CN104478940A - Organic photoelectric materials and application - Google Patents

Organic photoelectric materials and application Download PDF

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CN104478940A
CN104478940A CN201410750727.1A CN201410750727A CN104478940A CN 104478940 A CN104478940 A CN 104478940A CN 201410750727 A CN201410750727 A CN 201410750727A CN 104478940 A CN104478940 A CN 104478940A
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李晓常
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GUANMAT OPTOELECTRONIC MATERIALS (JIANGXI) Inc
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Abstract

The invention relates to a high-efficiency light-emitting phosphorescent material and application thereof to an organic photoelectric device. An aromatic heterocycte 6-5 matched bidentate complex is adopted as an auxiliary ligand, and through a chemical hybridization manner, a novel heavy metal ligand complex is obtained, thus the organic photoelectric material can be suitable for multi-color phosphorescent application, has excellent heat stability, electronic stability and easy-to-prepare characteristics, and is especially suitable for large flat-panel display screens and organic light-emitting devices for high-brightness lighting application.

Description

Organic photoelectrical material and application
Technical field
The present invention relates to organo-metallic ligand complex compound semi-conductor and use its organic electro-optic device, as Organic Light Emitting Diode and thin-film solar cells.
Background technology
Organic semiconductor functional materials belongs to novel optoelectronic materials, and its broad scale research is originating primarily from 1977 by Hideki Shirakawa, and A. Heeger and McDiamid has found that electric conductivity can reach the doped polyacetylene of copper level jointly.Subsequently, Kodak company in 1987, C.Tang etc. have invented organic molecule light emitting diode (Organic Light-Emitting Diode) OLED, R.Friend and A.Holmes of Cambridge University has invented polymer light-emitting diode P-OLED with nineteen ninety, and S.Forrest and M.Thomson in 1998 has invented the higher Phosphorescent light emitting diode PH-OLED of efficiency.Because it is numerous in variety that organic semiconductor material is expected acquisition, can be with adjustable, low cost benefit even as plastics film processing, add that organic semiconductor is at conductive film, xerox, photovoltaic solar cell, OTFT logical circuit, with the application of organic light emission OLED flat pannel display, Bai Chuan-Heeger-McDiamid three scientists 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. excellent electronic stability; 3. excellent hot-work stability; 4. suitable glow color; 5. material is prepared simple.In principle, major part conjugacy organic molecule, conjugacy polymkeric substance, electroluminescence performance is all possessed with the organic heavy metal complex compound launching group's part containing conjugacy, be applied in all kinds of photodiode, as organic molecule photodiode (OLED), polymer organic LED (P-OLED), Phosphorescent photodiode (PHOLED).The phosphorescence PHOLED dual-purpose luminescence mechanism of singlet (fluorescence) and triplet state (phosphorescence), has a luminous efficiency more much higher than small molecules OLED and polymer P-OLED.PHOLED technology and outstanding PHOLED material be all to realize low power consumption OLED display and lighting institute requisite.The external quantum efficiency of PHOLED and luminous efficiency are 4 times of fluorescence OLED material, therefore decrease the heat of generation and increase the selection of AMOLED backboard.This point provides and makes OLED can be applied in high-end dull and stereotyped total colouring and planar light with the considerable advantage that LCD shows and traditional light source contends with.Thus, phosphorescent OLED material has been mixed more or less in existing high-end OLED product.
Phosphorescence light-emitting semiconducting material forms ring metal-ligand complex compound by the organic chromophores containing certain conjugacy as bidentate chelating and heavy metal, under high energy light (as ultraviolet excitation) or charge injection (be electrically excited or electricity to luminous) condition, because ring metal-ligand charge transfer (MLCT) is excited rear generation exciton and cause luminescence.Existing many heavy metal organic ligand complex compounds, the spin-orbit effect strengthened by the impact of heavy metal, makes to become very strong and present excellent phosphorescent emissions and be applied as light-emitting diodes light by more weak phosphorescence.Such as, many iridium metals ligand complex compounds, the 1st triplet state according to its electronics can greatly little (T 1), and launch blue light, green glow, gold-tinted, orange light, ruddiness etc.One of example is that three (octyl benzene quinoline) iridium (III) coordinates complex compound,
there is excellent efficient red emission characteristic (Adv. Mater., 19,739(2007)), its electronic stability is strong, and the ageing-resistant time is also long especially.But it is high that its weak point is manufacturing cost.Moreover, because many rings of prosperity merge, add the complex compound that three-fold coordination body and heavy metal are formed, make its sublimation temperature higher than its decomposition temperature, bring very large purification problem and the luminescent device performance that causes to be difficult to constant control problem aborning thus.
For ensureing High Efficiency Luminescence, excellent color and manufacture low cost, nearest R. Kwong etc. (Chinese patent application 200980140491) disclose following light emitting molecule:
，
The complex compound that two parts of heavy metal iridium and substituted-phenyl quinoline are formed has full efficient ruddiness, methyl ethyl diketone root is adopted to replace three-fold coordination body as assistant ligand (assistant ligand means and do not participate in phosphorescent emissions directly) herein, both maintain original high efficiency phosphorescent performance, be conducive to low cost manufacture simultaneously.But methyl ethyl diketone root lacks flourishing p electron delocalization in itself, causes deficient in stability in electrochemical redox loop test.Thus, under the luminous working conditions of the OLED under long-term electron-hole injection mechanism, the comparatively worse long-term luminous stability of three parts-iridium (III) phosphorescent molecules can be shown as.Bring OLED display screen luminescent lifetime not long therefrom, easily under high illumination or in working temperature more than 70 obring " burn in " (grilling thoroughly) that display screen was lost efficacy under C.
In assistant ligand principle, similar main part, belongs to bidentate chelating ligand together and participates in chemical bonding, thus forms new metal-ligand compound (complex compound).Assistant ligand is not only affecting phosphorescence co-ordination complex electronic stability (lack its can not), heating evaporation process difficulty or ease, and cost control plays an important role, and in the adjustment of complex compound locus, and can affect on phosphorescence co-ordination complex luminescence feature and play an important role.Lamansky is in its US Patent No. 6,939, disclose in 624, when use 2, when 4-phenyl-difluoride pyridine iridium Fir is as blue emitting phosphor material, the phosphorescent emissions of different assistant ligand gained is selected to be: FirPic(selects 2-Pyridinecarboxylic Acid root) be 462 nanometers, Fir(acac) (selecting methyl ethyl diketone root) be 485 nanometers, Fir(ppy) (selecting phenylpyridine) be 515 nanometers.So far, the assistant ligand of most of phosphorescent light-emitting materials is if it were not for first wife's active ligand (Tsuboyama et al, JACS, 2003,125 (42), 12971-12979), be exactly part structure lacking electronic stability, as methyl ethyl diketone root, 2-Pyridinecarboxylic Acid root, amido ethylpyrazol (Li Zhongxia etc., CN1,876,, and beta-keto diimide (Bradley, US7 664), 582,757).Obviously, be necessary to find one to have low cost concurrently, efficiently, have again the phosphorescent light-emitting materials of electronic stability simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of photoconductive organic semiconductor material, the combining efficient phosphorescence characteristics of luminescence and low cost, excellent electron stability.Adopt bidentate title complex that fragrant heterocycle 6-5 arranges in pairs or groups as assistant ligand, by chemical hybrid form, obtain novel heavy metal ligand complex, applicable polychrome phosphorescence luminescence application, have excellent thermally-stabilised and electronic stability and easy feature processed concurrently.Especially the organic luminescent device of large-area flat-plate display screen and highlight illumination application is applicable to.Its molecular composition of heavy metal ligand complex of the present invention by phosphorescent part, assistant ligand and and part, assistant ligand forms the heavy metal of metal ligand charge transfer MLCT title complex.The general formula of expressing is:
Wherein in six-ring A, B, C, D(from A-D) or carbon atom, or nitrogen-atoms; E, F, G or carbon atom or nitrogen in five-ring, sulphur, Sauerstoffatom.Substituent R 1-R 7h, D, fluoro, chloro, iodo, or other hydrocarbon substituent, comprise alkyl to replace, aromatic ring replaces, fragrant heterocyclic substituted, aralkyl replaces, and fragrant Heterocyclylalkyl replaces, and alkoxyl group replaces, aryloxy replaces, and fragrant hetero-oxy replaces, and aralkoxy replaces, virtue heterocyclylalkoxy groups replaces, and replaces number and can be part or entirely replace.Atoms metal M system heavy metal, its nucleidic mass generally should be greater than 40, is mainly Ir, and Pt, Os, Re form, and first-selection is Ir, Pt.When atoms metal is Ir, Os, Re, phosphorescent chromophores part number n should be 2; When atoms metal is Pt, phosphorescent chromophores part number n should be 1.What should give explanation is, metal complex herein, also metal complexes can be expressed as, metal-ligand compound, or organometallic compound, because these are the organometallic compound that metal and bidentate ligand are formed, wherein existing metal-carbon covalent linkage, also has from ligand N atomic current to the coordinate bond (using solid line statement without exception herein) of atoms metal.
According to category of the present invention, a six-ring is had to contain the atom N of lone-pair electron in assistant ligand, with SP 2the C atom of hydridization forms aromatic heterocycle.Another five-ring contains the C=C key of at least one and heavy metal bonding.This 6,5 two fragrant heterocycle is bonded to a more flourishing dicyclo conjugated structure by chemical covalent, has both been conducive to making the luminous ligand L of phosphorescence as assistant ligand 2-M stabilization, and the flourishing bicyclic ring structures of the conjugation of self has electronic stability.Because assistant ligand is usually simple than transmitting part, can on the basis reaching high electronic stability and high heat-resistant stability, easily manufactured, be easy to reduce costs.The hexa-atomic fragrant heterocycle of assistant ligand comprises pyridine, pyridazine (pyridazine), and pyrimidine (pyrimidine) and pyrazine (pyrazine) stablize fragrant heterocycle; In assistant ligand, five Yuans fragrant heterocycles comprise thiophene, furans, thiazole ， oxazole, or its corresponding substituent.
The assistant ligand that one of feature of the present invention is made up of two fragrant heterocycles also comprises 1 to multiple replacement, not only be conducive to preparation, such as increase the methyl that solvability and carrying out replaces, ethyl, propyl group, sec.-propyl, and the alkyl of no more than 8 carbon atoms replaces, the alkoxyl group of no more than 8 carbon atoms replaces; And the aryl being conducive to increasing electronic stability further and carrying out or fragrant heterocyclic substituted, have but be not limited to example of the present invention, as phenyl, substituted-phenyl, pyridyl, substituted pyridinyl, carbazyl, substituted carbazole base, amido, aryl amine, substituted aromatic amines base; Or for increasing the halogen substiuted of ring stability, having but being not limited to example of the present invention, as fluoro, chloro, bromo, iodo, or isotropic substance is deuterated.The preferred assistant ligand structure of the present invention comprises but has not limited compound 1-12structure:
。
the luminous assistant ligand of first-selected phosphorescence
As pyridine, hexa-member heterocycle pyridazine (pyridazine), pyrimidine (pyrimidine) and pyrazine (pyrazine) are stable fragrant heterocycles.Many thermotolerance polymers have selected these fragrant heterocycles as main chain, and decomposition temperature reaches 450 oc.（J. Polym. Sci. Part A: Polym. Chem. 47: 4886–4984 (2009)）。Another five-ring contains the S of lone-pair electron, O, or N, as thiophene, and furans, thiazole ， oxazole.
As VISIBLE LIGHT EMISSION application (as display or illumination etc.), phosphorescent chromophores major part, containing bidentate chelating conjugated molecule structure, forms cyclic metal complexes bonding system with heavy metal.400-700 nanometer is chosen as, corresponding 1st triplet (T by regulating its phosphorescence light-emitting zone of chemical structure of part 1) be 3.10-1.77 eV; First-selection is 450-640 nanometer, and corresponding 1st triplet is 2.76-1.94eV.The luminous Ir part of known phosphorescence has much (Fig. 1), as the btp glowed; The pq sending out light orange; The bt of Yellow light-emitting low temperature; The ppy of green light.It is colour solid that all these phosphorescence are sent out, without prejudice under range of condition of the present invention, and can as phosphorescent moieties of the present invention.Difference is, the present invention uses the assorted two ring linkers of a kind of virtue as assistant ligand, it is the fragrant heterocyclic organic compounds being different from phosphorescence non-chromophoric ligand, be made up of six Yuans fragrant heterocycles containing at least one N=C key and five Yuans fragrant heterocycles containing at least one C=C key, these two rings form conjugacy assistant ligand by organic covalent chemical bonding.By chemical hybrid form, obtain novel heavy metal ligand complex, applicable polychrome phosphorescence luminescence application, have excellent thermally-stabilised and electronic stability and easy feature processed concurrently.Especially the organic luminescent device of large-area flat-plate display screen and highlight illumination application is applicable to.
The luminous main part of first-selected phosphorescence has the main part of A-P in following structure iron.Wherein in main part, R1-R4 is 1 to multiple substituting group.Substituting group comprises one or more methyl, ethyl, and is less than the alkyl of 8 carbon atoms; Substituting group comprises one or more methoxyl groups, oxyethyl group, and is less than the alkoxyl group of 8 carbon atoms; Substituting group comprises one or more phenyl, naphthyl, thienyl, pyrryl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl; Substituting group comprises one or more F, Cl, Br, I, D, CN, NO 2, NH 2, dimethylamino, phenylbenzene ammonia.Obviously, the various combinations between first-selected main part-assistant ligand all belong to category of the present invention,
。
the luminous main part of first-selected phosphorescence
According to category of the present invention, most of phosphorescence light emitting host all can combine with assistant ligand of the present invention in principle, forms novel phosphorescent light-emitting materials, reduces thermal evaporation temperature on the one hand, maintain the electronic stability of material on the other hand, reduce manufacturing cost.For convenience of explanation main part and assistant ligand combination and form heavy metal phosphorescent complexes of the present invention, following table lists some red phosphorescent luminescent materials, for some preferred but non-exhaustive all combinations, its first triplet is in 1.90-2.07eV, corresponding to emission wavelength 650 nanometer to 600 nanometer:
。
some emitting red light iridium (III) ligand complexes
For convenience of explanation main part and assistant ligand combination and form heavy metal phosphorescent complexes of the present invention, following table lists some phosphorescent light-emitting materials shorter compared with red wavelength (as green, yellow-green colour), but non-exhaustive all combinations, for some preferred but non-exhaustive all combinations, its first triplet is in 2.10-2.2.48eV, corresponding to emission wavelength 590 nanometer to 500 nanometer:
。
some green emitting iridium (III) ligand complexes
For convenience of explanation main part and assistant ligand combination and form heavy metal phosphorescent complexes of the present invention, following table lists some phosphorescent light-emitting materials shorter compared with green wavelength (as turquoise, blue, hyacinthine), but non-exhaustive all combinations, for some preferred but non-exhaustive all combinations, its first triplet is in 2.48-2.74eV, corresponding to emission wavelength 500 to 440 nanometer:
。
some blue-light-emitting iridium (III) ligand complexes
The present invention also comprises for the application of above-mentioned luminescent material at organic luminescent device (OLED).As organic semiconductor, material described in principle can as charge transport layer, barrier application.Economically consider, what is more important is as the application of luminescent layer.When being used as luminescent layer, for improving luminous efficiency, be necessary the gathering as far as possible avoiding light emitting molecule.Typically use concentration luminescence (weight) material of 0.2 to 25%, be doped in a material of main part.The doping content more optimized is 2-18%.Certainly, material of main part also can be 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 concentration luminescence (weight) material of 2 to 15%, be doped in a material of main part.What material of main part was conventional is containing carbazole or fragrant Ammonia material.A kind of material of main part is 4,4 '-N, N '-two carbazole-biphenyl (CBP):
。
For reaching excellent device performance, a flourishing organic light emitting diode also can comprise other organic semiconductor material multiple, and Fig. 2 is an illustrative device structure.On anode, can an optional hole injection layer, as blue or green in phthalein blue (CuPc) or other compounds containing fragrant ammonia (Appl.Phys.Lett., 69,2160 (1996),
。
Similarly, between hole injection layer and emission layer EML, also can select a hole transmission layer, as used 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, the example for barrier material is 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline (BCP), and its structure is:
。
Between blocking layer and negative electrode, also usually use electron transfer layer and electron injecting layer.Electron transport layer materials can optional metals quinoline compound, as three-(8-hydroxyl) aluminium (Alq3) ， oxadiazole or triazole species.The structure of Alq3 is:
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. 2 one typically constructs, but is not unique application structure.Wherein the general thickness of organic semiconductor layer is 50-250 nanometer, and preferred total thickness is 80-180 nanometer.
Use OLED luminescent device, can be used for flat screen display, as Mobile phone screen, i-Pack shields, TV screen, computer screen etc.Phosphor material of the present invention also may be used for plate lighting.For reaching white-light illuminating, be necessary that the OLED of use 2 kinds or three kinds different colours is by longitudinal stack, or level is mixed into white-light illuminating device.
The invention has the beneficial effects as follows, adopt bidentate title complex that fragrant heterocycle 6-5 arranges in pairs or groups as assistant ligand, by chemical hybrid form, obtain novel heavy metal ligand complex, applicable polychrome phosphorescence luminescence application, has excellent thermally-stabilised and electronic stability and easy feature processed concurrently.Especially the organic luminescent device of large-area flat-plate display screen and highlight illumination application is applicable to.
Accompanying drawing explanation
Fig. 1 is existing heavy metal-phosphorescent chromophores two part.
Fig. 2 is organic LED structure schematic diagram according to an embodiment of the invention.
Fig. 3 is for adopting red emitting material of the present invention 20electric shock emmission spectrum.
Fig. 4 is for adopting green light luminescent material of the present invention 28electric shock emmission spectrum.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with examples of implementation.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar popularization when intension of the present invention.Therefore the present invention is not by the restriction of following public specific embodiment.
embodiment 1: prepare containing the red phosphorescent iridium complex of thiophene pyridine:
。
Step 1(2-thiophene-pyridine 15preparation): in 50 ml 1,2-glycol dimethyl ethers, add the bromo-pyridine of 2-(7.90 g, 50.0 mmol), thienyl boric acid (7.68 g, 60.0 mmol), 0.28g palladium, 1.32g triphenyl phosphorus, 68 milliliters of 2M solution of potassium carbonate.Mixture is heated to backflow 18 hours under a nitrogen.After reactant cooling, add 50ml water and 50ml vinyl acetic monomer.After separatory, organic layer uses saturated brine cleaning, dried over mgso.Use 0,5% and 10% vinyl acetic monomer/normal hexane to make leacheate, by silicagel column, purifying obtains light color oily, then after normal hexane recrystallization, obtain product 2-thiophene-pyridine 15(86% productive rate). 1H NMR (300MHz， CDCl 3): δ=8.65（d,1H）;7.81(m,1H); 7.60(d,1H,);7.34(m,1H); 7.22(d,1H,); 7.0-7.1(m,2H)。
Tolyl between step 2(1-() isoquinoline 99.9 18preparation) :at 50 ml 1, in 2-glycol dimethyl ether and 40 ml distilled water, add 1-chloro isoquinoline 99.9 (10.0g, 61.12mmol), 3-methylphenylboronic acid (9.13g, 67.14mmol), palladium (0.68g, 3.06 mmol), triphenyl phosphorus (3.2 g, 12.2mmol), sodium carbonate (21.96g, 158.92mmol).Mixture is heated to backflow 16 hours under a nitrogen.After reactant cooling, add 60ml water and 60ml vinyl acetic monomer.After separatory, organic layer uses saturated brine cleaning, dried over mgso.Use 0,5% and 10% vinyl acetic monomer/normal hexane to make leacheate, by silicagel column, purifying obtains light color oily, then after normal hexane recrystallization, obtain tolyl between white powder product 1-() isoquinoline 99.9 18(74% productive rate).
Step 3(dichloro-bridged dimer 19synthesis): in mixing liquid cellosolvo (94ml) and pure water (24ml), add 1-(3-methylphenyl) isoquinoline 99.9 18(9.30g, 42.40 mmol) and IrCl 3(7.9g, 21.20 mmol).Reflux 48 hours under a nitrogen.After cooling, yellow solid is through filtration under diminished pressure, and methyl alcohol and vinyl acetic monomer obtain 9.6g(68% after drip washing respectively) chlorine bridge dimer 19.
Step 4(iridium (III) complex compound 20synthesis): in 155 milliliters of cellosolvos, add chlorine bridge dimer 19(9.6g, 7.2 mmol), three fluosulfonic acid silver (14.7mmol) and 2-thiophene-pyridine 15(4.37g, 29.3 mmol).Mixture is heated to 95 oc keeps 60 hours.Cooled and filtered, obtains head product 11.8g after methyl alcohol drip washing.Use 50% methylene dichloride/normal hexane to make leacheate, by silicagel column, purifying obtains red powder product 4.9 grams.Product, after distillation, obtains 2.7g pure products two-[between 1-toluene isoquinoline 99.9]-2-thiophene pyridine-iridium (III) complex compound 20.
embodiment 2: prepare containing the green phosphorescent iridium complex of thiophen pyrazine part:
。
Step 1(2-methyl-3-(2-thiophene) pyrazine 23preparation): in 50 ml 1,2-glycol dimethyl ethers, add the chloro-3-methylpyrazine of 2-(6.46g, 50.0 mmol), thienyl boric acid (5.76 g, 60.0 mmol), 0.28g palladium, 1.32g triphenyl phosphorus, 68 milliliters of 2M solution of potassium carbonate.Mixture is heated to backflow 18 hours under a nitrogen.After reactant cooling, add 50ml water and 50ml vinyl acetic monomer.After separatory, organic layer uses saturated brine cleaning, dried over mgso.Use 0,5% and 10% vinyl acetic monomer/normal hexane to make leacheate, by silicagel column, purifying obtains light color oily, then after normal hexane recrystallization, obtain white powder product 2-thiophene-3-Methyl-pyrazin 23(65% productive rate). 1H NMR (300MHz， CDCl 3): δ=8.40（d,2H）; 7.20(m,1H,);7.0-7.1(m,2H); 2.35(s,3H, -CH 3)。
Step 2(2-(3-biphenyl) pyridine 26synthesis): face in dimethylbenzene at 75 milliliters and add 3-bromo biphenyl (3.0g, 12.9mmol), 2-(tri-tert tin) pyridine (5.92g, 16.1 mmol) and PdCl 2(triphen phosphorus) (0.45g), heated under nitrogen refluxes 20 hours.Use 20% vinyl acetic monomer/normal hexane to make leacheate, by silicagel column, purifying obtains yellow oily 2-(3-biphenyl) pyridine 26product (2.90g, 97% productive rate).
Step 3(dichloro-bridged dimer 27synthesis): in mixing liquid cellosolvo (94ml) and pure water (24ml), add 2-(3-biphenyl) pyridine 23(8.8 g, 42.40 mmol) and IrCl 3(7.9g, 21.20 mmol).Reflux 48 hours under a nitrogen, after cooling, yellow solid is through filtration under diminished pressure, and methyl alcohol and vinyl acetic monomer obtain 9.0g(72% after drip washing respectively) chlorine bridge dimer 27.
Step 4(iridium (III) complexes preparation): in 155 milliliters of cellosolvos, add chlorine bridge dimer 27(9.0g, 7.4 mmol), three fluosulfonic acid silver (14.7mmol) and 2-methyl-3-(2-thiophene) pyrazine 23(5.16g, 29.3 mmol).Mixture is heated to 95 oc keeps 60 hours.Cooled and filtered, obtains head product 11.1g after methyl alcohol drip washing.Use 50% methylene dichloride/normal hexane to make leacheate, by silicagel column, purifying obtains yellow powder product 4.6 grams.Product, after distillation, obtains 2.1g pure products two-[2-(3-biphenyl) pyridine]-2-methyl-3-thiophen pyrazine-iridium (III) complex compound 28.
embodiment 3(POLED prepares and compares): reach 10 at a base vacuum -5in the Multisource evaporation OLED Preparation equipment of handkerchief, adopt following device architecture: ITO/CuPC(100)/NPD (400)/CBP:9% phosphorescent dopants (300)/BPhen(300)/Alq3(550)/LiF/Al, use different phosphorescence light-emitting dopants to prepare POLED luminescent device to compare.Wherein the vacuum moulding machine speed of each organic layer and electrode and time list in table 1.
Table 1:PHOLED device preparation condition (weight concentration 9% of adulterating in luminescent layer).
Use typical known green glow (PhPPY 3ir, (PhPPY) 2ir (acac)) and typical known ruddiness (PIQ 3ir, (Pig) 2ir (acac)) as a comparison, in conjunction with example one of the present invention and the phosphorescent dopants (compound cited by example two 28with 20), its chemical molecular formula is classified as follows:
，
The green glow adopting above-mentioned phosphorescent dopants obtained or ruddiness PHOLED, its electric extremely emmission spectrum is roughly similar, and (Fig. 3 Fig. 4 is respectively luminescent material of the present invention 20with 28electric shock launches EL spectrum).But difference shows high temperature (70 oc) (40mA/cm in accelerated weathering test 2under current density).Adopt the phosphorescent light-emitting materials that assistant ligand of the present invention is formed, its accelerated deterioration time (reducing to for 80% light intensity time) is all higher than the phosphorescent light-emitting materials of the 2 employing methyl ethyl diketone roots of accompanying.
Table 2: the different phosphate photodopant PHOLED characteristics of luminescence and stability test.
The above is only embodiments of the invention, not does any pro forma restriction to the present invention.Any those of ordinary skill in the art, are not departing under technical solution of the present invention ambit, the technology contents of above-mentioned announcement all can be utilized to make many possible variations and modification to technical solution of the present invention, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent variations and modification, all still belongs in the protection domain of technical solution of the present invention.

Claims (10)

1. a metal combination body complex compound, by phosphorescent chromophores part, atoms metal and assistant ligand formed, expressed by the following formula:
It is characterized by:
A. phosphorescent chromophores part is made up of (n=1 or 2) single or two part, and its phosphorescence light-emitting zone is 400-700 nanometer, corresponding 1st triplet (T 1) be 3.10-1.77 eV; First-selection is 450-640 nano luminescent region, and corresponding first-selected 1st triplet is 2.76-1.94eV;
B. atoms metal M is made up of Ir, Pt, Os, Re, and first-selection is Ir, Pt; When its metal is Pt, phosphorescent chromophores part number n is 1; When its metal is Ir, Os, Re, phosphorescent chromophores part number n is 2;
C. assistant ligand is different from phosphorescence non-chromophoric ligand, the bidentate ligand that the six Yuans fragrant heterocycles connected for covalent linkage and five yuan of fragrant heterocycles form; Wherein hexa-atomic fragrant heterocycle contains at least one N=C key, and five yuan of fragrant heterocycles contain at least one C=C key.
2. metal combination body complex compound according to claim 1, wherein A, B, C, D(are from A-D) or carbon atom, or nitrogen-atoms; E, F, G or carbon atom or nitrogen, sulphur, Sauerstoffatom; From R 1-R 7substituting group H, D, fluoro, chloro, iodo, or other hydrocarbon substituent, comprise alkyl to replace, aromatic ring replaces, fragrant heterocyclic substituted, aralkyl replaces, and fragrant Heterocyclylalkyl replaces, and alkoxyl group replaces, aryloxy replaces, and fragrant hetero-oxy replaces, and aralkoxy replaces, virtue heterocyclylalkoxy groups replaces, and replaces number and can be part or entirely replace.
3. metal combination body complex compound according to claim 2, its assistant ligand is different from phosphorescence non-chromophoric ligand, six Yuans fragrant heterocycles containing at least one N=C key for covalent linkage connection form conjugacy assistant ligand with the 5-membered aromatic ring containing at least one C=C key or fragrant heterocycle and form, one of them hexa-atomic fragrant heterocycle comprises pyridine, pyridazine (pyridazine), pyrimidine (pyrimidine) and pyrazine (pyrazine) stablize fragrant heterocycle; One of them five yuan of fragrant heterocycle comprises thiophene, furans, thiazole ， oxazole, or its corresponding substituent;
First-selected assistant ligand comprises 1-12structure:
R wherein 1-R 5substituting group H, D, fluoro, chloro, iodo, or other hydrocarbon substituent, comprise alkyl to replace, aromatic ring replaces, fragrant heterocyclic substituted, aralkyl replaces, and fragrant Heterocyclylalkyl replaces, and alkoxyl group replaces, aryloxy replaces, and fragrant hetero-oxy replaces, and aralkoxy replaces, virtue heterocyclylalkoxy groups replaces, and replaces number and can be part or entirely replace.
4. metal combination body complex compound according to claim 2, its phosphorescent chromophores light-emitting zone is 400-700 nanometer, corresponding 1st triplet (T 1) be 3.10-1.77 eV; First-selection is 450-640 nano luminescent region, and corresponding first-selected 1st triplet is 2.76-1.94eV;
The first-selected main part of chromophoric group is containing, for example lower structure a-P:
Wherein R in main part 1-R 4be 1 to multiple substituting group; Substituting group comprises one or more methyl, ethyl, and is less than the alkyl of 8 carbon atoms; Substituting group comprises one or more methoxyl groups, oxyethyl group, and is less than the alkoxyl group of 8 carbon atoms; Substituting group comprises one or more phenyl, naphthyl, thienyl, pyrryl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl; Substituting group comprises one or more F, Cl, Br, I, D, CN, NO 2, NH 2, dimethylamino, phenylbenzene ammonia.
5. metal combination body complex compound according to claim 2, its light to luminous or electricity to luminescence is red, and its first triplet is in 1.90-2.07eV, corresponding to emission wavelength 650 nanometer to 600 nanometer, comprises phosphorescent light-emitting materials as follows:
。
6. metal combination body complex compound according to claim 2, its photoluminescence or electroluminescent are green, and its first triplet is in 2.10-2.2.48eV, corresponding to emission wavelength 590 nanometer to 500 nanometer, comprises phosphorescent light-emitting materials as follows:
。
7. metal combination body complex compound according to claim 2, its photoluminescence or electroluminescent are blue, and its first triplet is in 2.48-2.74eV, corresponding to emission wavelength 500 to 440 nanometer, comprises phosphorescent light-emitting materials as follows:
。
8. metal combination body complex compound according to claim 2, its photoluminescence or electroluminescent are mixture colorss.
9. be applied to an organic luminescent device, comprise a transparency conductive electrode, a metal electrode, and the organic semiconductor between sandwiching, organic semiconductor wherein contains metal combination body complex compound according to claim 2.
10. a flat-plate luminous display screen, comprises one or more organic light emitting diodes in light emitting display wherein, this Organic Light Emitting Diode employs luminescent phosphor material according to claim 2.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108456230A (en) * 2017-02-22 2018-08-28 环球展览公司 Electroluminescent organic material and device

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1364847A (en) * 2000-12-01 2002-08-21 佳能株式会社 Metal ligand compound, luminous device and display device
CN1711275A (en) * 2002-11-08 2005-12-21 科文有机半导体有限公司 Palladium and platinum complexes
CN101429219A (en) * 2003-03-24 2009-05-13 南加利福尼亚大学 Phenyl-pyrazole complexes of Ir

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1364847A (en) * 2000-12-01 2002-08-21 佳能株式会社 Metal ligand compound, luminous device and display device
CN1711275A (en) * 2002-11-08 2005-12-21 科文有机半导体有限公司 Palladium and platinum complexes
CN101429219A (en) * 2003-03-24 2009-05-13 南加利福尼亚大学 Phenyl-pyrazole complexes of Ir

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108456230A (en) * 2017-02-22 2018-08-28 环球展览公司 Electroluminescent organic material and device
US11254697B2 (en) 2017-02-22 2022-02-22 Universal Display Corporation Organic electroluminescent materials and devices
US11760770B2 (en) 2017-02-22 2023-09-19 Universal Display Corporation Organic electroluminescent materials and devices

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