CN103694277A

CN103694277A - Red-phosphorescence organic light emitting diode (LED)

Info

Publication number: CN103694277A
Application number: CN201310671828.5A
Authority: CN
Inventors: 李晓常; 吴江
Original assignee: GUANMAT OPTOELECTRONIC MATERIALS (JIANGXI) Inc
Current assignee: GUANMAT OPTOELECTRONIC MATERIALS (JIANGXI) Inc
Priority date: 2013-12-12
Filing date: 2013-12-12
Publication date: 2014-04-02

Abstract

The invention relates to an organic light emitting diode (LED). The organic LED is characterized by consisting of a cathode, an anode and a luminescent layer between the cathode and the anode. The luminescent layer contains an organometallic compound, and the organometallic compound has a general formula shown in a drawing, wherein M is Ir, Os, Eu or Re, and m is 1-3. The organic LED is characterized in that 4-th and 7-th positions of a quinoline ring are provided with substituent, so that the improvement on the luminescence performance of the compound is facilitated and efficient and stable red luminescence performance is obtained.

Description

A kind of red phosphorescent Organic Light Emitting Diode

Technical field

The present invention relates to luminous organic material and apply at organic light-emitting device.

Background technology

Organic semiconductor material belongs to novel photoelectric material, and its broad scale research originates from 1977 by Hideki Shirakawa, and A. Heeger and A. McDiamid have found the doped polyacetylene of conduction Che Keda copper level jointly.Subsequently, the C. Tang of KodaK company in 1987 etc. has invented organic molecule photodiode (OLED), R. Friend and the A. Holmes of Cambridge University have invented polymer LED P-OLED with nineteen ninety, and S. Forrest in 1998 and M. Thomson have invented the higher organophosphorus light-emitting diode PHOLED of efficiency.Because organic semiconductor material has the easy tune of structure, can obtain numerous in variety, can be with adjustable, the low-cost benefit as plastics film processing even, add that organic semiconductor is at conductive film, xerox, photovoltaic solar cell application, OTFT logical circuit, with numerous application such as organic light emission OLED flat pannel display and illumination, tri-scientists of Bai Chuan-Heeger-McDiamid obtained Nobel chemistry Prize in 2000.

As the Organic Light Emitting Diode of flat panel display of future generation, organic photoelectric semi-conductor requires to have: 1. high-luminous-efficiency; 2. good electronics and hole stability; 3. suitable glow color; 4. good film forming processibility.In principle, most of conjugacy organic molecule (comprising star beam), conjugacy polymkeric substance, have and possess electroluminescence performance with the organic heavy metal complex compound that contains conjugacy chromophoric group part, be applied in all kinds of photodiodes, as organic molecule photodiode (OLED), polymer organic LED (POLED), organophosphorus light-emitting diode (PHOLED).Phosphorescence PHOLED dual-purpose the luminescence mechanism of single line excited state (fluorescence) and Triplet Excited State (phosphorescence), obviously than small molecules OLED and the much higher luminous efficiency of polymer POLED.PHOLED manufacturing technology and outstanding PHOLED material are all that to realize low power consumption OLED display and lighting institute requisite.The quantum yield of PHOLED and luminous efficiency are 3 ~ 4 times of fluorescence OLED material, have therefore also reduced the heat producing, and have increased the competitive power of OLED display panel.This point provides the possibility that makes OLED demonstration generally or illumination surmount LCD demonstration and conventional light source.Thereby, in existing high-end OLED device, mixed more or less phosphorescent OLED material.

Phosphorescent OLED material is as bidentate chelating by the organic light emission group of containing certain conjugacy, form ring metal-ligand complex compound with metallic element, high energy light according under under (as ultraviolet excitation) or charge injection (electricity excites) condition, because ring metal-ligand charge transfer (MLCT) becomes exciton, be then returned to ground state and cause luminous.In OLED device, the injection of electric charge is by applying after voltage at anode, from anode, inject electronics, negative electrode injected hole, through electron transfer layer and hole, transfer layer respectively, enter in the bulk material of emission layer simultaneously, the minimum end that electronics finally enters in light-emitting dopant accounts for molecular orbital(MO) (LUMO), and hole enters the highest occupied molecular orbital(HOMO) (HOMO) in light-emitting dopant and forms excited state light-emitting dopant molecule (exciton state).After exciton state replying agent ground state, be accompanied by transmitting luminous energy, its transmitting luminous energy wavelength is over against the energy gap (HOMO-LUMO energy level difference) of answering light emitting molecule doping agent.

The heavy metal organic ligand complex compounds of existing many report, are subject to the impact of heavy metal and have strengthened spin orbital effect, make to become compared with weak phosphorescence very strong and present good phosphorescent emissions.For example three of green light (phenylpyridines) coordinate complex compound according to (III), referred to as Ir (ppy) ₃, there is structural formula to be:

Ir(ppy) ₃，

The FirPic of transmitting blue light has following structural formula:

FirPic，

Main part 4 wherein, 6-phenyl-difluoride yl pyridines is being dominated glow color.Three (octyl quinoline) of red-emitting coordinate complex compound according to (III), have excellent efficient emitting performance (Adv. Mater.19,739(2007)), there is following structure:

Ir(piq-hex) ₃。

Summary of the invention

The invention provides a kind of 2-benzene yl-quinoline-metal and coordinate complex compound, it is characterized in that described cooperation complex compound has following general molecular formula:

molecular formula I

Wherein metal M can be the heavy metal that nucleidic mass is greater than 40, as Ir, and Os, Eu or Re.M=Ir，Os，Eu，Re，m=1~3；

It is characterized in that R ₁be a substituting group, be preferably carbonatoms and be 1 ~ 12 alkyl, carbonatoms is 1 ~ 12 alkoxyl group, and carbonatoms is 1 ~ 12 fluoro alcoxyl, carbonatoms is 1 ~ 12-and NR ₂, an aromatic ring or fragrant heterocycle, wherein aromatic ring or fragrant heterocycle are alternatively for replacing one or more replacements;

It is characterized in that R ₂for H, D, F, CL, NR ₂, CN, CO ₂r, COR, the alkyl that carbonatoms is 1 ~ 12, carbonatoms is 1 ~ 12 alkoxyl group, and carbonatoms is 1 ~ 12 fluoroalkyl, and carbonatoms is 1 ~ 12-NR ₂, an aromatic ring or a fragrant heterocycle, wherein aromatic ring or fragrant heterocycle are alternatively for replacing one or more substituting groups;

It is characterized in that R _{3 ~ 5}for H, D, F, Cl, CN, CO ₂r, COR, the alkyl that carbon atom is 1 ~ 12, carbonatoms is 1 ~ 12 alkoxyl group, and carbonatoms is 1 ~ 12 fluoro-alkyl, and carbonatoms is 1 ~ 12 fluoroalkyl, and carbonatoms is 1 ~ 12-NR ₂, an aromatic ring or a fragrant heterocycle, wherein aromatic ring or fragrant heterocycle are chosen as and replace one or more replacements.

In one case, when selecting metal according to part, described metal ligand complex compound has following molecular formula:

molecular formula II

M=2 ~ 3 wherein;

It is characterized in that R ₁be a substituting group, be preferably carbonatoms and be 1 ~ 12 alkyl, carbonatoms is 1 ~ 12 alkoxyl group, and carbonatoms is 1 ~ 12 fluoro alcoxyl, carbonatoms is 1 ~ 12-and NR ₂, an aromatic ring or a fragrant heterocycle, wherein aromatic ring or fragrant heterocycle are alternatively for replacing one or more replacements;

It is characterized in that R _{3 ~ 5}for H, D, F, Cl, CN, CO ₂r, COR, the alkyl that carbonatoms is 1 ~ 12, carbonatoms is 1 ~ 12 alkoxyl group, and carbonatoms is 1 ~ 12 fluoro-alkyl, and carbonatoms is 1 ~ 12 fluoroalkyl, and carbonatoms is 1 ~ 12-NR ₂, an aromatic ring or a fragrant heterocycle, wherein aromatic ring or fragrant heterocycle are chosen as and replace one or more replacements.

Described iridium metals ligand complex is characterised in that on quinoline ring, 4 bit strips have substituent R ₁, optional substituting group is alkyl, alkoxyl group, fluoro-alkyl, fluoroalkyl or amine alkyl-N (R) ₂.The amount of carbon atom of abovementioned alkyl is 1 ~ 12.In addition, the substituting group on 4-position is also chosen as aromatic ring, fragrant heterocycle, and wherein aromatic ring or fragrant heterocycle are chosen as and replace one or more rings.

Described metal ligand complex compound is characterised in that 7, quinoline ring is upper with substituent R ₂, optional substituting group is H, D, F, Cl, CN; Or optional substituting group is CO ₂r, COR, alkyl, alkoxyl group, fluoro-alkyl, fluoroalkyl or amine alkyl-N (R) ₂, the amount of carbon atom of alkyl described here is 1 ~ 12.Similarly, the replacement base on 7 is chosen as aromatic ring, fragrant heterocycle, and wherein aromatic ring or fragrant heterocycle are monosubstituted or a plurality of replacements alternatively.

Described metal ligand complex compound is characterised in that 3,4,5 positions at part phenyl ring are with being substituted by H, D, F, Cl, CN or optional substituting group is CO ₂r, COR, alkyl, alkoxyl group, fluoro-alkyl, fluoroalkyl or alkyl-N (R) ₂.The amount of carbon atom of alkyl described here is 1 ~ 12.Similarly, the replacement on phenyl ring on 3,4,5 is chosen as aromatic ring, fragrant heterocycle, and wherein aromatic ring or fragrant heterocycle are monosubstituted or polysubstituted alternatively.

The described L according in metal ligand complex molecules formula II is a bidentate assistant ligand.It is characterized in that L is bidentate chelating assistant ligand, its molecular weight is greater than 98.Described bidentate chelating assistant ligand L is chosen as:

A. O--O bidentate chelating assistant ligand:

, A wherein ₁～A ₃for carbonatoms is alkyl, the fluorinated alkyl of 1～16, aryl, fragrant heterocycle or its substituting group;

B. N--O bidentate chelating assistant ligand:

, B wherein ₁for one or more substituting groups, be preferably H, D, Cl, F, carbonatoms is alkyl, the fluorinated alkyl of 1～16, aryl, fragrant heterocycle or its substituting group;

C. N--C bidentate chelating assistant ligand: ,

, C wherein ₁～C ₄for one or more substituting groups, be preferably H, D, Cl, F, carbonatoms is alkyl, the fluorinated alkyl of 1-16, aryl, fragrant heterocycle or its substituting group;

D.

, X=C wherein, N, S, O; D ₁～D ₂for one or more substituting groups, be preferably H, D, Cl, F, carbonatoms is alkyl, the fluorinated alkyl of 1～16, aryl, fragrant heterocycle or its substituting group.

Described organometallic compound, it is characterized in that described bidentate chelating assistant ligand L is chosen as the bidentate chelating assistant ligand that molecular weight is greater than 98, described bidentate chelating assistant ligand on a polymer lateral chain or main chain, is characterized in that described bidentate chelating assistant ligand L is preferably by chemical bonding:

Backbone chain type bidentate chelating assistant ligand:

,

Side chain type bidentate chelating assistant ligand:

.

In one case, when assistant ligand is O---O part, described metal ligand molecular formula is:

molecule formula III

A wherein ₁～A ₃for carbonatoms is alkyl, the fluorinated alkyl of 1～16, aryl, fragrant heterocycle or its substituting group; In another situation, the described optional object of assistant ligand according in metal ligand complex molecules formula also can be:

；

Therefore, do not limiting under the scope of the invention, concrete metal ligand complex molecules structural formula example has following structural formula compound:

(1)

(2)

(3)

(4)

(5)

(6)

(7)

(8)

(9)

(10)

(11)

(12)

(13)

(14)

(15)

(16)

(17)

(18)

(19)

(20)

(21)

(22)

(23)

(24)

(25)

(26)

(27)

(28)

(29) (30)

(31) (32)

(33)

(34)

(35)

(36)

(37)

(38)

(39) (40)

(41)

(42)

(43)

(44)

(45)

(46)

(47)

(48)

(49) (50)

(51)

(52)。

The invention provides an organic luminescent device, include a negative electrode, an anode and a sandwich luminescent layer between negative electrode and positive electrode, wherein contain following structural formula compound in luminescent layer:

M=Ir wherein, Os, Eu, Re, m=2 ~ 3;

It is characterized in that R ₁be a substituting group, be preferably carbon atom and be 1 ~ 12 alkyl, carbon atom is 1 ~ 12 alkoxyl group, and carbon atom is 1 ~ 12 fluoroalkyl, and carbon atom is 1 ~ 12-NR _2,one aromatic ring or fragrant heterocycle, wherein aromatic ring or fragrant heterocycle are alternatively for replacing one or more replacements;

It is characterized in that R ₂for H, D, F, Cl ,-NR ₂, CN, CO ₂r, COR, the alkyl that carbon atom is 1 ~ 12, carbon atom is 1 ~ 12 alkoxyl group, and carbonatoms is 1 ~ 12 fluoroalkyl, and carbonatoms is 1 ~ 12-NR ₂, an aromatic ring or a fragrant heterocycle, wherein aromatic ring or fragrant heterocycle are alternatively for replacing one or more replacements;

It is characterized in that R _{3 ~ 5}for H, D, F, Cl, CN, CO ₂r, COR, the alkyl that carbon atom is 1 ~ 12, carbonatoms is 1 ~ 12 alkoxyl group, and carbonatoms is 1 ~ 12 fluoro-alkyl, and carbonatoms is 1 ~ 12 fluoroalkyl, and carbonatoms is 1 ~ 12-NR ₂, an aromatic ring or a fragrant heterocycle, wherein aromatic ring or fragrant heterocycle are chosen as and replace one or more replacements;

It is characterized in that L is bidentate chelating assistant ligand, its molecular weight is greater than 98.

In one case, work as M=Ir, m=3, compound has following structural formula:

R wherein ₁be a substituting group, be preferably carbon atom and be 1 ~ 12 alkyl, carbon atom is 1 ~ 12 alkoxyl group, and carbon atom is 1 ~ 12 fluoro alcoxyl, and carbon atom is 1 ~ 12-NR ₂; Aromatic ring or fragrant heterocycle, wherein aromatic ring or fragrant heterocycle are alternatively for replacing one or more replacements; R ₂for H, D, F, Cl, NR ₂, CN, CO ₂r, COR, the alkyl that carbon atom is 1 ~ 12, carbon atom is 1 ~ 12 alkoxyl group, and carbon atom grain is 1 ~ 12 fluoroalkyl, and carbon atom is 1 ~ 12-NR ₂, an aromatic ring or a fragrant heterocycle, wherein aromatic ring or fragrant heterocycle are alternatively for replacing one or more substituting groups; R _{3 ~ 5}for H, D, F, Cl, CN, CO ₂r, COR, the alkyl that carbonatoms is 1 ~ 12, carbonatoms is 1 ~ 12 alkoxyl group, and carbonatoms is 1 ~ 12 fluoro-alkyl, and carbonatoms is 1 ~ 12 fluoroalkyl, and carbonatoms is 1 ~ 12-NR ₂, an aromatic ring or a fragrant heterocycle, wherein aromatic ring or fragrant heterocycle are chosen as and replace one or more replacements.

In another situation, in the luminescent layer of luminescent device, contain bidentate chelating assistant ligand by chemical bonding on a polymer lateral chain or main chain.Polymer chain generally should be conjugacy conductive polymers, and bidentate chelating assistant ligand L is preferably:

Backbone chain type bidentate chelating assistant ligand:

;

Side chain type bidentate chelating assistant ligand:

.

Wherein-N=C-C=C-and-O=C-C-O-makes luminous metal complex as bidentate chelating assistant ligand functional group, as Ir (main part) ₂, chemical bonding is on polymer chain.

In being applied to Organic Light Emitting Diode, described compound is normally mixed to form luminescent layer with a bulk material.Mixing film forming can be total to vapor-deposited film by vacuum, or is dissolved in spin coating in solution by mixing, spraying or solution impact system.The present invention also comprises the application at organic luminescent device (OLED) for above-mentioned luminescent material.As organic semiconductor, described material can be used as charge transport layer, barrier application in principle.From considering economically, what is more important is as the application of luminescent layer.When as luminescent layer, for improving luminous efficiency, be necessary to avoid the gathering of light emitting molecule as far as possible.Typically use 0.2 to 20% concentration luminous (weight) material, be doped in a material of main part.The doping content of more optimizing is 2-15%.Certainly, material of main part can be also the hybrid agent material more than a kind of material.

An OLED comprises generally:

A body material, as glass, tinsel, or polymeric film;

An anode, as transparent conductive oxide indium tin;

A negative electrode, as electroconductibility aluminium or other metal;

One or more layers organic semiconductor, emission layer wherein contains described phosphorescent light-emitting materials.Typically use 2 to 15% concentration luminous (weight) material, be doped in a material of main part.

In the luminescent layer of luminescent device of the present invention, contain described luminescent material, by coevaporation or solution coating process, form luminescent layer with there being a bulk material; Light emitting layer thickness is 5-50 nanometer, and its triplet of described bulk material is 2.2-2.9 EV.In one case, bulk material is:

CBP：；

In another case, bulk material is:

BAlq2：

；

Or CBBPy:

.

For reaching good device performance, a flourishing organic light emitting diode also can comprise multiple other organic semiconductor material, and Fig. 1 is an illustrative device structure.On anode, can an optional hole injection layer, as blue or green in phthalein blue (CuPc) or other compound (Appl.Phys.Lett., 69,2160 (1996) containing fragrant ammonia.

Similarly, between hole injection layer and emission layer EML, also can select a hole transmission layer, as use 4,4 '-bis-[N-(1-naphthyl)-N-phenylamino] biphenyl (α-NPD).

For the injection in balance electronic and hole, improve luminous efficiency, can an optional exciton (exciton) blocking layer, for the example of barrier material, be 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline (BCP).

Between blocking layer and negative electrode, also conventionally use electron transfer layer and electron injecting layer.Electric transmission layer material can optional metals quinoline compound, as three-(8-hydroxyl) aluminium (Alq3), oxadiazole or triazole species.

The electron injecting layer metal Lithium that normally work content is lower, or its compound is as LiF, 8-hydroxyl Lithium (Liq) etc.

Therefore, OLED luminescent device is the multilayered structure of a complexity, and Fig. 1 is a typical structure, but is not unique application structure.Wherein the general thickness of organic semiconductor layer is 50～250 nanometers, and preferably total thickness is 80～180 nanometers.

The present invention is characterised in that described luminescent device is the emitting red light device of an efficient stable, and emission wavelength is 570～640 nm, is applied to organic light emission panel display screen, as Mobile phone screen, and i-Pack screen, TV screen, computer screen etc.Phosphor material of the present invention also can be for plate lighting.For reaching white-light illuminating, be necessary to use the OLED of two kinds or three kinds different colours by vertical stack, or level is mixed into white-light illuminating device.For example, the two knot white light parts that use an organic light emitting device in blue color (emission wavelength 445-485 nm) and an orange red organic luminescent device (emission wavelength 570-610nm) to form.More complicated white light emitting device consists of red (570-640nm), green (505-565nm) and blue (445-485nm) three knot white light parts.

The invention has the beneficial effects as follows, on quinoline ring, be above with substituting groups for 4,7, be conducive to improve the luminescent properties of compound, obtain efficient, stable red luminous performance.

Accompanying drawing explanation

Fig. 1 is organic LED structure schematic diagram according to an embodiment of the invention.

Embodiment

For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with examples of implementation, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar popularization without prejudice to intension of the present invention in the situation that.Therefore the present invention is not subject to the restriction of following public specific embodiment.

embodiment 1

< the synthetic > of compound (1)

1. part lead compound 2-is chloro-4,7-dimethyl quinoline synthetic

(1) reaction equation

(2) building-up process

1) tolyl-butyramide synthetic between 3-oxo-N-

a. feed ratio

b. reactions steps

Take 2,2 of the 3-monomethylaniline of 6 grams and 7.2 grams, 6-trimethylammonium-1,3-dioxa cyclohexene-4-ketone, in the bottle with two necks of 50mL, measures the dimethylbenzene of 30mL in flask, stirs, and vacuumizes nitrogen replacement 5 times; Be warming up to boiling, return stirring 2 hours, stopped reaction, underpressure distillation desolventizes and obtains head product, and through silicagel column column chromatography for separation, for eluting solvent, normal hexane, ethyl acetate=5:1 separation and purification obtain 5.6 grams of water white oily matter products.Yield=52%, M/z=191.

2) 4,7-dimethyl quinoline ketone synthetic

a. feed ratio

b. reactions steps

Take that between 1.9 grams of 3-oxo-N-, tolyl-butyramide is in the round-bottomed flask of 50ml, the vitriol oil that measures 10ml with graduated cylinder slowly joins in flask, opens and stirs; Be warming up to 100 ℃, stopped reaction after continuation stirring 2h, be cooled to room temperature, reaction solution is poured in the frozen water of 50ml, has a large amount of white precipitates to separate out, under room temperature, stir 30min, by Bush's funnel, filter again, with normal hexane 50ml washing, collect solid, put into the product that oven for drying obtains 1.3 grams.Yield=75%, M/z=173, HPLC=97%.

3) 4,7-dimethyl-2-chloroquinoline synthetic

a. feed ratio

b. reactions steps

Take 4 of 0.65g oven dry, 7-dimethyl quinoline ketone is in the bottle with two necks of 50mL, the phosphorus oxychloride that measures 5ml with graduated cylinder slowly joins in flask, stir, be warming up to boiling, continue return stirring 2h, stopped reaction, be cooled to room temperature, again reaction solution is slowly poured in frozen water, stirred, with the sodium hydroxide solution of 1M, adjust PH to 5-7, be extracted with ethyl acetate, separatory is collected organic phase, the concentrated dry crude product that obtains, then pass through silica gel column chromatography separating purification, eluent normal hexane: methylene dichloride=1:1 obtains 0.5 gram of colorless oil product, yield=70%.

2. part and compound (1) is synthetic

(1) reaction equation

(2) building-up process

1) 4,7-dimethyl-2-(3,5-3,5-dimethylphenyl)-quinoline synthetic

A. feed ratio

b. experimental procedure

Take 4 of 1.8g, 7-dimethyl-2 chloroquinoline, 3 of 1.8g, 5-dimethyl benzene ylboronic acid, the Pd (PPh of 0.36g ₃) ₄with 4.4g salt of wormwood in there-necked flask; Measure the distilled water of 30mL DME and 30ml in there-necked flask, stir; Vacuumize, nitrogen replacement five times, then be warming up to boiling, continue to stir; After having reacted, by diatomite filtration, remove insolubles magazine, use separating funnel separatory, water extracts with EA50Ml*3, collects organic phase, then uses saturated common salt water washing three times, with anhydrous sodium sulfate drying; Filter, underpressure distillation desolventizes, then crosses post with chromatography column, normal hexane: DCM=1:1, obtain faint yellow crude product solid, and with methyl alcohol room temperature making beating 2h, filtering drying obtains 3.1 grams of white solids, yield 90%.

2) ruddiness compound (1) iridium is dimeric synthetic

a. feed ratio

b. experimental procedure

Take 1.1g 4,7-dimethyl-2-(3,5-3,5-dimethylphenyl)-quinoline, 0.48g iridous chloride trihydrate, in 50ML single port bottle, adds the distilled water of 9ml cellosolvo and 3ml, vacuumizes nitrogen replacement 5 times; Be warming up to boiling, continue return stirring and spend the night; Stopped reaction, is cooled to room temperature, filters and obtains brown solid; First use washing with alcohol 4 times (50ml*4), then use normal hexane (50ml*4) washing; Collect brown solid, enter oven drying.Obtain 0.8 gram of product, yield 77%.

3) ruddiness compound (1) is synthetic

a. feed ratio

b. experimental procedure:

Take 0.4g iridium dimer in the there-necked flask of 50ml, 0.6g 2,2,6,6-tetramethyl--2, and 5-heptadione, the 2-methyl cellosolve of 0.4g sodium carbonate and 10ml is added in round-bottomed flask, stirs, and vacuumizes nitrogen replacement 5 times; Start to be warming up to boiling, solution becomes scarlet, continues return stirring and spends the night; After having reacted, reaction solution is filtered with Bush's funnel, remove filtrate, obtain red crude product, use again DCM dissolution of solid, add distilled water, stirring at room 10 minutes, uses separating funnel separatory again, collect organic phase, the most solvent of vacuum concentration, finally adds Virahol recrystallization to separate out red solid, stirring at room 20 minutes; Decompress filter desolventizes, and collects solid product, and vacuum drying oven is dried, and obtains 0.4 gram of product.Yield: 56%, HPLC=99.2%.

embodiment 2

the synthetic > of < compound (2)

(1) reaction equation

(2) building-up process

1) 4,7-dimethyl-2-(4-tert-butyl-phenyl)-quinoline is synthetic

A. feed ratio

b. experimental procedure

Take 4 of 1.8g, 7-dimethyl-2 chloroquinoline, the 4-tert.-butylbenzene ylboronic acid of 2.2g, the Pd of 0.36g (PPh3) ₄with 4.4g salt of wormwood in there-necked flask; Measure the distilled water of 30mlDME and 30ml in there-necked flask, stir; Vacuumize, nitrogen replacement five times, then be warming up to boiling, continue to stir; After having reacted, by diatomite filtration, remove insolubles magazine, use separating funnel separatory, water extracts with EA50ml*3, collects organic phase, then uses saturated common salt water washing three times, with anhydrous sodium sulfate drying; Filter, underpressure distillation desolventizes, then crosses post with chromatography column, normal hexane: DCM=2:1, obtain faint yellow crude product solid, and with methyl alcohol room temperature making beating 2h, filtering drying obtains 2.2 grams of white solids, yield 76%.m/z=289，hplc=99.1%。

2) compound (2) iridium is dimeric synthetic

a. feed ratio

b. experimental procedure

Take 2.2g 4,7-dimethyl-2-(4-tert-butyl-phenyl)-quinoline, 0.89g iridous chloride trihydrate, in 50ml single port bottle, adds the distilled water of 18ml cellosolvo and 6ml, vacuumizes nitrogen replacement 5 times; Be warming up to boiling, continue return stirring and spend the night; Stopped reaction, is cooled to room temperature, filters and obtains brown color solid; First use washing with alcohol 4 times (50ml*4), then use normal hexane (50ml*4) washing; Collect brown solid, enter oven drying.Obtain 0.94 gram of product, yield 46%.

3) compound (2) is synthetic

a. feed ratio

b. experimental procedure:

Take 0.4g iridium dimer in the there-necked flask of 50 ml, 0.4g methyl ethyl diketone, the 2-methyl cellosolve of 0.4g sodium carbonate and 10ml is added in round-bottomed flask, stirs, and vacuumizes nitrogen replacement 5 times; Start to be warming up to boiling, solution becomes scarlet, continues return stirring and spends the night; After having reacted, reaction solution is filtered with Bush's funnel, remove filtrate, obtain orange crude product, use again DCM dissolution of solid, add distilled water, stirring at room 10 minutes, uses separating funnel separatory again, collect organic phase, the most solvent of vacuum concentration, finally adds Virahol recrystallization to separate out red solid, stirring at room 20 minutes; Decompress filter desolventizes, and collects solid product, and vacuum drying oven is dried, and obtains 0.18 gram of product; Yield, 42%, HPLC=98.2%, m/z=868.

embodiment 3

the synthetic > of < compound (3)

(1) reaction equation

(2) building-up process

1) 4,7-dimethyl-2-(4-p-methoxy-phenyl)-quinoline is synthetic

A. feed ratio

b. experimental procedure

Take 4 of 1.8g, 7-dimethyl-2 chloroquinoline, the 4-anisole ylboronic acid of 2g, the Pd of 0.36g (PPh3) ₄with 4.4g salt of wormwood in there-necked flask; Measure the distilled water of 30ml DME and 30ml in there-necked flask, stir; Vacuumize, nitrogen replacement five times, then be warming up to boiling, continue to stir; After having reacted, by diatomite filtration, remove insolubles magazine, use separating funnel separatory, water extracts with EA50ml*3, collects organic phase, then uses saturated common salt water washing three times.With anhydrous sodium sulfate drying; Filter, underpressure distillation desolventizes, then crosses post with chromatography column, normal hexane: EA=5:1, obtains 2.2 grams of white sterling solids, yield 83%, HPLC=98.2%.

2) compound (3) iridium is dimeric synthetic

a. feed ratio

b. experimental procedure

Take 2.2g 4,7-dimethyl-2-(4-p-methoxy-phenyl)-quinoline, 0.98g iridous chloride trihydrate, in 50ml single port bottle, adds the distilled water of 18ml cellosolvo and 6ml, vacuumizes nitrogen replacement 5 times; Be warming up to boiling, continue return stirring and spend the night; Stopped reaction, is cooled to room temperature, filters and obtains brown color solid; First use washing with alcohol 4 times (50ml*4), then use normal hexane (50ml*4) washing; Collect brown solid, enter oven drying.Obtain 1.4 grams of products, yield 67%.

3) compound (3) end product is synthetic

a. feed ratio

b. experimental procedure:

Take 0.4g iridium dimer in the there-necked flask of 50ml, 0.42g methyl ethyl diketone, the 2-methyl cellosolve of 0.46g sodium carbonate and 10ml is added in round-bottomed flask, stirs, and vacuumizes nitrogen replacement 5 times; Start to be warming up to boiling, solution becomes safran, continues return stirring and spends the night; After having reacted, reaction solution is filtered with Bush's funnel, remove filtrate, obtain orange crude product, use again DCM dissolution of solid, add distilled water, stirring at room 10 minutes, uses separating funnel separatory again, collect organic phase, the most solvent of vacuum concentration, finally adds Virahol recrystallization to separate out safran solid, stirring at room 20 minutes; Decompress filter desolventizes, and collects solid product, and vacuum drying oven is dried, and obtains 0.25 gram of product.Yield: 58%, HPLC=98.8%.m/z=815.

embodiment 4

< compound (4) >

1. the chloro-4-trifluoromethyl-7-of part 2-toluquinoline is synthetic

(1) reaction equation

(2) building-up process

1) SM1's is synthetic

b. reactions steps

The trifluoroacetic ethyl acetoacetate that takes 10 grams is dissolved in 70mL toluene, takes 11.1 grams of triethylamines and joins in flask, more slowly add 6.9 grams of 3-monomethylanilines, stirs, and vacuumizes nitrogen replacement 5 times; Be warming up to boiling, return stirring 2 hours, stopped reaction, underpressure distillation desolventizes and obtains head product, through silicagel column column chromatography for separation, eluting solvent normal hexane: ethyl acetate=2:1 separation and purification obtains 11 grams of white solid products.Yield=83%, M/z=245.

2) SM2's is synthetic

a. feed ratio

b. reactions steps

Take 11.5g SM1 in the round-bottomed flask of 50ml, the vitriol oil that measures 50ml with graduated cylinder slowly joins in flask, opens and stirs; Be warming up to 100 ℃, stopped reaction after continuation stirring 2h, is cooled to room temperature, reaction solution is poured in the frozen water of 250ml, there are a large amount of white precipitates to separate out, under room temperature, stir 30min, then filter by Bush's funnel, with normal hexane 50ml, wash, collect solid, with the ethanol room temperature making beating of 50ml, except magazine, filter, collect product, put into the product that oven for drying obtains 5.4g.Yield=50.6%, M/z=227.

3) 4-trifluoromethyl-7-methyl-2-chloroquinoline is synthetic

a. feed ratio

b. reactions steps

Take the 4-trifluoromethyl that 5.4g is dried, 7-toluquinoline ketone is in the bottle with two necks of 50ml, the phosphorus oxychloride that measures 30ml with graduated cylinder slowly joins in flask, stir, be warming up to boiling, continue return stirring 2h, stopped reaction, be cooled to room temperature, again reaction solution is slowly poured in frozen water, stirred, with the sodium hydroxide solution of 1M, adjust PH to 5-7, be extracted with ethyl acetate, separatory is collected organic phase, the concentrated dry crude product that obtains, then pass through silica gel column chromatography separating purification, eluent normal hexane: methylene dichloride=1:1 obtains 6 grams of white solid products, yield=87%.

2. compound (4) part and final thing is synthetic

(1) reaction equation

(2) building-up process

1) 4-trifluoromethyl-7-methyl-2-benzene yl-quinoline is synthetic

A. feed ratio

b. experimental procedure

Take 4-trifluoromethyl-7-methyl-2 chloroquinoline of 1.1g, the phenyl-boron dihydroxide of 0.71g, the Pd (PPh of 0.15G ₃) ₄with 1.86G salt of wormwood in there-necked flask; Measure the distilled water of 30ml DME and 30ml in there-necked flask, stir; Vacuumize, nitrogen replacement five times, then be warming up to boiling, continue to stir; After having reacted, by diatomite filtration, remove insolubles magazine, use separating funnel separatory, EA 50MLx3 extraction for water, collects organic phase, then uses saturated common salt water washing three times, with anhydrous sodium sulfate drying; Filter, underpressure distillation desolventizes, then crosses post with chromatography column, normal hexane: DCM=2:1, obtain faint yellow crude product solid, and with methyl alcohol room temperature making beating 2h, filtering drying obtains 1.2 grams of white solids, yield 93%.

2) compound (4) iridium is dimeric synthetic

a. feed ratio

b. experimental procedure

Take 0.41g 4-trifluoromethyl-7-methyl-2-benzene yl-quinoline, 0.2g iridous chloride trihydrate, in 50ml single port bottle, adds the distilled water of 12ml cellosolvo and 4ml, vacuumizes nitrogen replacement 5 times; Be warming up to boiling, continue return stirring and spend the night; Stopped reaction, is cooled to room temperature, filters and obtains red solid; First use washing with alcohol 4 times (50ml*4), then use normal hexane (50ml*4) washing; Collect brown solid, enter oven drying.Obtain 0.32 gram of product, yield 68%.

3) compound (4) end product is synthetic

a. feed ratio

b. experimental procedure

Take 0.32g iridium dimer in the there-necked flask of 50 ml, 0.5g methyl ethyl diketone, the 2-methyl cellosolve of 0.35g sodium carbonate and 8ml is added in round-bottomed flask, stirs, and vacuumizes nitrogen replacement 5 times; Start to be warming up to boiling, solution becomes scarlet, continues return stirring and spends the night; After having reacted, reaction solution is filtered with Bush's funnel, remove filtrate, obtain red crude product, use again DCM dissolution of solid, add distilled water, stirring at room 10 minutes, uses separating funnel separatory again, collect organic phase, the most solvent of vacuum concentration, finally adds Virahol recrystallization to separate out red solid, stirring at room 20 minutes; Decompress filter desolventizes, and collects solid product, and vacuum drying oven is dried, and obtains 0.28 gram of product.Yield: 81%, HPLC=98.1%.

embodiment 5

the synthetic > of < compound (10)

(1) reaction equation

1) 4-trifluoromethyl-7-methyl-2-(4-trifluoromethyl)-quinoline is synthetic

A. feed ratio

b. experimental procedure

Take 4-trifluoromethyl 7-methyl-2 chloroquinoline of 0.55g, the 4-trifluoromethyl phenyl boronic acid of 0.55g, the Pd of 0.1g (PPh3) ₄with 0.93g salt of wormwood in there-necked flask; Measure the distilled water of 30ml DME and 30ml in there-necked flask, stir; Vacuumize, nitrogen replacement five times, then be warming up to boiling, continue to stir; After having reacted, by diatomite filtration, remove insolubles magazine, use separating funnel separatory, water extracts with EA50ml*3, collects organic phase, then uses saturated common salt water washing three times.With anhydrous sodium sulfate drying; Filter, underpressure distillation desolventizes, then crosses post with chromatography column, normal hexane: DCM=5:1, obtains 0.75 gram of look solid of white, yield 90%.

2) compound (10) iridium is dimeric synthetic

a. feed ratio

b. experimental procedure

Take 0.41g 4-trifluoromethyl-7-methyl-2-(4-trifluoromethyl)-quinoline, 0.2g iridous chloride trihydrate, in 50ml single port bottle, adds the distilled water of 12ml cellosolvo and 4ml, vacuumizes nitrogen replacement 5 times; Be warming up to boiling, continue return stirring and spend the night; Stopped reaction, is cooled to room temperature, filters and obtains red solid; Collect red solid, enter oven drying.Obtain 0.46 gram of crude product, yield 83%.

3) compound (10) end product is synthetic

a. feed ratio

b. experimental procedure

Take 0.46g iridium dimer in the there-necked flask of 50 ml, 0.6g methyl ethyl diketone, the 2-methyl cellosolve of 0.6g sodium carbonate and 8ml is added in round-bottomed flask, stirs, and vacuumizes nitrogen replacement 5 times; Start to be warming up to boiling, solution becomes scarlet, continues return stirring and spends the night; After having reacted, reaction solution is filtered with Bush's funnel, remove filtrate, obtain red crude product, use again DCM dissolution of solid, add distilled water, stirring at room 10 minutes, uses separating funnel separatory again, collect organic phase, the most solvent of vacuum concentration, finally adds Virahol recrystallization to separate out red solid, stirring at room 20 minutes; Decompress filter desolventizes, and collects solid product, and vacuum drying oven is dried, and obtains 0.1 gram of product.Yield: 20%.

embodiment 6

the synthetic > of < compound (11)

(1) reaction equation

(2) building-up process

1) 4-trifluoromethyl-7-methyl-2-(4-fluorophenyl)-quinoline is synthetic

A. feed ratio

b. experimental procedure

Take 4-trifluoromethyl 7-methyl-2 chloroquinoline of 0.55g, the 4-fluorophenyl boric acid of 0.5g, the Pd (PPh of 0.1g ₃) ₄with 0.93g salt of wormwood in there-necked flask; Measure the distilled water of 15ml DME and 15ml in there-necked flask, stir; Vacuumize, nitrogen replacement five times, then be warming up to boiling, continue to stir; After having reacted, by diatomite filtration, remove insolubles magazine, use separating funnel separatory, EA 50Ml*3 extraction for water, collects organic phase, then uses saturated common salt water washing three times, with anhydrous sodium sulfate drying; Filter, underpressure distillation desolventizes, then crosses post with chromatography column, normal hexane: DCM=5:1, obtains 0.65 gram of look solid of white, yield 95%.

2) compound (11) iridium is dimeric synthetic

a. feed ratio

b. experimental procedure

Take 0.65g 4-trifluoromethyl-7-methyl-2-(4-fluorophenyl)-quinoline, 0.3g iridous chloride trihydrate, in 50ml single port bottle, adds the distilled water of 12ml cellosolvo and 4ml, vacuumizes nitrogen replacement 5 times; Be warming up to boiling, continue return stirring and spend the night; Stopped reaction, is cooled to room temperature, filters and obtains red solid; Collect red solid, enter oven drying.Obtain 0.56 gram of crude product, yield 78.5%.

3) compound (11) end product is synthetic

a. feed ratio

b. experimental procedure

Take 0.46g iridium dimer in the there-necked flask of 50 ml, 0.65g tertiary butyl methyl ethyl diketone, the 2-methyl cellosolve of 0.6g sodium carbonate and 8ml is added in round-bottomed flask, stirs, and vacuumizes nitrogen replacement 5 times; Start to be warming up to boiling, solution becomes scarlet, continues return stirring and spends the night; After having reacted, reaction solution is filtered with Bush's funnel, remove filtrate, obtain red crude product, use again DCM dissolution of solid, add distilled water, stirring at room 10 minutes, uses separating funnel separatory again, collect organic phase, the most solvent of vacuum concentration, finally adds Virahol recrystallization to separate out red solid, stirring at room 20 minutes; Decompress filter desolventizes, and collects solid product, and vacuum drying oven is dried, and obtains 0.46 gram of product.Yield: 78%.

embodiment 7

Ito glass (14 Ω/), through washings, deionized water, cleans with Virahol after acetone ultrasonic cleaning, finally in 80 ^ounder C, dry 30 minutes, substrate is processed 30 minutes at UV-ozone plasma again; Under high vacuum, the hole-injecting material HIL CuPc evaporation that thickness is 100 is on ITO surface.Afterwards, 400 NPB evaporation on CuPc as HTL.As luminescent layer EML be by BAlq as bulk material (device a-e), or by CBBPy as bulk material (device f), adopt coevaporation to mix luminescent material (8% weight), total thickness 300.Afterwards, 50 BAlq are as blocking layer BL, 450 thickness A lq ₃as electron transfer layer ETL.10 LiF are as electron injecting layer EIL, and 1000 aluminium cover EIL above as encapsulation and minute surface reflective surface afterwards.Last OLED adds hygroscopic agent by glass cover, with testing after epoxy glue encapsulation.

Material structure used in OLED device is:

control compounds I

CBBPy：

Table 1 luminophor performance of the present invention table

Table 2 luminescent material OLED device performance

Claims

1. an organometallic compound, has following general formula:

M=Ir wherein, Os, Eu, Re, m=2 ~ 3;

It is characterized in that R ₁be a substituting group, be preferably carbon atom and be 1 ~ 12 alkyl, carbon atom is 1 ~ 12 alkoxyl group, and carbon atom is 1 ~ 12 fluoroalkyl, and carbon atom is 1 ~ 12-NR ₂, an aromatic ring or fragrant heterocycle, wherein aromatic ring or fragrant heterocycle are alternatively for replacing one or more replacements;

It is characterized in that R ₂for H, D, F, Cl ,-NR ₂, CN, CO ₂r, COR, the alkyl that carbon atom is 1 ~ 12, carbon atom is 1 ~ 12 alkoxyl group, and carbon atom is 1 ~ 12 fluoroalkyl, and carbon atom is 1 ~ 12-NR ₂, an aromatic ring or a fragrant heterocycle, wherein aromatic ring or fragrant heterocycle are alternatively for replacing one or more replacements;

It is characterized in that R _{3 ~ 5}for H, D, F, Cl, CN, CO ₂r, COR, the alkyl that carbon atom is 1 ~ 12, carbonatoms is 1 ~ 12 alkoxyl group, and carbon atom is 1 ~ 12 fluoro-alkyl, and carbonatoms is 1 ~ 12 fluoroalkyl, and carbon atom is 1 ~ 12-NR ₂, an aromatic ring or a fragrant heterocycle, wherein aromatic ring or fragrant heterocycle are chosen as and replace one or more replacements;

2. organometallic compound according to claim 1, is characterized in that described bidentate chelating assistant ligand L is chosen as the bidentate chelating assistant ligand that molecular weight is greater than 98;

It is characterized in that described bidentate chelating assistant ligand L is chosen as:

A. O--O bidentate chelating assistant ligand:

, A wherein ₁-A ₃for carbonatoms is individual alkyl, fluorinated alkyl of 1-16, aryl, fragrant heterocycle or its substituting group;

B. N--O bidentate chelating assistant ligand:

, B wherein ₁for one or more substituting groups, be preferably H, D, Cl, F, carbonatoms is alkyl, the fluorinated alkyl of 1-16, aryl, fragrant heterocycle or its substituting group;

C. N--C bidentate chelating assistant ligand:

,

, C wherein ₁-C ₄for one or more substituting groups, be preferably H, D, Cl, F, carbonatoms is alkyl, the fluorinated alkyl of 1-16, aryl, fragrant heterocycle or its substituting group;

D:

, X=C wherein, N, S, O; D ₁-D ₂for one or more substituting groups, be preferably H, D, Cl, F, carbonatoms is alkyl, the fluorinated alkyl of 1-16, aryl, fragrant heterocycle or its substituting group.

3. organometallic compound according to claim 2, it is characterized in that described bidentate chelating assistant ligand L is chosen as the bidentate chelating assistant ligand that molecular weight is greater than 98, bidentate chelating assistant ligand described in it is characterized in that on a polymer lateral chain or main chain, is characterized in that described bidentate chelating assistant ligand L is preferably by chemical bonding:

Backbone chain type bidentate chelating assistant ligand:

,

Side chain type bidentate chelating assistant ligand:

.

4. an organic luminescent device, is characterized in that described organic luminescent device is comprised of following several parts:

(a) negative electrode

(b) anode

(c) a sandwich luminescent layer between negative electrode and positive electrode, wherein contains following structural formula compound in luminescent layer:

M=Ir wherein, Os, Eu, Re, m=2 ~ 3;

5. organic luminescent device according to claim 4, is characterized in that M=Ir, m=3, and compound has following structural formula:

It is characterized in that R ₁be a substituting group, be preferably carbon atom and be 1 ~ 12 alkyl, carbon atom is 1 ~ 12 alkoxyl group, and carbon atom is 1 ~ 12 fluoro alcoxyl, and carbon atom is 1 ~ 12-NR ₂; Aromatic ring or fragrant heterocycle, wherein aromatic ring or fragrant heterocycle are alternatively for replacing one or more replacements;

It is characterized in that R ₂for H, D, F, CL, NR ₂, CN, CO ₂r, COR, the alkyl that carbon atom is 1 ~ 12, carbon atom is 1 ~ 12 alkoxyl group, and carbon atom grain is 1 ~ 12 fluoroalkyl, and carbon atom is 1 ~ 12-NR ₂, an aromatic ring or a fragrant heterocycle, wherein aromatic ring or fragrant heterocycle are alternatively for replacing one or more substituting groups;

6. organic luminescent device according to claim 4, is characterized in that containing in described luminescent layer following structural formula compound:

(1)

(2)

(3)

(4)

(5)

(6)

(7)

(8)

(9)

(10)

(11) (12)

(13)

(14)

(15)

(16)

(17)

(18)

(19)

(20)

(21)

(22)

(23)

(24)

(25)

(26)

(27) (28)

(29)

(30)

(31) (32)

(33)

(34)

(35)

(36)

(37) (38)

(39) (40)

(41)

(42)

(43)

(44)

(45)

(46)

(47)

(48)

(49) (50)

(51)

(52)。

7. organic luminescent device according to claim 4, it is characterized in that containing in described luminescent layer bidentate chelating assistant ligand by chemical bonding on a polymer lateral chain or main chain, it is characterized in that described bidentate chelating assistant ligand L is preferably:

Backbone chain type bidentate chelating assistant ligand: ;

Side chain type bidentate chelating assistant ligand: .

8. organic luminescent device according to claim 4, is characterized in that containing described luminescent material in described luminescent layer, forms luminescent layer with there being a bulk material by coevaporation or solution coating process; Described light emitting layer thickness is 5～50 nanometers, and its triplet of described bulk material is 2.2～2.9 EV.

9. organic luminescent device according to claim 8, is characterized in that described bulk material is preferably:

BAlq2：

。

10. organic luminescent device according to claim 8, is characterized in that described bulk material is preferably:

CBBPy：

。