1)

Ultimate analysis (%) C32H24BCl4IrN12 theoretical value: C, 41.71; H, 2.63; B, 1.17; Cl, 15.39; Ir, 20.86; N, 18.24; Measured value: C, 41.61; H, 2.65; B, 1.20; Cl, 15.35; Ir, 20.89; N, 18.30.

Embodiment 3

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (3-trifluoromethyl-5-(pyridine-2 '-yl)-1,2,4-triazole) close iridium

(1) 2,6-bis-is chloro-4, the synthesis step of 2 '-dipyridyl

The step (1) of this step embodiment 1 is identical;

The step (2) of this step embodiment 1 is identical;

(3) two (2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C for title complex ²') (3-trifluoromethyl-5-(pyridine-2 '-yl)-1,2,4-triazole) close the synthetic of iridium

Under nitrogen protection; 0.64g (3mmol) 3-trifluoromethyl-5-(pyridine-2-yl)-1; 2; 4-triazole and 1.35g (1mmol) part is 2; 6-bis-is chloro-4, and being dissolved in 60mL trichloromethane containing iridium dichloro dimer of 2 '-dipyridyl, under the katalysis of 0.54g (10mmol) sodium methylate; stirring heating is warming up to reflux state, reaction 24h.Naturally be chilled to after room temperature, concentrate and remove a part of solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, successively with deionized water, ether washing for several times, the product of acquisition is dry obtains 0.71g pure products by by tubing string chromatography purification to solid, and yield is 41.7%.

Mass spectrum (m/z): 854.0 (M ⁺+ 1)

Ultimate analysis (%) C28H14Cl4F3IrN8 theoretical value: C, 39.40; H, 1.65; Cl, 16.62; F, 6.68; Ir, 22.52; N, 13.13; Measured value: C, 39.33; H, 1.67; Cl, 16.65; F, 6.65; Ir, 22.55; N, 13.15.

Embodiment 4

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (5-(pyridine-2 '-yl)-pyrrotriazole) close iridium

(1) 2,6-bis-is chloro-4, the synthesis step of 2 '-dipyridyl

The step (1) of this step embodiment 1 is identical;

The step (2) of this step embodiment 1 is identical;

(3) two (2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C for title complex ²') (5-(pyridine-2 '-yl)-pyrrotriazole) close the synthetic of iridium

Under nitrogen protection; 0.64g (3mmol) 5-(pyridine-2 '-yl)-1; 2; 3,4-tetrazolium and 1.35g (1mmol) part is 2,6-bis-chloro-4; being dissolved in 60mL trichloromethane containing iridium dichloro dimer of 2 '-dipyridyl; under the katalysis of 0.54g (10mmol) sodium methylate, stirring heating is warming up to reflux state, reaction 24h.Naturally be chilled to after room temperature, concentrate and remove a part of solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, successively with deionized water, ether washing for several times, the product of acquisition is dry obtains 0.60g pure products by by tubing string chromatography purification to solid, and yield is 38.1%.

Mass spectrum (m/z): 787.0 (M ⁺+ 1)

Ultimate analysis (%) C26H14Cl4IrN9 theoretical value: C, 39.71; H, 1.79; Cl, 18.03; Ir, 24.44; N, 16.03; Measured value: C, 39.65; H, 1.76; Cl, 18.10; Ir, 24.41; N, 16.08.

Embodiment 5

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (4-methyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (2-pyridine formyl) close iridium

(1) chloro-4 '-methyl-4 of 2,6-bis-, 2 '-dipyridyl synthetic

Under argon shield, (0.69g, 4.00mmol) 4-methyl-2-bromopyridine, (0.92g, 4.80mmol) 2, the chloro-4-pyridine of 6-bis-boric acid, (2.12g, 20mmol) Na ₂cO ₃and (0.1404g, 0.20mmol) Pd (PPh ₃) ₂cl ₂be dissolved in the mixing solutions of 30mL toluene and 5mL water, be heated to reflux state, stirring reaction 25h.Be chilled to after room temperature, by the aqueous phase separation in reaction mixture, and with ethyl acetate 100mL extraction three times, merge organic phase.The organic phase merging with salt water washing, anhydrous magnesium sulfate drying.Filter, rotation is steamed and is desolventized to obtain crude product.The ethyl acetate that the volume ratio of take is 1:5 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain white solid thing 0.61g, and yield is 63.8%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 238.0 (M ⁺+ 1)

Ultimate analysis: C ₁₁h ₈cl ₂n ₂theoretical value: C.55.26; H.3.37; Cl.29.66; N.11.72; Measured value: C.55.25; H.3.36; Cl.29.67; N.11.73.

(2) part is chloro-4 '-methyl-4 of 2,6-bis-, 2 '-dipyridyl dimeric synthetic containing iridium dichloro

Under argon shield; 1.05g (4.4mmol) 4-methyl-2; 6-bis-is chloro-2, and 4 '-dipyridyl and 0.63g (2mmol) three hydration iridous chlorides are dissolved in 30mL cellosolvo/water (3/1) mixed solution, stirring reaction 24h under reflux state.Liquid cooling to be mixed, to room temperature, has Precipitation in mixed solution.Rotation is steamed except partial solvent, adds appropriate distilled water, filters.Solid with distilled water, methyl alcohol, washing with acetone, obtains white solid thing 0.79g with this after vacuum-drying, yield is 56.1%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 1407.8 (M ⁺+ 1)

Ultimate analysis (%) C43H26Cl10Ir2N8 theoretical value C, 37.54; H, 2.00; Cl, 25.18; Ir, 27.31; N, 7.96; Measured value: C, 37.50; H, 2.04; Cl, 25.13; Ir, 27.33; N, 7.99.

(3) two (4-methyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C for title complex ²') (2-pyridine formyl) close the synthetic of iridium

Under argon shield; 1.41g (1mmol) part is chloro-4 '-methyl-4 of 2,6-bis-, being dissolved in 30mL cellosolvo containing iridium dichloro dimer and 0.27g (2.20mmol) 2-pyridine carboxylic acid of 2 '-dipyridyl; be heated to reflux state, stirring reaction 24h.Naturally be chilled to after room temperature, progressively drip the 1N HCl aqueous solution, in reaction solution, have Precipitation.Filter, solid is used a small amount of normal hexane, the ultrasonic lower washing of ether successively.Methylene dichloride/sherwood oil mixed solution that the volume ratio of take is 1:2, as elutriant carries out silica gel column chromatography separation, obtains final title complex 0.63g, and yield is 39.8%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 789.0 (M ⁺+ 1)

Ultimate analysis (%) C28H18Cl4IrN5O2 theoretical value: C, 42.54; H, 2.30; Cl, 17.94; Ir, 24.32; N, 8.86; O, 4.05; Measured value: C, 42.47; H, 2.32; Cl, 17.99; Ir, 24.16; N, 8.85; O, 4.12.

Embodiment 6

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (4-methyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (four pyrazoles boron) close iridium

(1) chloro-4 '-methyl-4 of 2,6-bis-, the synthesis step of 2 '-dipyridyl

The step (1) of this step embodiment 5 is identical;

(2) part is chloro-4 '-methyl-4 of 2,6-bis-, 2 '-dipyridyl containing the dimeric synthesis step of iridium dichloro

The step (2) of this step embodiment 5 is identical;

(3) title complex two (2 ', 6 '-bis-chloro-4-methyl-2,4 '-dipyridyl-N, C2 ') (four pyrazoles boron) closes the synthetic of iridium

Under argon shield; it is 2 containing 1.39g (1mmol) part that 50mL is slowly added drop-wise to 60mL containing the methanol solution of 0.54g (2.1mmol) AgOTf; chloro-4 '-methyl-4 of 6-bis-, 2 '-dipyridyl containing in the dimeric dichloromethane solution of iridium dichloro, stirring reaction 2h under room temperature.Whizzer separation obtains settled solution after removing AgCl, and rotary evaporation desolventizes.Under argon shield, residue and 0.95 (3mmol) KBpz ₄be dissolved in 50mL acetonitrile back flow reaction 24h.Be chilled to room temperature, filter, the appropriate washed with dichloromethane of filter residue, merging filtrate, rotation is steamed and is desolventized, and obtains crude product.Crude product is used methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization obtains pure products 0.51g, and productive rate is 26.8%.

Mass spectrum (m/z): 948.1 (M ⁺+ 1)

Ultimate analysis (%) C34H28BCl4IrN12 theoretical value: C, 43.01; H, 2.97; B, 1.14; Cl, 14.94; Ir, 20.24; N, 17.70; Measured value: C, 43.07; H, 2.91; B, 1.11; Cl, 14.97; Ir, 20.21; N, 17.73.

Embodiment 7

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (4-methyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (3-trifluoromethyl-5-(pyridine-2 '-yl)-1,2,4-triazole) close iridium

(1) chloro-4 '-methyl-4 of 2,6-bis-, the synthesis step of 2 '-dipyridyl

The step (1) of this step embodiment 5 is identical;

The step (2) of this step embodiment 5 is identical;

(3) two (2 ', 6 '-bis-chloro-4 '-methyl-2,4 '-dipyridyl-N, C of title complex ²') (3-trifluoromethyl-5-(pyridine-2 '-yl)-1,2,4-triazole) close the synthetic of iridium

Under argon shield; 0.64g (3mmol) 3-trifluoromethyl-5-(pyridine-2-yl)-1; 2; 4-triazole and 1.39g (1mmol) part is 4 '-methyl-2; 6-bis-is chloro-4, and being dissolved in 60mL trichloromethane containing iridium dichloro dimer of 2 '-dipyridyl, under the katalysis of 0.54g (10mmol) sodium methylate; stirring heating is warming up to reflux state, reaction 24h.Naturally be chilled to after room temperature, concentrate and remove a part of solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, successively with deionized water, ether washing for several times, the product of acquisition is dry obtains 0.67g pure products by by tubing string chromatography purification to solid, and yield is 38.0%.

Mass spectrum (m/z): 882.0 (M ⁺+ 1)

Ultimate analysis (%) C30H18Cl4F3IrN8 theoretical value: C, 40.87; H, 2.06; Cl, 16.09; F, 6.47; Ir, 21.80; N, 12.71; Measured value: C, 40.80; H, 2.09; Cl, 16.05; F, 6.50; Ir, 21.82; N, 12.74.

Embodiment 8

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (4-methyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (5-(pyridine-2 '-yl)-pyrrotriazole) close iridium

(1) chloro-4 '-methyl-4 of 2,6-bis-, the synthesis step of 2 '-dipyridyl

The step (1) of this step embodiment 5 is identical;

The step (2) of this step embodiment 5 is identical;

(3) two (4-methyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C for title complex ²') (5-(pyridine-2 '-yl)-pyrrotriazole) close the synthetic of iridium

Under argon shield; 0.64g (3mmol) 5-(pyridine-2 '-yl)-1; 2; 3,4-tetrazolium and 1.39g (1mmol) part is chloro-4 '-methyl-4 of 2,6-bis-; being dissolved in 60mL trichloromethane containing iridium dichloro dimer of 2 '-dipyridyl; under the katalysis of 0.54g (10mmol) sodium methylate, stirring heating is warming up to reflux state, reaction 24h.Naturally be chilled to after room temperature, concentrate and remove a part of solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, successively with deionized water, ether washing for several times, the product of acquisition is dry obtains 0.49g pure products by by tubing string chromatography purification to solid, and yield is 30.1%.

Mass spectrum (m/z): 815.0 (M ⁺+ 1)

Ultimate analysis (%) C28H18Cl4IrN9 theoretical value: C, 41.29; H, 2.23; Cl, 17.41; Ir, 23.60; N, 15.48; Measured value: C, 41.21; H, 2.25; Cl, 17.46; Ir, 23.65; N, 15.44.

Embodiment 9

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (the 4-tertiary butyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (2-pyridine formyl) close iridium

(1) chloro-4 '-tertiary butyl-4 of 2,6-bis-, 2 '-dipyridyl synthetic

Under protecting with argon gas gas mixture, (0.86g, 4.00mmol) 4-tertiary butyl-2-bromopyridine, (0.92g, 4.80mmol) 2, the chloro-4-pyridine of 6-bis-boric acid, (1.656g, 12mmol) K ₂cO ₃and (0.231g, 0.20mmol) Pd (PPh ₃) ₄be dissolved in the mixing solutions of 30mL toluene and 5mL water, be heated to reflux state, stirring reaction 25h.Be chilled to after room temperature, by the aqueous phase separation in reaction mixture, and with ethyl acetate 100mL extraction three times, merge organic phase.The organic phase merging with salt water washing, anhydrous magnesium sulfate drying.Filter, rotation is steamed and is desolventized to obtain crude product.The ethyl acetate that the volume ratio of take is 1:3 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain white solid thing 0.67g, and yield is 60.0%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 280.1.0 (M ⁺+ 1)

Ultimate analysis: C ₁₄h ₁₄cl ₂n ₂theoretical value: C.59.80; H.5.02; Cl.25.22; N.9.96; Measured value: C.59.82; H.5.00; Cl.25.27; N.9.91.

(2) part is chloro-4 '-tertiary butyl-4 of 2,6-bis-, 2 '-dipyridyl dimeric synthetic containing iridium dichloro

Under nitrogen and the protection of argon gas gas mixture; 1.24g (4.4mmol) the 4-tertiary butyl-2; 6-bis-is chloro-2, and 4 '-dipyridyl and 0.63g (2mmol) three hydration iridous chlorides are dissolved in 30mL2-ethoxy ethanol/water (3/1) mixed solution, stirring reaction 24h under reflux state.Liquid cooling to be mixed, to room temperature, has Precipitation in mixed solution.Rotation is steamed except partial solvent, adds appropriate distilled water, filters.Solid with distilled water, methyl alcohol, washing with acetone, obtains white solid thing 0.80g with this after vacuum-drying, yield is 50.8%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 1574.0 (M ⁺+ 1)

Ultimate analysis (%) C56H52Cl10Ir2N8 theoretical value C, 42.68; H, 3.33; Cl, 22.50; Ir, 24.39; N, 7.11; Measured value: C, 42.62; H, 3.40; Cl, 22.54; Ir, 24.36; N, 7.09.

(3) two (the 4-tertiary butyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C for title complex ²') (2-pyridine formyl) close the synthetic of iridium

Under nitrogen and the protection of argon gas gas mixture; 1.58g (1mmol) part is 2; chloro-4 '-tertiary butyl-4 of 6-bis-; being dissolved in 30mL2-ethoxy ethanol containing iridium dichloro dimer and 0.27g (2.20mmol) 2-pyridine carboxylic acid of 2 '-dipyridyl; be heated to reflux state, stirring reaction 24h.Naturally be chilled to after room temperature, progressively drip the 1N HCl aqueous solution, in reaction solution, have Precipitation.Filter, solid is used a small amount of normal hexane, the ultrasonic lower washing of ether successively.Methylene dichloride/sherwood oil mixed solution that the volume ratio of take is 1:2, as elutriant carries out silica gel column chromatography separation, obtains final title complex 0.61g, and yield is 34.9%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 875.1 (M ⁺+ 1)

Ultimate analysis (%) C34H30Cl4IrN5O2 theoretical value: C, 46.69; H, 3.46; Cl, 16.21; Ir, 21.98; N, 8.01; O, 3.66; Measured value: C, 46.61; H, 3.49; Cl, 16.20; Ir, 21.95; N, 8.07; O, 3.69.

Embodiment 10

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (the 4-tertiary butyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (four pyrazoles boron) close the synthetic of iridium

(1) chloro-4 '-tertiary butyl-4 of 2,6-bis-, the synthesis step of 2 '-dipyridyl

The step (1) of this step embodiment 9 is identical;

(2) part is chloro-4 '-tertiary butyl-4 of 2,6-bis-, 2 '-dipyridyl containing the dimeric synthesis step of iridium dichloro

The step (1) of this step embodiment 9 is identical;

(3) title complex two (2 ', 6 '-bis-chloro-4-tertiary butyl-2,4 '-dipyridyl-N, C2 ') (four pyrazoles boron) closes the synthetic of iridium

Under nitrogen and the protection of argon gas gas mixture; it is 2 containing 1.57g (1mmol) part that 50mL is slowly added drop-wise to 60mL containing the methanol solution of 0.54g (2.1mmol) AgOTf; chloro-4 '-tertiary butyl-4 of 6-bis-; containing in the dimeric dichloromethane solution of iridium dichloro of 2 '-dipyridyl, stirring reaction 2h under room temperature.Whizzer separation obtains settled solution after removing AgCl, and rotary evaporation desolventizes.Under nitrogen and the protection of argon gas gas mixture, residue and 0.95 (3mmol) KBpz ₄be dissolved in 50mL acetonitrile back flow reaction 24h.Be chilled to room temperature, filter, the appropriate washed with dichloromethane of filter residue, merging filtrate, rotation is steamed and is desolventized, and obtains crude product.Crude product is used methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization obtains pure products 0.45g, and productive rate is 21.8%.

Mass spectrum (m/z): 1034.2 (M ⁺+ 1)

Ultimate analysis (%) C40H40BCl4IrN12 theoretical value: C, 46.48; H, 3.90; B, 1.05; Cl, 13.72; Ir, 18.60; N, 16.26; Measured value: C, 46.41; H, 3.95; B, 1.07; Cl, 13.75; Ir, 18.62; N, 16.21.

Embodiment 11

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (the 4-tertiary butyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (3-trifluoromethyl-5-(pyridine-2 '-yl)-1,2,4-triazole) close iridium

The step (1) of this step embodiment 9 is identical;

The step (2) of this step embodiment 9 is identical;

(3) two (2 ', 6 '-bis-chloro-4 '-tertiary butyl-2,4 '-dipyridyl-N, C of title complex ²') (3-trifluoromethyl-5-(pyridine-2 '-yl)-1,2,4-triazole) close the synthetic of iridium

Under nitrogen and the protection of argon gas gas mixture; 0.64g (3mmol) 3-trifluoromethyl-5-(pyridine-2-yl)-1; 2; 4-triazole and 1.57g (1mmol) part is 4 '-tertiary butyl-2; 6-bis-is chloro-4, and being dissolved in 60mL trichloromethane containing iridium dichloro dimer of 2 '-dipyridyl, under the katalysis of 0.54g (10mmol) sodium methylate; stirring heating is warming up to reflux state, reaction 24h.Naturally be chilled to after room temperature, concentrate and remove a part of solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, successively with deionized water, ether washing for several times, the product of acquisition is dry obtains 0.67g pure products by by tubing string chromatography purification to solid, and yield is 34.7%.

Mass spectrum (m/z): 964.1 (M ⁺+ 1)

Ultimate analysis (%) C36H30Cl4F3IrN8 theoretical value: C, 44.77; H, 3.13; Cl, 14.68; F, 5.90; Ir, 19.90; N, 11.60; Measured value: C, 44.70; H, 3.19; Cl, 14.69; F, 5.97; Ir, 19.87; N, 11.56.

Embodiment 12

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (the 4-tertiary butyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (5-(pyridine-2 '-yl)-pyrrotriazole) close iridium

The step (1) of this step embodiment 9 is identical;

The step (2) of this step embodiment 9 is identical;

(3) two (the 4-tertiary butyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C for title complex ²') (5-(pyridine-2 '-yl)-pyrrotriazole) close the synthetic of iridium

Under nitrogen and the protection of argon gas gas mixture; 0.64g (3mmol) 5-(pyridine-2 '-yl)-1; 2; 3,4-tetrazolium and 1.57g (1mmol) part is chloro-4 '-tertiary butyl-4 of 2,6-bis-; being dissolved in 60mL trichloromethane containing iridium dichloro dimer of 2 '-dipyridyl; under the katalysis of 0.54g (10mmol) sodium methylate, stirring heating is warming up to reflux state, reaction 24h.Naturally be chilled to after room temperature, concentrate and remove a part of solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, successively with deionized water, ether washing for several times, the product of acquisition is dry obtains 0.54g pure products by by tubing string chromatography purification to solid, and yield is 30.1%.

Mass spectrum (m/z): 897.1 (M ⁺+ 1)

Ultimate analysis (%) C34H30Cl4IrN9 theoretical value: C, 45.44; H, 3.36; Cl, 15.78; Ir, 21.39; N, 14.03; Measured value: C, 45.47; H, 3.31; Cl, 15.74; Ir, 21.44; N, 14.04.

Embodiment 13

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (4-n-hexyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (2-pyridine formyl) close iridium

(1) chloro-4 '-n-hexyl-4 of 2,6-bis-, 2 '-dipyridyl synthetic

Under nitrogen protection, (0.97g, 4.00mmol) 4-n-hexyl-2-bromopyridine, (0.92g, 4.80mmol) 2, the chloro-4-pyridine of 6-bis-boric acid, (1696g, 16mmol) Na ₂cO ₃and (0.2311g, 0.20mmol) Pd (PPh ₃) ₄be dissolved in the mixing solutions of 30mL toluene and 5mL water, be heated to reflux state, stirring reaction 25h.Be chilled to after room temperature, by the aqueous phase separation in reaction mixture, and with ethyl acetate 100mL extraction three times, merge organic phase.The organic phase merging with salt water washing, anhydrous magnesium sulfate drying.Filter, rotation is steamed and is desolventized to obtain crude product.The ethyl acetate that the volume ratio of take is 1:4 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain white solid thing 0.68g, and yield is 55.0%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 308.1 (M ⁺+ 1)

Ultimate analysis: C ₁₆h ₁₈cl ₂n ₂theoretical value: C.62.14; H.5.87; Cl.22.93; N.9.06; Measured value: C.62.10; H.5.85; Cl.22.97; N.9.08.

(3) part is chloro-4 '-n-hexyl-4 of 2,6-bis-, 2 '-dipyridyl dimeric synthetic containing iridium dichloro

Under nitrogen protection; 1.36g (4.4mmol) 4-n-hexyl-2; 6-bis-is chloro-2, and 4 '-dipyridyl and 0.63g (2mmol) three hydration iridous chlorides are dissolved in 30mL2-ethoxy ethanol/water (3/1) mixed solution, stirring reaction 24h under reflux state.Liquid cooling to be mixed, to room temperature, has Precipitation in mixed solution.Rotation is steamed except partial solvent, adds appropriate distilled water, filters.Solid with distilled water, methyl alcohol, washing with acetone, obtains white solid thing 0.81g with this after vacuum-drying, yield is 48.0%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 1686.2 (M ⁺+ 1)

The theoretical C of ultimate analysis (%) C64H68Cl10Ir2N8,45.53; H, 4.06; Cl, 21.00; Ir, 22.77; N, 6.64; Measured value: C, 45.57; H, 4.00; Cl, 21.08; Ir, 22.71; N, 6.64.

(3) two (4-n-hexyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C for title complex ²') (2-pyridine formyl) close the synthetic of iridium

Under nitrogen protection; 1.69g (1mmol) part is chloro-4 '-n-hexyl-4 of 2,6-bis-, being dissolved in 30mL2-ethoxy ethanol containing iridium dichloro dimer and 0.27g (2.20mmol) 2-pyridine carboxylic acid of 2 '-dipyridyl; be heated to reflux state, stirring reaction 24h.Naturally be chilled to after room temperature, progressively drip the 1N HCl aqueous solution, in reaction solution, have Precipitation.Filter, solid is used a small amount of normal hexane, the ultrasonic lower washing of ether successively.Methylene dichloride/sherwood oil mixed solution that the volume ratio of take is 1:5, as elutriant carries out silica gel column chromatography separation, obtains final title complex 0.61g, and yield is 32.8%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 929.1 (M ⁺+ 1)

Ultimate analysis (%) C38H38Cl4IrN5O2 theoretical value: C, 49.04; H, 4.12; Cl, 15.24; Ir, 20.65; N, 7.52; O, 3.44; Measured value: C, 49.08; H, 4.10; Cl, 15.27; Ir, 20.60; N, 7.57; O, 3.39.

Embodiment 14

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (4-n-hexyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (four pyrazoles boron) close iridium

(1) chloro-4 '-n-hexyl-4 of 2,6-bis-, the synthesis step of 2 '-dipyridyl

The step (1) of this step embodiment 13 is identical;

(2) part is chloro-4 '-n-hexyl-4 of 2,6-bis-, 2 '-dipyridyl containing the dimeric synthesis step of iridium dichloro

The step (2) of this step embodiment 13 is identical;

(3) title complex two (2 ', 6 '-bis-chloro-4-n-hexyl-2,4 '-dipyridyl-N, C2 ') (four pyrazoles boron) closes the synthetic of iridium

Under nitrogen protection; it is 2 containing 1.69g (1mmol) part that 50mL is slowly added drop-wise to 60mL containing the methanol solution of 0.54g (2.1mmol) AgOTf; chloro-4 '-tertiary butyl-4 of 6-bis-, 2 '-dipyridyl containing in the dimeric dichloromethane solution of iridium dichloro, stirring reaction 2h under room temperature.Whizzer separation obtains settled solution after removing AgCl, and rotary evaporation desolventizes.Under nitrogen protection, residue and 0.95 (3mmol) KBpz ₄be dissolved in 50mL acetonitrile back flow reaction 24h.Be chilled to room temperature, filter, the appropriate washed with dichloromethane of filter residue, merging filtrate, rotation is steamed and is desolventized, and obtains crude product.Crude product is used methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization obtains pure products 0.44g, and productive rate is 20.2%.

Mass spectrum (m/z): 1090.3 (M ⁺+ 1)

Ultimate analysis (%) C44H48BCl4IrN12 theoretical value: C, 48.49; H, 4.44; B, 0.99; Cl, 13.01; Ir, 17.64; N, 15.42; Measured value: C, 48.41; H, 4.48; B, 0.96; Cl, 13.05; Ir, 17.62; N, 15.48.

Embodiment 15

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (4-n-hexyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (3-trifluoromethyl-5-(pyridine-2 '-yl)-1,2,4-triazole) close iridium

(1) chloro-4 '-n-hexyl-4 of 2,6-bis-, the synthesis step of 2 '-dipyridyl

The step (1) of this step embodiment 13 is identical;

The step (2) of this step embodiment 13 is identical;

(3) two (2 ', 6 '-bis-chloro-4 '-n-hexyl-2,4 '-dipyridyl-N, C of title complex ²') (3-trifluoromethyl-5-(pyridine-2 '-yl)-1,2,4-triazole) close the synthetic of iridium

Under nitrogen protection; 0.64g (3mmol) 3-trifluoromethyl-5-(pyridine-2-yl)-1; 2; 4-triazole and 1.69g (1mmol) part is 4 '-n-hexyl-2; 6-bis-is chloro-4, and being dissolved in 60mL trichloromethane containing iridium dichloro dimer of 2 '-dipyridyl, under the katalysis of 0.54g (10mmol) sodium methylate; stirring heating is warming up to reflux state, reaction 24h.Naturally be chilled to after room temperature, concentrate and remove a part of solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, successively with deionized water, ether washing for several times, the product of acquisition is dry obtains 0.61g pure products by by tubing string chromatography purification to solid, and yield is 29.8%.

Mass spectrum (m/z): 1022.1 (M ⁺+ 1)

Ultimate analysis (%) C40H38Cl4F3IrN8 theoretical value: C, 47.02; H, 3.75; Cl, 13.88; F, 5.58; Ir, 18.81; N, 10.97; Measured value: C, 47.07; H, 3.70; Cl, 13.83; F, 5.55; Ir, 18.86; N, 11.00.

Embodiment 16

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (4-n-hexyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (5-(pyridine-2 '-yl)-pyrrotriazole) close iridium

(1) chloro-4 '-n-hexyl-4 of 2,6-bis-, the synthesis step of 2 '-dipyridyl

The step (1) of this step embodiment 13 is identical;

The step (2) of this step embodiment 13 is identical;

(3) two (4-n-hexyl-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C for title complex ²') (5-(pyridine-2 '-yl)-pyrrotriazole) close the synthetic of iridium

Under nitrogen protection; 0.64g (3mmol) 5-(pyridine-2 '-yl)-1; 2; 3,4-tetrazolium and 1.69g (1mmol) part is chloro-4 '-n-hexyl-4 of 2,6-bis-; being dissolved in 60mL trichloromethane containing iridium dichloro dimer of 2 '-dipyridyl; under the katalysis of 0.54g (10mmol) sodium methylate, stirring heating is warming up to reflux state, reaction 24h.Naturally be chilled to after room temperature, concentrate and remove a part of solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, successively with deionized water, ether washing for several times, the product of acquisition is dry obtains 0.57g pure products by by tubing string chromatography purification to solid, and yield is 29.8%.

Mass spectrum (m/z): 953.2 (M ⁺+ 1)

Ultimate analysis (%) C38H38Cl4IrN9 theoretical value: C, 47.80; H, 4.01; Cl, 14.85; Ir, 20.13; N, 13.20; Measured value: C, 47.87; H, 4.00; Cl, 14.80; Ir, 20.10; N, 13.22.

Embodiment 17

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (4-methoxyl group-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (2-pyridine formyl) close iridium

(1) chloro-4 '-methoxyl group-4 of 2,6-bis-, 2 '-dipyridyl synthetic

Under nitrogen protection, (0.75g, 4.00mmol) 4-methoxyl group-2-bromopyridine, (0.92g, 4.80mmol) 2, the chloro-4-pyridine of 6-bis-boric acid, (0.2484g, 18mmol) K ₂cO ₃and (0.2311g, 0.20mmol) Pd (PPh ₃) ₄be dissolved in the mixing solutions of 30mL toluene and 5mL water, be heated to reflux state, stirring reaction 25h.Be chilled to after room temperature, by the aqueous phase separation in reaction mixture, and with ethyl acetate 100mL extraction three times, merge organic phase.The organic phase merging with salt water washing, anhydrous magnesium sulfate drying.Filter, rotation is steamed and is desolventized to obtain crude product.The ethyl acetate that the volume ratio of take is 1:4 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain white solid thing 0.61g, and yield is 69.8%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 254.0 (M ⁺+ 1)

Ultimate analysis: C11H8Cl2N2O theoretical value: C, 51.79; H, 3.16; Cl, 27.80; N, 10.98; O, 6.27; Measured value: C, 51.75; H, 3.18; Cl, 27.82; N, 10.95; O, 6.20.

(2) part is chloro-4 '-methoxyl group-4 of 2,6-bis-, 2 '-dipyridyl dimeric synthetic containing iridium dichloro

Under nitrogen protection; 1.05g (4.4mmol) 4-methoxyl group-2; 6-bis-is chloro-2, and 4 '-dipyridyl and 0.63g (2mmol) three hydration iridous chlorides are dissolved in 30mL2-ethoxy ethanol/water (3/1) mixed solution, stirring reaction 24h under reflux state.Liquid cooling to be mixed, to room temperature, has Precipitation in mixed solution.Rotation is steamed except partial solvent, adds appropriate distilled water, filters.Solid with distilled water, methyl alcohol, washing with acetone, obtains white solid thing 0.78g with this after vacuum-drying, yield is 55.0%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 1473.8 (M ⁺+ 1)

Ultimate analysis (%) C43H26Cl10Ir2N8 theoretical value C, 35.91; H, 1.92; Cl, 24.09; Ir, 26.12; N, 7.61; O, 4.35; Measured value: C, 35.96; H, 1.90; Cl, 24.06; Ir, 26.15; N, 7.60; O, 4.33.

(3) two (4-methoxyl group-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C for title complex ²') (2-pyridine formyl) close the synthetic of iridium

Under nitrogen protection; 1.47g (1mmol) part is chloro-4 '-methoxyl group-4 of 2,6-bis-, being dissolved in 30mL2-ethoxy ethanol containing iridium dichloro dimer and 0.27g (2.20mmol) 2-pyridine carboxylic acid of 2 '-dipyridyl; be heated to reflux state, stirring reaction 24h.Naturally be chilled to after room temperature, progressively drip the 1N HCl aqueous solution, in reaction solution, have Precipitation.Filter, solid is used a small amount of normal hexane, the ultrasonic lower washing of ether successively.Methylene dichloride/sherwood oil mixed solution that the volume ratio of take is 1:3, as elutriant carries out silica gel column chromatography separation, obtains final title complex 0.63g, and yield is 38.3%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 821.0 (M ⁺+ 1)

Ultimate analysis (%) C28H18Cl4IrN5O4 theoretical value: C, 40.89; H, 2.21; Cl, 17.24; Ir, 23.37; N, 8.51; O, 7.78; Measured value: C, 40.83; H, 2.20; Cl, 17.26; Ir, 23.38; N, 8.54; O, 7.79.

Embodiment 18

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (4-methoxyl group-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (four pyrazoles boron) close iridium

(1) chloro-4 '-methoxyl group-4 of 2,6-bis-, the synthesis step of 2 '-dipyridyl

The step (1) of this step embodiment 17 is identical;

(2) part is chloro-4 '-methoxyl group-4 of 2,6-bis-, 2 '-dipyridyl containing the dimeric synthesis step of iridium dichloro

The step (2) of this step embodiment 17 is identical;

(3) two (2 ', 6 '-bis-chloro-4-methoxy-2,4 '-dipyridyl-N, C2 ') (the four pyrazoles boron) of title complex closes the synthetic of iridium

Under nitrogen protection; it is 2 containing 1.47g (1mmol) part that 50mL is slowly added drop-wise to 60mL containing the methanol solution of 0.54g (2.1mmol) AgOTf; chloro-4 '-methoxyl group-4 of 6-bis-, 2 '-dipyridyl containing in the dimeric dichloromethane solution of iridium dichloro, stirring reaction 2h under room temperature.Whizzer separation obtains settled solution after removing AgCl, and rotary evaporation desolventizes.Under nitrogen protection, residue and 0.95 (3mmol) KBpz ₄be dissolved in 50mL acetonitrile back flow reaction 24h.Be chilled to room temperature, filter, the appropriate washed with dichloromethane of filter residue, merging filtrate, rotation is steamed and is desolventized, and obtains crude product.Crude product is used methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization obtains pure products 0.49g, and productive rate is 25.0%.

Mass spectrum (m/z): 980.1 (M ⁺+ 1)

Ultimate analysis (%) C34H28BCl4IrN12O2 theoretical value: C, 41.61; H, 2.88; B, 1.10; Cl, 14.45; Ir, 19.58; N, 17.12; O, 3.26; Measured value: C, 41.65; H, 2.84; B, 1.16; Cl, 14.40; Ir, 19.57; N, 17.10; O, 3.28.

Embodiment 19

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (4-methoxyl group-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (3-trifluoromethyl-5-(pyridine-2 '-yl)-1,2,4-triazole) close iridium

The step (1) of this step embodiment 17 is identical;

The step (2) of this step embodiment 17 is identical;

(3) two (2 ', 6 '-bis-chloro-4 '-methoxyl group-2,4 '-dipyridyl-N, C of title complex ²') (3-trifluoromethyl-5-(pyridine-2 '-yl)-1,2,4-triazole) close the synthetic of iridium

Under nitrogen protection; 0.64g (3mmol) 3-trifluoromethyl-5-(pyridine-2-yl)-1; 2; 4-triazole and 1.47g (1mmol) part is 4 '-methoxyl group-2; 6-bis-is chloro-4, and being dissolved in 60mL trichloromethane containing iridium dichloro dimer of 2 '-dipyridyl, under the katalysis of 0.54g (10mmol) sodium methylate; stirring heating is warming up to reflux state, reaction 24h.Naturally be chilled to after room temperature, concentrate and remove a part of solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, successively with deionized water, ether washing for several times, the product of acquisition is dry obtains 0.66g pure products by by tubing string chromatography purification to solid, and yield is 36.1%.

Mass spectrum (m/z): 914.0 (M ⁺+ 1)

Ultimate analysis (%) C30H18Cl4F3IrN8O2 theoretical value: C, 39.44; H, 1.99; Cl, 15.52; F, 6.24; Ir, 21.04; N, 12.27; O, 3.50; Measured value: C, 39.41; H, 1.95; Cl, 15.59; F, 6.20; Ir, 21.05; N, 12.24; O, 3.56

Embodiment 20

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (4-methoxyl group-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (5-(pyridine-2 '-yl)-pyrrotriazole) close iridium

The step (1) of this step embodiment 17 is identical;

The step (2) of this step embodiment 17 is identical;

(3) two (4-methoxyl group-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C for title complex ²') (5-(pyridine-2 '-yl)-pyrrotriazole) close the synthetic of iridium

Under nitrogen protection; 0.64g (3mmol) 5-(pyridine-2 '-yl)-1; 2; 3,4-tetrazolium and 1.47g (1mmol) part is chloro-4 '-methoxyl group-4 of 2,6-bis-; being dissolved in 60mL trichloromethane containing iridium dichloro dimer of 2 '-dipyridyl; under the katalysis of 0.54g (10mmol) sodium methylate, stirring heating is warming up to reflux state, reaction 24h.Naturally be chilled to after room temperature, concentrate and remove a part of solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, successively with deionized water, ether washing for several times, the product of acquisition is dry obtains 0.57g pure products by by tubing string chromatography purification to solid, and yield is 33.7%.

Mass spectrum (m/z): 847.0 (M ⁺+ 1)

Ultimate analysis (%) C28H18Cl4IrN9O2 theoretical value: C, 39.73; H, 2.14; Cl, 16.75; Ir, 22.71; N, 14.89; O, 3.78; Measured value: C, 39.77; H, 2.10; Cl, 16.78; Ir, 22.70; N, 14.84; O, 3.81.

Embodiment 21

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (4-positive propoxy-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (2-pyridine formyl) close iridium

(1) chloro-4 '-positive propoxy-4 of 2,6-bis-, 2 '-dipyridyl synthetic

Under nitrogen protection, (0.86g, 4.00mmol) 4-positive propoxy-2-bromopyridine, (0.92g, 4.80mmol) 2, the chloro-4-pyridine of 6-bis-boric acid, (0.276g, 20mmol) K ₂cO ₃and (0.2311g, 0.20mmol) Pd (PPh ₃) ₄be dissolved in the mixing solutions of 30mL toluene and 5mL water, be heated to reflux state, stirring reaction 25h.Be chilled to after room temperature, by the aqueous phase separation in reaction mixture, and with ethyl acetate 100mL extraction three times, merge organic phase.The organic phase merging with salt water washing, anhydrous magnesium sulfate drying.Filter, rotation is steamed and is desolventized to obtain crude product.The ethyl acetate that the volume ratio of take is 1:4 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain white solid thing 0.68g, and yield is 60.0%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 282.0 (M ⁺+ 1)

Ultimate analysis: C13H12Cl2N2O theoretical value: C, 55.14; H, 4.27; Cl, 25.04; N, 9.89; O, 5.65; Measured value: C, 55.11; H, 4.23; Cl, 25.08; N, 9.84; O, 5.73.

(2) part is chloro-4 '-positive propoxy-4 of 2,6-bis-, 2 '-dipyridyl dimeric synthetic containing iridium dichloro

Under nitrogen protection; 1.25g (4.4mmol) 4-positive propoxy-2; 6-bis-is chloro-2, and 4 '-dipyridyl and 0.63g (2mmol) three hydration iridous chlorides are dissolved in 30mL2-ethoxy ethanol/water (3/1) mixed solution, stirring reaction 24h under reflux state.Liquid cooling to be mixed, to room temperature, has Precipitation in mixed solution.Rotation is steamed except partial solvent, adds appropriate distilled water, filters.Solid with distilled water, methyl alcohol, washing with acetone, obtains white solid thing 0.84g with this after vacuum-drying, yield is 53.0%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 1582.0 (M ⁺+ 1)

Ultimate analysis (%) C52H44Cl10Ir2N8O4 theoretical value C, 39.43; H, 2.80; Cl, 22.38; Ir, 24.27; N, 7.07; O, 4.04; Measured value: C, 39.47; H, 2.81; Cl, 22.33; Ir, 24.24; N, 7.03; O, 4.11.

(3) two (4-positive propoxy-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C for title complex ²') (2-pyridine formyl) close the synthetic of iridium

Under nitrogen protection; 1.58g (1mmol) part is chloro-4 '-positive propoxy-4 of 2,6-bis-, being dissolved in 30mL2-ethoxy ethanol containing iridium dichloro dimer and 0.27g (2.20mmol) 2-pyridine carboxylic acid of 2 '-dipyridyl; be heated to reflux state, stirring reaction 24h.Naturally be chilled to after room temperature, progressively drip the 1N HCl aqueous solution, in reaction solution, have Precipitation.Filter, solid is used a small amount of normal hexane, the ultrasonic lower washing of ether successively.Methylene dichloride/sherwood oil mixed solution that the volume ratio of take is 1:3, as elutriant carries out silica gel column chromatography separation, obtains final title complex 0.65g, and yield is 37.0%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 879.0 (M ⁺+ 1)

Ultimate analysis (%) C32H26Cl4IrN5O4 theoretical value: C, 43.74; H, 2.98; Cl, 16.14; Ir, 21.88; N, 7.97; O, 7.28; Measured value: C, 43.78; H, 2.93; Cl, 16.11; Ir, 21.87; N, 7.99; O, 7.31.

Embodiment 22

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (4-positive propoxy-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (four pyrazoles boron) close iridium

(1) chloro-4 '-positive propoxy-4 of 2,6-bis-, the synthesis step of 2 '-dipyridyl

The step (1) of this step embodiment 21 is identical;

The step (2) of this step embodiment 21 is identical;

(3) title complex two (2 ', 6 '-bis-chloro-4-positive propoxy-2,4 '-dipyridyl-N, C2 ') (four pyrazoles boron) closes the synthetic of iridium

Under nitrogen protection; it is 2 containing 1.58g (1mmol) part that 50mL is slowly added drop-wise to 60mL containing the methanol solution of 0.54g (2.1mmol) AgOTf; chloro-4 '-positive propoxy-4 of 6-bis-, 2 '-dipyridyl containing in the dimeric dichloromethane solution of iridium dichloro, stirring reaction 2h under room temperature.Whizzer separation obtains settled solution after removing AgCl, and rotary evaporation desolventizes.Under nitrogen protection, residue and 0.95 (3mmol) KBpz ₄be dissolved in 50mL acetonitrile back flow reaction 24h.Be chilled to room temperature, filter, the appropriate washed with dichloromethane of filter residue, merging filtrate, rotation is steamed and is desolventized, and obtains crude product.Crude product is used methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization obtains pure products 0.50g, and productive rate is 24.1%.

Mass spectrum (m/z): 1038.1 (M ⁺+ 1)

Ultimate analysis (%) C38H36BCl4IrN12O2 theoretical value: C, 43.99; H, 3.50; B, 1.04; Cl, 13.67; Ir, 18.52; N, 16.20; O, 3.08; Measured value: C, 43.95; H, 3.55; B, 1.03; Cl, 13.69; Ir, 18.50; N, 16.25; O, 3.03.

Embodiment 23

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (4-positive propoxy-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (3-trifluoromethyl-5-(pyridine-2 '-yl)-1,2,4-triazole) close iridium

The step (1) of this step embodiment 21 is identical;

(2) part is chloro-4 '-positive propoxy-4 of 2,6-bis-, 2 '-dipyridyl containing the dimeric synthesis step of iridium dichloro

The step (2) of this step embodiment 21 is identical;

(3) two (2 ', 6 '-bis-chloro-4 '-positive propoxy-2,4 '-dipyridyl-N, C of title complex ²') (3-trifluoromethyl-5-(pyridine-2 '-yl)-1,2,4-triazole) close the synthetic of iridium

Under nitrogen protection; 0.64g (3mmol) 3-trifluoromethyl-5-(pyridine-2-yl)-1; 2; 4-triazole and 1.58g (1mmol) part is 4 '-positive propoxy-2; 6-bis-is chloro-4, and being dissolved in 60mL trichloromethane containing iridium dichloro dimer of 2 '-dipyridyl, under the katalysis of 0.54g (10mmol) sodium methylate; stirring heating is warming up to reflux state, reaction 24h.Naturally be chilled to after room temperature, concentrate and remove a part of solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, successively with deionized water, ether washing for several times, the product of acquisition is dry obtains 0.64g pure products by by tubing string chromatography purification to solid, and yield is 33.0%.

Mass spectrum (m/z): 968.0 (M ⁺+ 1)

Ultimate analysis (%) C34H26Cl4F3IrN8O2 theoretical value: C, 42.11; H, 2.70; Cl, 14.63; F, 5.88; Ir, 19.82; N, 11.56; O, 3.30; Measured value: C, 42.17; H, 2.72; Cl, 14.60; F, 5.86; Ir, 19.84; N, 11.52; O, 3.29.

Embodiment 24

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (4-positive propoxy-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (5-(pyridine-2 '-yl)-pyrrotriazole) close iridium

The step (1) of this step embodiment 21 is identical;

The step (2) of this step embodiment 21 is identical;

(3) two (4-positive propoxy-2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C for title complex ²') (5-(pyridine-2 '-yl)-pyrrotriazole) close the synthetic of iridium

Under nitrogen protection; 0.64g (3mmol) 5-(pyridine-2 '-yl)-1; 2; 3,4-tetrazolium and 1.58g (1mmol) part is chloro-4 '-positive propoxy-4 of 2,6-bis-; being dissolved in 60mL trichloromethane containing iridium dichloro dimer of 2 '-dipyridyl; under the katalysis of 0.54g (10mmol) sodium methylate, stirring heating is warming up to reflux state, reaction 24h.Naturally be chilled to after room temperature, concentrate and remove a part of solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, successively with deionized water, ether washing for several times, the product of acquisition is dry obtains 0.58g pure products by by tubing string chromatography purification to solid, and yield is 32.1%.

Mass spectrum (m/z): 903.1 (M ⁺+ 1)

Ultimate analysis (%) C32H26Cl4IrN9O2 theoretical value: C, 42.58; H, 2.90; Cl, 15.71; Ir, 21.30; N, 13.97; O, 3.55; Measured value: C, 42.51; H, 2.95; Cl, 15.74; Ir, 21.32; N, 13.95; O, 3.56.

Embodiment 25

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (the positive hexyloxy-2 ' of 4-, 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (2-pyridine formyl) close iridium

Chloro-4 '-positive hexyloxy-4 of (1) 2,6-bis-, 2 '-dipyridyl synthetic

Under nitrogen protection, the positive hexyloxy-2-of (1.03g, 4.00mmol) 4-bromopyridine, (0.92g, 4.80mmol) 2, the chloro-4-pyridine of 6-bis-boric acid, (0.1484g, 14mmol) Na ₂cO ₃and (0.1404g, 0.20mmol) Pd (PPh ₃) ₂cl ₂be dissolved in the mixing solutions of 30mL toluene and 5mL water, be heated to reflux state, stirring reaction 25h.Be chilled to after room temperature, by the aqueous phase separation in reaction mixture, and with ethyl acetate 100mL extraction three times, merge organic phase.The organic phase merging with salt water washing, anhydrous magnesium sulfate drying.Filter, rotation is steamed and is desolventized to obtain crude product.The ethyl acetate that the volume ratio of take is 1:5 and normal hexane mixed solution are separated as eluent carries out silica gel column chromatography, obtain white solid thing 0.71g, and yield is 54.6%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 324.1 (M ⁺+ 1)

Ultimate analysis: C16H18Cl2N2O theoretical value: C, 59.09; H, 5.58; Cl, 21.80; N, 8.61; O, 4.92; Measured value: C, 59.05; H, 5.54; Cl, 21.85; N, 8.62; O, 4.94.

(2) part is 2,6-bis-chloro-4 '-positive hexyloxy-4,2 '-dipyridyl dimeric synthetic containing iridium dichloro

Under nitrogen protection; positive hexyloxy-2 of 1.25g (4.4mmol) 4-; 6-bis-is chloro-2, and 4 '-dipyridyl and 0.63g (2mmol) three hydration iridous chlorides are dissolved in 30mL2-ethoxy ethanol/water (3/1) mixed solution, stirring reaction 24h under reflux state.Liquid cooling to be mixed, to room temperature, has Precipitation in mixed solution.Rotation is steamed except partial solvent, adds appropriate distilled water, filters.Solid with distilled water, methyl alcohol, washing with acetone, obtains white solid thing 0.88g with this after vacuum-drying, yield is 50.2%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 1752.1 (M ⁺+ 1)

Ultimate analysis (%) C64H68Cl10Ir2N8O4 theoretical value C, 43.87; H, 3.91; Cl, 20.23; Ir, 21.94; N, 6.39; O, 3.65; Measured value: C, 43.81; H, 3.95; Cl, 20.25; Ir, 21.91; N, 6.38; O, 3.69.

(3) two (the positive hexyloxy-2 ' of 4-, 6 '-bis-is chloro-2,4 '-dipyridyl-N, C for title complex ²') (2-pyridine formyl) close the synthetic of iridium

Under nitrogen protection; 1.75g (1mmol) part is chloro-4 '-positive hexyloxy-4 of 2,6-bis-, being dissolved in 30mL2-ethoxy ethanol containing iridium dichloro dimer and 0.27g (2.20mmol) 2-pyridine carboxylic acid of 2 '-dipyridyl; be heated to reflux state, stirring reaction 24h.Naturally be chilled to after room temperature, progressively drip the 1N HCl aqueous solution, in reaction solution, have Precipitation.Filter, solid is used a small amount of normal hexane, the ultrasonic lower washing of ether successively.Methylene dichloride/sherwood oil mixed solution that the volume ratio of take is 1:4, as elutriant carries out silica gel column chromatography separation, obtains final title complex 0.67g, and yield is 34.8%.Product detection data and reaction equation are as follows:

Mass spectrum (m/z): 961.1 (M ⁺+ 1)

Ultimate analysis (%) C38H38Cl4IrN5O4 theoretical value: C, 47.41; H, 3.98; Cl, 14.73; Ir, 19.97; N, 7.27; O, 6.65; Measured value: C, 47.45; H, 3.95; Cl, 14.76; Ir, 19.95; N, 7.24; O, 6.68.

Embodiment 26

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (the positive hexyloxy-2 ' of 4-, 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (four pyrazoles boron) close iridium

Chloro-4 '-positive hexyloxy-4 of (1) 2,6-bis-, the synthesis step of 2 '-dipyridyl

The step (1) of this step embodiment 25 is identical;

(2) part is 2,6-bis-chloro-4 '-positive hexyloxy-4,2 '-dipyridyl containing the dimeric synthesis step of iridium dichloro

The step (2) of this step embodiment 25 is identical;

Under nitrogen protection; it is 2 containing 1.75g (1mmol) part that 50mL is slowly added drop-wise to 60mL containing the methanol solution of 0.54g (2.1mmol) AgOTf; chloro-4 '-positive hexyloxy-4 of 6-bis-, 2 '-dipyridyl containing in the dimeric dichloromethane solution of iridium dichloro, stirring reaction 2h under room temperature.Whizzer separation obtains settled solution after removing AgCl, and rotary evaporation desolventizes.Under nitrogen protection, residue and 0.95 (3mmol) KBpz ₄be dissolved in 50mL acetonitrile back flow reaction 24h.Be chilled to room temperature, filter, the appropriate washed with dichloromethane of filter residue, merging filtrate, rotation is steamed and is desolventized, and obtains crude product.Crude product is used methyl alcohol, deionized water wash successively, and ethanol/methylene mixed solution recrystallization obtains pure products 0.52g, and productive rate is 23.2%.

Mass spectrum (m/z): 1122.2 (M ⁺+ 1)

Ultimate analysis (%) C44H48BCl4IrN12O2 theoretical value: C, 47.11; H, 4.31; B, 0.96; Cl, 12.64; Ir, 17.14; N, 14.98; O, 2.85; Measured value: C, 47.16; H, 4.30; B, 0.93; Cl, 12.61; Ir, 17.15; N, 14.99; O, 2.86.

Embodiment 27

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (the positive hexyloxy-2 ' of 4-, 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (3-trifluoromethyl-5-(pyridine-2 '-yl)-1,2,4-triazole) close the synthetic of iridium

The step (1) of this step embodiment 25 is identical;

(3) two (2 ', 6 '-bis-chloro-4 '-positive hexyloxy-2,4 '-dipyridyl-N, C of title complex ²') (3-trifluoromethyl-5-(pyridine-2 '-yl)-1,2,4-triazole) close the synthetic of iridium

Under nitrogen protection; 0.64g (3mmol) 3-trifluoromethyl-5-(pyridine-2-yl)-1; 2; 4-triazole and 1.75g (1mmol) part is 4 '-positive hexyloxy-2; 6-bis-is chloro-4, and being dissolved in 60mL trichloromethane containing iridium dichloro dimer of 2 '-dipyridyl, under the katalysis of 0.54g (10mmol) sodium methylate; stirring heating is warming up to reflux state, reaction 24h.Naturally be chilled to after room temperature, concentrate and remove a part of solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, successively with deionized water, ether washing for several times, the product of acquisition is dry obtains 0.63g pure products by by tubing string chromatography purification to solid, and yield is 29.9%.

Mass spectrum (m/z): 1054.1 (M ⁺+ 1)

Ultimate analysis (%) C40H38Cl4F3IrN8O2 theoretical value: C, 45.59; H, 3.63; Cl, 13.46; F, 5.41; Ir, 18.24; N, 10.63; O, 3.04; Measured value: C, 45.55; H, 3.67; Cl, 13.49; F, 5.43; Ir, 18.22; N, 10.65; O, 3.09.

Embodiment 28

The blue light organic phosphorescent electroluminescent materials of the present embodiment, two (the positive hexyloxy-2 ' of 4-, 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (5-(pyridine-2 '-yl)-pyrrotriazole) close iridium

The step (1) of this step embodiment 25 is identical;

The step (2) of this step embodiment 25 is identical;

(3) two (the positive hexyloxy-2 ' of 4-, 6 '-bis-is chloro-2,4 '-dipyridyl-N, C for title complex ²') (5-(pyridine-2 '-yl)-pyrrotriazole) close the synthetic of iridium

Under nitrogen protection; 0.64g (3mmol) 5-(pyridine-2 '-yl)-1; 2; 3,4-tetrazolium and 1.75g (1mmol) part is chloro-4 '-positive hexyloxy-4 of 2,6-bis-; being dissolved in 60mL trichloromethane containing iridium dichloro dimer of 2 '-dipyridyl; under the katalysis of 0.54g (10mmol) sodium methylate, stirring heating is warming up to reflux state, reaction 24h.Naturally be chilled to after room temperature, concentrate and remove a part of solvent, the appropriate distilled water of impouring, has solid to separate out.Filter, collect crude product, successively with deionized water, ether washing for several times, the product of acquisition is dry obtains 0.59g pure products by by tubing string chromatography purification to solid, and yield is 29.9%.

Mass spectrum (m/z): 985.2 (M ⁺+ 1)

Ultimate analysis (%) C38H38Cl4IrN9O2 theoretical value: C, 46.25; H, 3.88; Cl, 14.37; Ir, 19.48; N, 12.77; O, 3.24; Measured value: C, 46.25; H, 3.88; Cl, 14.37; Ir, 19.48; N, 12.77; O, 3.24.

Embodiment 29

The present embodiment is organic electroluminescence device, the blue light organic phosphorescent electroluminescent materials that it makes with embodiment 1, and it is two that (2 ', 6 '-bis-is chloro-2,4 '-dipyridyl-N, C ²') (2-pyridine formyl) close iridium (representing with P1) as luminescent layer material of main part.

As shown in Figure 2, this organic electroluminescence device comprises glass substrate 101, conductive anode layer 102, hole injection layer 103, hole transmission layer 104, electronic barrier layer 105, luminescent layer 106, hole blocking layer 107, electron transfer layer 108, electronic injection buffer layer 109 and the cathode layer 110 stacking gradually.

The preparation technology of this device is as follows:

First, on a glass substrate 101, by magnetron sputtering equipment, depositing a layer thickness is that 100nm, square resistance are that the tin indium oxide (ITO) of 10 ~ 20 Ω/mouths is as transparent conductive anode layer 102;

Secondly, on ITO layer 102 surface, stack gradually the following functional layer of evaporation:

Thickness is the hole injection layer 103 that 40nm, material are m-MTDATA;

Thickness is the hole transmission layer 104 that 20nm, material are NPB;

Thickness is the electronic barrier layer 105 that 10nm, material are mCP;

Thickness is that 30nm, material are that P1 is doped to according to 7wt% mass percent the luminescent layer 106 that mCP forms doping mixing material;

Thickness is the hole blocking layer 107 that 10nm, material are BCP;

Thickness is the electron transfer layer 108 that 35nm, material are Alq3;

Layer thickness is the electronic injection buffer layer 109 that 1nm, material are LiF; And

On electronic injection buffer layer 109, vacuum plating deposit thickness is that 120nm, material are the cathode layer 110 of metal A l;

After above-mentioned technique finishes, make organic electroluminescence device, its structure is:

Glass/ITO/m-MTDATA/NPB/mCP/mCP:P1/BCP/Alq3/LiF/Al.

This electroluminescent device due in luminescent layer, contain purity of color and phosphorescence quantum yield higher containing iridium blue phosphorescent organic electroluminescent material, it has higher effciency of energy transfer and luminous efficiency, can be widely used in the luminous fields such as blueness or white.

Should be understood that, the above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, and scope of patent protection of the present invention should be as the criterion with claims.

Claims

1. a blue light organic phosphorescent electroluminescent materials, is characterized in that, this material has following structural formula:

2. blue light organic phosphorescent electroluminescent materials according to claim 1, is characterized in that, R is C ₁~ C ₆straight chained alkyl or C ₁~ C ₆branched-chain alkyl.

3. blue light organic phosphorescent electroluminescent materials according to claim 1, is characterized in that, R is C ₁~ C ₆straight chain alkoxyl group or C ₁~ C ₆branched alkoxy.

4. a preparation method for blue light organic phosphorescent electroluminescent materials, is characterized in that, comprises the steps:

Under protection of inert gas, by structural formula, be

compound D and structural formula be

compd A according to 1: 1.2 ratio of mol ratio, join in the first solvent that contains alkali and catalyzer, obtain mixing solutions, then mixing solutions is heated to 100 ℃, stirring reaction 20h, is chilled to after room temperature, obtains structural formula to be compd B;

compound C;

Under protection of inert gas; the represented contained assistant ligand of iridium metal complex of the Compound C that is 1:2.2 ~ 3:1 by mol ratio and LK is dissolved in cellosolvo, and heated solution is warming up to reflux state, stirring reaction 24h; naturally be chilled to after room temperature, obtain structural formula and be described blue light organic phosphorescent electroluminescent materials;

Above-mentioned various in, R is hydrogen atom, C ₁~ C ₆alkyl or C ₁~ C ₆alkoxyl group; LK is the contained assistant ligand of iridium metal complex, and LK is respectively the assistant ligand with following structural formula:

5. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 4, is characterized in that, R is C ₁~ C ₆straight chained alkyl or C ₁~ C ₆branched-chain alkyl.

6. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 4, is characterized in that, R is C ₁~ C ₆straight chain alkoxyl group or C ₁~ C ₆branched alkoxy.

7. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 4, is characterized in that, described alkali is K ₂cO ₃or Na ₂cO ₃; The molar weight of described alkali is 2 ~ 5 times of Compound D molar weight.

8. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 4, is characterized in that, described catalyzer is tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride, and the molar weight of catalyzer is 0.05 times of Compound D molar weight.

9. the preparation method of blue light organic phosphorescent electroluminescent materials according to claim 4, is characterized in that, described the first solvent is that volume ratio is the toluene of 6:1 and the mixed solvent of water or DMF and water.

10. the arbitrary described blue light organic phosphorescent electroluminescent materials of claims 1 to 3 is as the application of the luminescent layer material of organic electroluminescence device.