CN103665048A - Metal complex and application thereof in organic electroluminescent device - Google Patents
Metal complex and application thereof in organic electroluminescent device Download PDFInfo
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Abstract
The invention relates to a novel metal complex and application thereof in an organic luminescent device. The structural general formula of the metal iridium complex for near infrared luminescence is LnIrX(3-n), wherein X is selected from acetylacetone, dibenzoylmethane, dipivaloylmethane or picolinic acid; n is selected from 1, 2 or 3; L is selected from the following structural formula L1, L2 or L3; R1-R9 are independently selected from H, C1-10 alkyl, C1-10 alkoxy, C1-10 alkylamino, carbazolyl, F, trifluoromethyl and C5-18 aryl respectively; and Ar represents C5-18 aryl and C5-18 heterocyclic aryl. The metal complex has the advantages of short luminescence life and high luminescence efficiency; and an organic luminescent device prepared from the luminescent material has the characteristic of high luminescence efficiency under high current density. The structural formula L1, the structural formula L2 and the structural formula L3 are shown in the specification.
Description
Technical field
The present invention relates to a kind of novel metal complexes and the application in organic luminescent device thereof.The organic luminescent device that is specifically related to the near-infrared luminous transition metal complex of a class and comprises this class material, belongs to organic light emitting display technical field.
Background technology
One section of wave spectrum of wavelength region from 700 to 1500 nanometers is known as near-infrared region.There is 50% sun power nearly to fall within this region; It is minimum that the near-infrared light source of 1.31 and 1.55 microns can make the loss of optical fiber drop to; In addition, bio-tissue main component oxyphorase and water are the most weak to 650 photoabsorption of arriving in 900nm wavelength region.Therefore, exploitation near infrared material and technology all have important pushing effect for numerous areas such as the energy, communication, bio-imaging, sensing and demonstrations.
Near infrared material, different according near infrared ray and the material mode of action, can be divided near infrared absorption, reflection and emissive material etc.Wherein near infrared absorption material is a modal class near infrared material, is widely used in storage, false proof, phototherapy and solar cell etc.Near-infrared reflection material is widely used as the coating of ir reflector or heat reflector, can be coated on the article of deck, clothes, tent and some indoor and outdoors of boats and ships with reflected sunlight, plays the effect of cooling energy-saving.The range of application of near-infrared light-emitting material is very extensive, in fields such as demonstration at night, stealthy technique, optical-fibre communications and bio-imagings, all demonstrate huge application potential and wide market outlook, but it is very rare that wavelength surpasses the high efficiency light-emitting material of 800nm, and existing research work mainly concentrates on inorganic materials.Compare with inorganic materials, organic materials has the advantages such as complete processing is simple, material source abundant, the easy adjusting of optical characteristics, therefore, has started over the past two years the research boom of developing organic near-infrared light-emitting material.
The near-infrared light-emitting material that is seen at present report substantially can be divided into pure organic molecule, nanocrystalline, rare earth metal complex and the large class of transition metal complex four.
Pure organic molecule type near infrared material generally has large π structure or D-A structure (Donor-Acceptor), (Chem.-Asian J.2010 for the people such as Wang, 5,1006-1029) and the people (Curr.Opin.Chem.Biol.2010 such as Escobedo, 14,64-70) it has been carried out at large summary.When this type of material is used for to organic luminescent device (Organic Light-Emitting Diodes, OLEDs), due to the luminous excited singlet (S that comes from
1→ S
0), device efficiency is generally not high.2011, the people such as Emami (Opt Express2011,19,3619-3626) OLED device luminous the be positioned at 900 ~ 1150nm of report based on a class A-D-A oligomer, the highest external quantum efficiency η
eQE=3.3%(current density, J=2 * 10
-2mA/cm
2), almost reached the limit of this class material.
Nanocrystalline, claim again quantum dot, be a class luminescent material emerging along with the development of nanosecond science and technology.Unique nanometer size effect and Dielectric confinement effect make quantum dot have adjustable emission wavelength and higher quantum yield, but toxicity and stability are also when this type of material of development, not allow the problem ignored.Recently, and the people such as Sun (Nat Nanotechnol2012,7,369-373) the OLED device the highest external quantum efficiency of report based on PbS quantum dot reaches 2%, than the data of reporting before this, improved twice.
Rare earth metal complex is the near-infrared light-emitting material that a class is more traditional, ion centered by the rare earth metals such as Nd, Yb, Er, Pr, Po, the characteristic line spectrum of tool, but luminous quantum yield lower (<1%).2011, and the people such as Katkova (J.Mater.Chem.2011,21,16611-16620) OLED device luminous the be positioned at 982nm of report based on ytterbium complex, power efficiency reaches 1.22mW/W, and research more before this improves a lot.
Transition metal complex is a class phosphorescent light-emitting materials that has atoms metal centered by the transition metal such as iridium, platinum, osmium, copper.This class material emission wavelength is easily adjusted, and quantum yield is higher, but cost is also high, and according to the difference of central metal atom, the emission wavelength of title complex and efficiency etc. can present larger difference.At present with the people such as Graham (Chem.Mater.2011,23,5305-5312) report based on platinum porphyrins derivative Pt-Ar
4the OLED device performance of TBP is the highest, the luminous 764nm that is positioned at, maximum external quantum efficiency η
eQE=9.2%.
In sum, the OLED device efficiency with transition metal complex in four class materials is the highest, but this class material also exists the problem of needing solution badly---efficiency roll-off.With Pt-Ar
4tBP is example, although the maximum external quantum efficiency of its device is up to 9.2%, is in current density, J <1 * 10
-2mA/cm
2lower acquisition; When current density increases to 10mA/cm
2time, η
eQEdropped to half of peak value, and at 1000mA/cm
2, device is luminous hardly.Do not address this problem the requirement that cannot meet practical application.
In research before, applicant finds the neutral compound Ir (pbq-g) of metal iridium
2acac(J.Mater.Chem.2009,19,6573-6580) and derivative (CN101077971), with ionic complex [Ir (pbq-g)
2(Bphen)]
+pF
6 -[Ir (mpbqx-g)
2(Bphen)]
+pF
6 -(J Phys Chem C2012,116,11658-11664), all there is near-infrared luminous characteristic, and their OLED device efficiency roll-offs very little.Device ITO/NPB (40nm)/Alq3:10%Ir (pbq-g) wherein
2acac (40nm)/Alq
3(10nm) the maximum η of/Mg:Ag
eQE=1.1%, and current density is up to 1000mA/cm
2, η
eQEstill be greater than 1%, efficiency does not almost decline.
Do why transition metal platinum complex and complex of iridium have so different performance? bibliographical information platinum complex Pt-Ar
4tBP(Chem.Mater.2011,23, in the exciton life-span long (32 μ s) 5296-5304), rate of irradiation is less by (1.0 * 10
4s
-1), and planar configuration makes intermolecularly more easily mutually to pile up, and causes triplet excitons excessive concentration and buries in oblivion between two.Relatively, complex of iridium Ir (pbq-g)
2the exciton life-span short (0.57 μ s) of acac, rate of irradiation large (4.4 * 10
4s
-1), and molecule is octoploids structure, is difficult for bumping and quencher between exciton.Therefore,, from the angle of practical application, complex of iridium has huge development potentiality near infrared band.
Yet the current near infrared complex of iridium of having reported only has very few several.2006, the people such as Chen reported a series of quinoxaline complex of iridium (Can.J.Chem.2006,84,309-318), in solution, luminescence peak surpasses 900nm.In the same year, the people such as Williams have reported performance (Appl.Phys.Lett.2006,89,083506 of iloquinoline derivative near infrared material in organic luminescent device; US2008269491-A1), its electroluminescent phosphorescence peak value is positioned at 720nm, and radiant exitance surpasses 100 μ W/cm
2, maximum external quantum efficiency approaches 0.1%.In the recent period, the people such as Palmer reported take encircle greatly the complex of iridium that corroles is part (Angew Chem Int Edit2011,50,9433-9436), in solution luminescence peak in about 800nm, Φ
p≈ 1%.Therefore, obtain efficient near-infrared luminous complex of iridium with deep excavation complex of iridium the advantage near infrared band, be an important topic urgently breaking through.
Summary of the invention
The object of the invention is to propose a class photochromic pure and there is the near-infrared light-emitting material of suitable luminous efficiency, be applied to organic luminescent device, by introducing large pi-conjugated structure and steric group, reduce the collision between dyestuff triplet excitons, overcome the problem of device efficiency roll-off under high current density.
Because phosphor material can utilize 75% triplet exciton and 25% singlet state exciton, and fluorescent material only utilizes 25% singlet state exciton, and phosphor material has the luminous efficiency higher than fluorescent material.Anthracene is good fluorescence radiation parent, containing the compound of anthracene receive much concern in luminescent material because luminous efficiency is high (KanY, et al., Appl.Phys.Lett., 2004,84,1513; Tao S, et al, Chem.Phys.Lett., 2004,397,1-4).In phosphor material, introduce class anthracene structure, prediction can, in conjunction with the two efficient feature, obtain well behaved material.In addition, in the research in early stage, find ionic complex [Ir (mpbqx-g)
2(Bphen)]
+pF
6 -(JPhys Chem C2012,116,11658-11664) there is near-infrared luminous characteristic, the OLED device luminescence peak of preparing with it is positioned at 753nm, and maximum external quantum efficiency is 0.33%, and maximum radiation emittance is 95 μ W/cm
2, and the nearly unavailable rate problem of roll-offing.On this basis, in order further to improve the luminous efficiency of device, need to start with from the angle of molecular designing.
The present invention is based on above consideration, the neutral metal complex of iridium with class anthracene structure has been synthesized in design, obtains efficient near-infrared light-emitting material.
Near-infrared light-emitting material metal iridium complex provided by the invention, its general structure is L
nirX
(3-n),
Wherein X is selected from methyl ethyl diketone, phenyl phenacyl ketone, dipivaloylmethane(DPVM) or pyridine carboxylic acid etc.;
N=1 wherein, 2 or 3;
Wherein L is selected from following structure:
Wherein, R
1-R
9be independently selected from hydrogen atom, carbonatoms, 1-respectively? alkyl, carbonatoms be 1-? alkoxyl group, carbonatoms be 1-? alkylamino, carbazyl, fluorine atom, trifluoromethyl and carbonatoms be?-? aromatic group; Does Ar represent that carbonatoms is?-? aryl, carbonatoms be?-? heterocyclic aryl.
In order more to clearly demonstrate content of the present invention, the preferred structure in the type of compounds that lower mask body narration the present invention relates to:
It is short that metal complexes of the present invention has luminescent lifetime, the advantage that luminous efficiency is high, and the organic luminescent device that uses this luminescent material to prepare, has the characteristic of high-luminous-efficiency under high current density.
Accompanying drawing explanation
Fig. 1 is the electroluminescent graph of embodiments of the invention device OLED-6.
Fig. 2 is current-voltage and the radiant exitance-voltage pattern of embodiments of the invention device OLED-6.
Fig. 3 is external quantum efficiency efficiency-current density figure of embodiments of the invention device OLED-6.
Fig. 4 is the nmr spectrum of embodiments of the invention ligand L-1.
Fig. 5 is the nmr spectrum of embodiments of the invention material C 1-1.
Fig. 6 is the ESI mass spectrum of embodiments of the invention material C 1-1.
Embodiment:
Ligand L-1 of the present invention can reference literature (J Phys Chem C2012,116,11658-11664), by following route preparation.
Reaction formula:
Process: by 1.66g(10.5mmol) 2,3-diaminonaphthalene and 1.48g(10mmol) 1-phenyl-1,2-propanedione is dissolved in the dehydrated alcohol of 30mL, return stirring 5 hours.After being chilled to room temperature, concentrate gained solution, column chromatography for separation, take petrol ether/ethyl acetate=12/1 as elutriant, obtains yellow solid powder, and productive rate is 80%.
Use with substituent 2,3-diaminonaphthalene and with substituent aromatic base-1,2-propanedione can obtain different parts.The part that belongs to general formula L1 all obtains by above path.
Ligand L-2 of the present invention can reference literature (J Phys Chem C2012,116,11658-11664), by following route preparation.
Reaction formula:
Process: by 1.9g(12mmol) 2,3-diaminonaphthalene and 1.9g(12mmol) naphthoquinones is dissolved in 60mL dehydrated alcohol, return stirring 5 hours.Be chilled to room temperature, filter, discard filter cake.Column chromatography for separation, with sherwood oil/dichloromethane solvent system wash-out, obtains yellow solid, productive rate 87%.
Use with substituent 2 3-diaminonaphthalene and can obtain different parts with substituent naphthoquinones.The part that belongs to general formula L2 all obtains by above path.
Ligand L-3 of the present invention can reference literature (J.Org.Chem.1994,59,823-828; Thin Solid Films2008,516,6186-6190), by following route preparation.
Reaction formula:
Process: synthetic minute four steps are carried out first slowly drips the 5mL vitriol oil in 50mL methyl alcohol, transfers in constant pressure funnel stand-by after completing.Separately the 30mL vitriol oil is slowly added in 60mL methyl alcohol, adds afterwards 5.0g(27mmol) 3-amino-2-naphthoic acid, reflux 10 minutes, more slowly drip reserve liquid in reaction system, backflow is spent the night.After cooling, be concentrated into without methyl alcohol, be slowly poured in frozen water, with sodium bicarbonate, adjust PH to neutral, filter.Use methylene dichloride dissolving filter cake, dry 6 hours of concentrated final vacuum, obtains 5.05g khaki color solid, productive rate 94%.
Product is dissolved in 50mL anhydrous tetrahydro furan, under the abundant cooling and stirring condition of ice-water bath, slowly drips the suspension liquid of 1.8g Lithium Aluminium Hydride (48mmol) and 70mL anhydrous tetrahydro furan, continue ice-water bath stirring reaction 3 hours, afterwards with methyl alcohol cancellation reaction.Suction filtration, with tetrahydrofuran (THF) drip washing filter cake, concentrated filtrate, vacuum-drying 6 hours, obtains 4.24g light yellow solid, productive rate 99%.
Again by 2.05g light yellow solid obtained in the previous step (12mmol) and 1.75g(12mmol) α-Tetralone an intermediate of Sertraline, 1.34g(12mmol) potassium tert.-butoxide and 2.18g(12mmol) benzophenone is dissolved in 40mL dioxane, and in argon atmosphere, 100 ℃ are stirred 15 hours.Filtered while hot, after filtrate is cooling, adds the saturated NH of 60mL
4cl, separates out yellow solid, then suction filtration.With deionized water drip washing filter cake, remove inorganic salt, obtain yellow solid powder, productive rate 82%.
By 1.60g(5.7mmol) previous step product and 1.48g(6.5mmol) DDQ is dissolved in 100mL dioxane, and in argon atmosphere, 100 ℃ are stirred 20 hours.After being chilled to room temperature, reaction solution is poured in 10% sodium hydroxide solution (300mL), separated out yellow solid, filter.Column chromatography for separation, obtains orange solid, productive rate 75%.
Use with substituent 3-amino-2-naphthoic acid and can obtain different parts with substituent Tetralone an intermediate of Sertraline.The part that belongs to general formula L3 all obtains by above path.
The synthetic example of metal complexes of the present invention below:
Embodiment mono-: Compound C 1-1
Reaction formula:
Process:
By IrCl
3xH
2o(58%Ir) and 2.2 times of stoichiometric parts are dissolved in the mixed solvent of ethylene glycol monomethyl ether and deionized water (v/v=3/1).Under Ar atmosphere, 100 ℃ of return stirrings are 24 hours.After being chilled to room temperature, filter, filter cake is washed till neutrality with deionized water, then uses successively 10mL ethanol, 200mL ether drip washing filter cake.Finally use methylene dichloride dissolving filter cake, collect filtrate, revolve and steam except desolventizing, 70 ℃ of vacuum-drying 5 hours, obtains reddish brown solid, and productive rate 89%, without the directly input the next step of further purifying.
1H-NMR(CDCl
3,300MHz,δ[ppm]):2.81(s,3H),5.66~5.69(d,1H),6.13~6.18(t,1H),6.74~6.79(t,1H),7.51~7.61(m,2H),7.74~7.78(t,1H),7.95~7.98(d,1H),8.06(s,1H),8.86(s,1H).ESI-MS[m/z]:1497[M-Cl]
+.
By 0.26g(0.17mmol) dichloro bridging intermediate, 0.05g(0.5mmol) methyl ethyl diketone and 0.056g(0.5mmol) potassium tert.-butoxide is dissolved in the mixed solvent of 12mL methylene dichloride/ethanol (v/v=3/1).Reaction system argon shield, 30 ℃ of return stirrings 24 hours.Be chilled to after room temperature, solvent evaporated, then dissolve with methylene dichloride, deionized water extraction 3 times, uses anhydrous MgSO
4dry organic phase.Filter, steaming desolventizes, column chromatography for separation, the product band of collection black.After concentrated, use again methylene dichloride/ether recrystallization, obtain black solid, productive rate 40%.
1H-NMR(CDCl
3,300MHz,δ[ppm]):1.52(s,6H),3.35(s,6H),4.49(s,H),6.65~6.66(d,2H),7.04~7.10(m,2H),7.37~7.58(m,4H),7.88~7.91(d,2H),8.10~8.13(d,2H),8.37~8.40(d,2H),8.63(s,2H),8.90(s,2H).
ESI-MS[m/z]: 831[M+H]
+. ultimate analysis (C43H33N4IrO2): Anal.Calcd.:C, 62.23; H, 4.01; N, 6.75.Found:C, 62.15; H, 3.88; N, 6.63.
Embodiment bis-: Compound C 1-2
Change the methyl ethyl diketone in example one into pyridine carboxylic acid, adopt similar method to obtain title complex, productive rate 45%.
1H-NMR(CDCl
3,600MHz,δ[ppm]):2.68(s,6H),7.41(t,2H),7.51(m,4H),7.65(m,4H),7.79(d,2H),7.88(t,1H),7.98(t,1H),8.06(s,4H),8.16(d,4H),8.29(d,1H),9.01(d,1H).
ESI-MS[m/z]: 854[M+H]
+. ultimate analysis (C44H30N5IrO2): Anal.Calcd.:C, 61.96; H, 3.55; N, 8.21.Found:C, 62.02; H, 3.60; N, 8.19.
Embodiment tri-: Compound C 1-3
By 0.76g(0.5mmol) dichloro bridging intermediate, 0.30g(1.1mmol) main part and 0.28g(1.1mmol) silver trifluoromethanesulfonate is in 50mL ethylene glycol monomethyl ether.Reaction system argon shield, shading, return stirring 24 hours.Be chilled to after room temperature, filter, with a small amount of ethylene glycol monomethyl ether drip washing.Use methylene dichloride wash-out again, collect filtrate, steaming desolventizes, column chromatography for separation, the product band of collection black.After concentrated, use again methylene dichloride/ether recrystallization, obtain black solid, productive rate 30%.
1H-NMR(CDCl
3,300MHz,δ[ppm]):2.81(s,3H),5.66~5.69(d,1H),6.13~6.18(t,1H),6.74~6.79(t,1H),7.51~7.61(m,2H),7.74~7.78(t,1H),7.95~7.98(d,1H),8.06(s,1H),8.86(s,1H).
ESI-MS[m/z]: 1001[M+H]
+. ultimate analysis (C57H39N6Ir): Anal.Calcd.:C, 68.45; H, 3.93; N, 8.40.Found:C, 68.42; H, 3.68; N, 8.35.
Embodiment tetra-: Compound C 1-4
Synthetic and ligand L-1 of main part is similar, and reference literature (J Phys Chem C2012,116,11658-11664); Title complex synthetic with reference to embodiment mono-, productive rate 52%.
ESI-MS[m/z]: 859[M+H]
+. ultimate analysis (C45H37N4IrO2): Anal.Calcd.:C, 62.99; H, 4.35; N, 6.53.Found:C, 62.95; H, 4.36; N, 6.57.
Embodiment five: Compound C 1-5
Main part and title complex synthetic with reference to embodiment mono-, productive rate 43%.
ESI-MS[m/z]: 983[M+H]
+. ultimate analysis (C55H41N4IrO2): Anal.Calcd.:C, 67.26; H, 4.21; N, 5.70.Found:C, 67.30; H, 4.19; N, 5.75.
Embodiment six: Compound C 1-6
Main part and title complex synthetic with reference to embodiment mono-, productive rate 50%.
ESI-MS[m/z]: 859[M+H]
+. ultimate analysis (C45H37N4IrO2): Anal.Calcd.:C, 62.99; H, 4.35; N, 6.53.Found:C, 62.96; H, 4.33; N, 6.58.
Embodiment seven: Compound C 1-7
Main part and title complex synthetic with reference to embodiment mono-, productive rate 55%.
ESI-MS[m/z]: 891[M+H]
+. ultimate analysis (C45H37N4IrO4): Anal.Calcd.:C, 60.73; H, 4.19; N, 6.30.Found:C, 60.75; H, 4.23; N, 6.26.
Embodiment eight: Compound C 1-8
Main part and title complex synthetic with reference to embodiment mono-, productive rate 55%.
ESI-MS[m/z]: 917[M+H]
+. ultimate analysis (C47H43N6IrO2): Anal.Calcd.:C, 61.62; H, 4.73; N, 9.17.Found:C, 61.60; H, 4.77; N, 9.17.
Embodiment nine: Compound C 1-9
Main part and title complex synthetic with reference to embodiment mono-, productive rate 48%.
ESI-MS[m/z]: 833[M+H]
+. ultimate analysis (C41H31N6IrO2): Anal.Calcd.:C, 59.19; H, 3.76; N, 10.10.Found:C, 59.23; H, 3.73; N, 10.07.
Embodiment ten: Compound C 1-10
Main part and title complex synthetic with reference to embodiment mono-, productive rate 40%.
ESI-MS[m/z]: 931[M+H]
+. ultimate analysis (C51H37N4IrO2): Anal.Calcd.:C, 65.86; H, 4.01; N, 6.02.Found:C, 65.85; H, 4.02; N, 6.05.
Embodiment 11: Compound C 1-11
Main part and title complex synthetic with reference to embodiment mono-, productive rate 35%.
ESI-MS[m/z]: 843[M+H]
+. ultimate analysis (C39H29N4IrO2S2): Anal.Calcd.:C, 55.63; H, 3.47; N, 6.65.Found:C, 55.66; H, 3.43; N, 6.63.
Embodiment 12: Compound C 1-12
Main part and title complex synthetic with reference to embodiment mono-, productive rate 42%.
ESI-MS[m/z]: 943[M+H]
+. ultimate analysis (C47H33N4IrO2S2): Anal.Calcd.:C, 59.92; H, 3.53; N, 5.95.Found:C, 59.89; H, 3.55; N, 5.98.
Embodiment 13: Compound C 2-1
The synthetic of main ligand L-2 sees above, title complex synthetic with reference to embodiment mono-, productive rate 38%.
ESI-MS[m/z]: 851[M+H]
+. ultimate analysis (C45H29N4IrO2): Anal.Calcd.:C, 63.59; H, 3.44; N, 6.59.Found:C, 63.53; H, 3.45; N, 6.57.
Embodiment 14: Compound C 2-2
By 1.9g(12mmol) 2,3-diaminonaphthalene and 2.2g(12mmol) 3,4-dimethyl naphthoquinones is dissolved in 60mL dehydrated alcohol, return stirring 5 hours.Be chilled to room temperature, filter, with ethyl alcohol recrystallization, obtain yellow solid, productive rate 85%.
By IrCl
3xH
2o(58%Ir) and 2.2 times of stoichiometric parts are dissolved in the mixed solvent of ethylene glycol monomethyl ether and deionized water (v/v=3/1).Under Ar atmosphere, 90 ℃ of return stirrings are 24 hours.After being chilled to room temperature, filter, filter cake is washed till neutrality with deionized water, then use ethanol successively, ether drip washing filter cake.Finally use methylene dichloride dissolving filter cake, collect filtrate, revolve and steam except desolventizing, 80 ℃ of vacuum-drying 5 hours, obtains brown solid, and productive rate 84%, without the directly input the next step of further purifying.
By 0.25g(0.15mmol) dichloro bridging intermediate, 0.05g(0.5mmol) methyl ethyl diketone and 0.056g(0.5mmol) potassium tert.-butoxide is dissolved in the mixed solvent of 12mL methylene dichloride/ethanol (v/v=3/1).Reaction system argon shield, 35 ℃ of return stirrings 20 hours.Be chilled to after room temperature, solvent evaporated, then dissolve with methylene dichloride, deionized water extraction 3 times, uses anhydrous MgSO
4dry organic phase.Filter, steaming desolventizes, column chromatography for separation, the product band of collection black.After concentrated, use again methylene dichloride/ether recrystallization, obtain black solid, productive rate 35%.
1H-NMR(CDCl
3,600MHz,δ[ppm]):1.61(s,6H),2.57(d,2H),2.99(d,2H),4.54(s,H),7.55(t,2H),7.60(d,2H),7.67(m,4H),8.06(s,4H),8.10(d,2H),8.16(d,4H).
ESI-MS[m/z]: 907[M+H]
+. ultimate analysis (C49H37N4IrO2): Anal.Calcd.:C, 64.95; H, 4.12; N, 6.18.Found:C, 64.82; H, 4.18; N, 6.14.
Embodiment 15: Compound C 2-3
Adopt with the similar method of embodiment bis-and obtain title complex, productive rate 44%.
ESI-MS[m/z]: 930[M+H]
+. ultimate analysis (C50H34N5IrO2): Anal.Calcd.:C, 64.64; H, 3.69; N, 7.54.Found:C, 64.58; H, 3.63; N, 7.57.
Embodiment 16: Compound C 2-4
Adopt with the similar method of embodiment tri-and obtain title complex, productive rate 30%.
ESI-MS[m/z]: 1115[M+H]
+. ultimate analysis (C66H45N6Ir): Anal.Calcd.:C, 71.14; H, 4.07; N, 7.54.Found:C, 71.20; H, 4.05; N, 7.59.
Embodiment 17: Compound C 2-5
Adopt with the similar method of embodiment 14 and obtain main part and corresponding title complex, productive rate 38%.
ESI-MS[m/z]: 907[M+H]
+. ultimate analysis (C49H37N4IrO2): Anal.Calcd.:C, 64.95; H, 4.12; N, 6.18.Found:C, 65.02; H, 4.15; N, 6.13.
Embodiment 18: Compound C 2-6
Adopt with the similar method of embodiment 14 and obtain main part and corresponding title complex, productive rate 40%.
ESI-MS[m/z]: 879[M+H]
+. ultimate analysis (C47H33N4IrO2): Anal.Calcd.:C, 64.29; H, 3.79; N, 6.38.Found:C, 64.33; H, 3.75; N, 6.34.
Embodiment 19: Compound C 2-7
Adopt with the similar method of embodiment 14 and obtain main part and corresponding title complex, productive rate 25%.
ESI-MS[m/z]: 951[M+H]
+. ultimate analysis (C53H33N4IrO2): Anal.Calcd.:C, 67.00; H, 3.50; N, 5.90.Found:C, 67.03; H, 3.53; N, 5.89.
Embodiment 20: Compound C 2-8
By 1.0g(6.3mmol) 2,3-diaminonaphthalene and 1.5g(6.3mmol) 3,6-dimethyl phenanthrenequione is dissolved in the dehydrated alcohol of 30mL, return stirring 5 hours.After being chilled to room temperature, separate out solid, filter, obtain orange/yellow solid, productive rate 94%.
By IrCl
3xH
2o(58%Ir) and 2.2 times of stoichiometric parts are dissolved in the mixed solvent of ethylene glycol monomethyl ether and deionized water (v/v=3/1).Under Ar atmosphere, 90 ℃ of return stirrings are 24 hours.After being chilled to room temperature, filter, filter cake is washed till neutrality with deionized water, then use ethanol successively, ether drip washing filter cake.Finally use methylene dichloride dissolving filter cake, collect filtrate, revolve and steam except desolventizing, 80 ℃ of vacuum-drying 5 hours, obtains brown solid, and productive rate 75%, without the directly input the next step of further purifying.
By 0.28g(0.15mmol) dichloro bridging intermediate, 0.05g(0.5mmol) methyl ethyl diketone and 0.056g(0.5mmol) potassium tert.-butoxide is dissolved in the mixed solvent of 12mL methylene dichloride/ethanol (v/v=3/1).Reaction system argon shield, 35 ℃ of return stirrings 24 hours.Be chilled to after room temperature, solvent evaporated, then dissolve with methylene dichloride, deionized water extraction 3 times, uses anhydrous MgSO
4dry organic phase.Filter, steaming desolventizes, column chromatography for separation, the product band of collection black.After concentrated, use again methylene dichloride/ether recrystallization, obtain black solid, productive rate 28%.
1H-NMR(CDCl
3,600MHz,δ[ppm]):1.50(s,6H),2.45(s,12H),4.47(s,H),7.60(m,4H),7.67(t,4H),8.00(d,2H),8.07(s,4H),8.16(d,4H),8.70(m,4H).
ESI-MS[m/z]: 1007[M+H]
+. ultimate analysis (C57H41N4IrO2): Anal.Calcd.:C, 68.04; H, 4.11; N, 5.57.Found:C, 67.98; H, 4.19; N, 5.50.
Embodiment 21: Compound C 2-9
Adopt with the similar method of embodiment bis-and obtain title complex, productive rate 32%.
ESI-MS[m/z]: 1030[M+H]
+. ultimate analysis (C58H38N5IrO2): Anal.Calcd.:C, 67.69; H, 3.72; N, 6.80.Found:C, 67.67; H, 3.75; N, 6.79.
Embodiment 22: Compound C 2-10
Adopt with the similar method of embodiment tri-and obtain title complex, productive rate 15%.
ESI-MS[m/z]: 1265[M+H]
+. ultimate analysis (C78H51N6Ir): Anal.Calcd.:C, 74.09; H, 4.07; N, 6.65.Found:C, 74.10; H, 4.05; N, 6.63.
Embodiment 23: Compound C 2-11
Adopt with method like embodiment eicosanoid and obtain main part and corresponding title complex, productive rate 30%.
ESI-MS[m/z]: 1071[M+H]
+. ultimate analysis (C57H41N4IrO6): Anal.Calcd.:C, 63.97; H, 3.86; N, 5.24.Found:C, 64.01; H, 3.85; N, 5.28.
Embodiment 24: Compound C 2-12
Adopt with the similar method of embodiment 14 and obtain main part and corresponding title complex, productive rate 26%.
ESI-MS[m/z]: 1007[M+H]
+. ultimate analysis (C57H41N4IrO2): Anal.Calcd.:C, 68.04; H, 4.11; N, 5.57.Found:C, 68.01; H, 4.07; N, 5.59.
Embodiment 25: Compound C 3-1
By IrCl
3xH
2o(58%Ir) and 2.2 times of stoichiometric parts are dissolved in the mixed solvent of ethylene glycol monomethyl ether and deionized water (v/v=3/1).Under Ar atmosphere, 100 ℃ of return stirrings are 24 hours.After being chilled to room temperature, filter, filter cake is washed till neutrality with deionized water, then use ethanol successively, ether drip washing filter cake.Finally use methylene dichloride dissolving filter cake, collect filtrate, revolve and steam except desolventizing, 75 ℃ of vacuum-drying 6 hours, obtains Vandyke brown solid, and productive rate 85%, without the directly input the next step of further purifying.
By 0.23g(0.15mmol) dichloro bridging intermediate, 0.05g(0.5mmol) methyl ethyl diketone and 0.056g(0.5mmol) potassium tert.-butoxide is dissolved in the mixed solvent of 12mL methylene dichloride/ethanol (v/v=3/1).Reaction system argon shield, 40 ℃ of return stirrings 24 hours.Be chilled to after room temperature, solvent evaporated, then dissolve with methylene dichloride, deionized water extraction 3 times, uses anhydrous MgSO
4dry organic phase.Filter, steaming desolventizes, column chromatography for separation, the product band of collection black.After concentrated, use again methylene dichloride/ether recrystallization, obtain black solid, productive rate 38%.
1H-NMR(CDCl
3,600MHz,δ[ppm]):1.55(s,6H),5.21(s,H),7.55(m,2H),7.60(d,2H),7.67(m,4H),7.81(d,2H),7.88(s,2H),8.07(m,4H),8.16(d,4H),8.20(s,2H),8.25(s,2H).
ESI-MS[m/z]: 849[M+H]
+. ultimate analysis (C47H31N4IrO2): Anal.Calcd.:C, 66.57; H, 3.68; N, 3.30.Found:C, 66.60; H, 3.61; N, 3.35.
Embodiment 26: Compound C 3-2
Adopt with the similar method of embodiment 25 and obtain main part and corresponding title complex, productive rate 24%.
ESI-MS[m/z]: 877[M+H]
+. ultimate analysis (C49H35N2IrO2): Anal.Calcd.:C, 67.18; H, 4.03; N, 3.20.Found:C, 67.20; H, 4.05; N, 3.19.
Embodiment 27: Compound C 3-3
Adopt with the similar method of embodiment 25 and obtain main part and corresponding title complex, productive rate 25%.
ESI-MS[m/z]: 877[M+H]
+. ultimate analysis (C49H35N2IrO2): Anal.Calcd.:C, 67.18; H, 4.03; N, 3.20.Found:C, 67.22; H, 4.04; N, 3.15.
Embodiment 28: Compound C 3-4
By 2.05g(12mmol) 3-amino-2-naphthalene methyl alcohol and 2.09g(12mmol) 3,4-dimethyl-3,4-dihydro-1-naphthalenone, 1.34g(12mmol) potassium tert.-butoxide and 2.18g(12mmol) benzophenone is dissolved in 40mL dioxane, and in argon atmosphere, 100 ℃ are stirred 15 hours.Filtered while hot, after filtrate is cooling, adds saturated NH
4cl separates out yellow solid, then suction filtration.With deionized water drip washing filter cake, remove inorganic salt, obtain yellow solid powder, productive rate 75%.
By 1.85g(6.0mmol) previous step product and 1.48g(6.5mmol) DDQ is dissolved in 100mL dioxane, and in argon atmosphere, 100 ℃ are stirred 24 hours.After being chilled to room temperature, reaction solution is poured in 10% sodium hydroxide solution, separated out yellow solid, filter.Column chromatography for separation, obtains orange solid, productive rate 80%.
By IrCl
3xH
2o(58%Ir) and 2.2 times of stoichiometric parts are dissolved in the mixed solvent of ethylene glycol monomethyl ether and deionized water (v/v=3/1).Under Ar atmosphere, 90 ℃ of return stirrings are 24 hours.After being chilled to room temperature, filter, filter cake is washed till neutrality with deionized water, then use ethanol successively, ether drip washing filter cake.Finally use methylene dichloride dissolving filter cake, collect filtrate, revolve and steam except desolventizing, 75 ℃ of vacuum-drying 6 hours, obtains Vandyke brown solid, and productive rate 80%, without the directly input the next step of further purifying.
By 0.25g(0.15mmol) dichloro bridging intermediate, 0.05g(0.5mmol) methyl ethyl diketone and 0.056g(0.5mmol) potassium tert.-butoxide is dissolved in the mixed solvent of 12mL methylene dichloride/ethanol (v/v=3/1).Reaction system argon shield, 40 ℃ of return stirrings 24 hours.Be chilled to after room temperature, solvent evaporated, then dissolve with methylene dichloride, deionized water extraction 3 times, uses anhydrous MgSO
4dry organic phase.Filter, steaming desolventizes, column chromatography for separation, the product band of collection black.After concentrated, use again methylene dichloride/ether recrystallization, obtain black solid, productive rate 40%.
1H-NMR(CDCl
3,600MHz,δ[ppm]):1.54(s,6H),2.80(d,2H),2.99(d,2H),5.19(s,H),7.54(m,2H),7.60(d,2H),7.68(m,4H),7.88(s,2H),8.08(d,2H),8.16(d,4H),8.22(s,2H),8.28(s,2H).
ESI-MS[m/z]: 905[M+H]
+. ultimate analysis (C51H39N4IrO2): Anal.Calcd.:C, 67.75; H, 4.35; N, 3.10.Found:C, 67.62; H, 4.40; N, 3.03.
Embodiment 29: Compound C 3-5
Adopt with the similar method of embodiment bis-and obtain title complex, productive rate 35%.
ESI-MS[m/z]: 928[M+H]
+. ultimate analysis (C52H36N3IrO2): Anal.Calcd.:C, 67.37; H, 3.91; N, 4.53.Found:C, 67.40; H, 3.95; N, 4.54.
Embodiment 30: Compound C 3-6
Adopt with the similar method of embodiment tri-and obtain title complex, productive rate 16%.
ESI-MS[m/z]: 1112[M+H]
+. ultimate analysis (C69H48N3Ir): Anal.Calcd.:C, 74.57; H, 4.35; N, 3.78.Found:C, 74.55; H, 4.35; N, 3.76.
Embodiment 31: Compound C 3-7
Adopt with the similar method of embodiment 10 and obtain main part and corresponding title complex, productive rate 18%.
ESI-MS[m/z]: 949[M+H]
+. ultimate analysis (C55H35N2IrO2): Anal.Calcd.:C, 69.68; H, 3.72; N, 2.95.Found:C, 69.70; H, 3.75; N, 2.99.
The Application Example of the compounds of this invention below:
Prepare organic light-emitting device preferred implementation:
The typical structure of OLED device is: substrate/anode/hole transmission layer (HTL)/organic luminous layer (EL)/hole blocking layer (HBL)/electron transfer layer (ETL)/negative electrode.
(1) substrate can be used the substrate in traditional organic luminescent device, for example: glass or plastics.Substrate is transparent, waterproof, there is smooth surface, easily process.Anode constituent material can adopt transparent high-conductive metal, indium tin oxygen (ITO) for example, indium zinc oxygen (IZO), tindioxide (SnO
2), zinc oxide (ZnO) etc., preferably ITO.
(2) thickness of hole transmission layer is generally at 5nm-5 μ m, preferred compound comprises phthalocyanine compound, aromatic amine compounds etc., the most frequently used as 4,4 '-bis-[N-(1-naphthyl)-N-phenyl amino] biphenyl (referred to as NPB), N, N'-bis-(3-aminomethyl phenyl)-N, N'-phenylbenzene biphenyl (TPD); 1,3,5-tri-(3-methyldiphenyl is amino) benzene (m-MTDATA) etc.The preferred NPB of the present invention.
(3) material of hole blocking layer, preferably have 2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline (referred to as BCP), 4,7-phenylbenzene-1,10-phenanthroline (referred to as Bphen) and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (referred to as TPBI) etc.The preferred TPBI of the present invention and Bphen.
(4) electron transfer layer, is generally a metal-organic complex, as oxine aluminium (Alq
3) and derivative etc., also can select the material identical with hole blocking layer.The preferred Alq of the present invention
3, TPBI and Bphen.
(5) negative electrode constituent material can adopt the metal or alloy of the low work functions such as lithium, magnesium, aluminium, calcium, Al-Li alloy, magnesium silver alloys, magnesium indium alloy,
Or the electrode layer that alternately forms of metal and metal fluoride, the preferred Mg:Ag/Ag electrode of the present invention and LiF/Al electrode.
Organic luminous layer of the present invention, the method for employing Doping Phosphorus photoinitiator dye in material of main part.Available material of main part has the broad varietys such as carbazoles conjugation small molecules, aryl silicon micromolecular and metal complexes, as 4, and 4 '-(N, N '-bis-carbazyl)-biphenyl (CBP), oxine aluminium (Alq
3), gallium binuclear chelate Ga
2(saph)
2q
2, two (10-hydroxy benzo [h] quinoline) beryllium (Bebq2) etc.The phosphorescent coloring that the present invention proposes, the doping consumption in main body is in approximately 1% to approximately 30% scope of luminescent layer total mass.When the amount of phosphorescent coloring more than total amount approximately 30% time, triplet state cancellation, reduces the efficiency of device.When the amount of phosphorescence main body be less than total amount approximately 1% time, the quantity not sufficient of luminescent material, the efficiency of device and life-span reduce.
Organic luminescent device is except comprising anode, hole transmission layer, and organic luminous layer, electron transfer layer and negative electrode, can further include one or two middle layer and hole injection layer, electron injecting layer, electronic barrier layer etc.
A series of organic electroluminescence device of the present invention is prepared in accordance with the following methods: use the steps such as clean-out system, deionized water and UV-irradiation to clean the glass substrate with anode; Vacuum evaporation hole transmission layer; The luminescent layer that vacuum evaporation comprises material of main part and phosphorescent coloring of the present invention; Vacuum evaporation electron transfer layer; Vacuum evaporation negative electrode.
Embodiment 32 fabricate devices OLED-1～OLED-3
Preparation OLED-1: will be coated with sheet glass supersound process in commercial clean-out system of ITO transparency conducting layer, in deionized water, rinse, at acetone: ultrasonic oil removing in alcohol mixed solvent, under clean environment, be baked to and remove moisture content completely, by UV-light and ozone clean, and with low energy positively charged ion bundle bombarded surface.
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 * 10
-5～9 * 10
-3pa, on above-mentioned anode tunic, vacuum evaporation NPB is as hole transmission layer, and evaporation speed is 0.1nm/s, and evaporation thickness is 40nm;
The Ga of vacuum evaporation one deck Doping Phosphorus luminescent material C1-1 on hole transmission layer
2(saph)
2q
2as the luminescent layer of device, C1-1 and Ga
2(saph)
2q
2evaporation speed ratio be 2:10, C1-1 is at Ga
2(saph)
2q
2in doping content be 20% weight ratio (20wt%), the total speed of its evaporation is 0.1nm/s, evaporation total film thickness is 40nm;
Vacuum evaporation one deck Alq on organic luminous layer
3material is as the electron transfer layer of device, and its evaporation speed is 0.1nm/s, and evaporation total film thickness is 30nm;
On electron transfer layer, vacuum evaporation Mg:Ag alloy layer and Ag layer are as the negative electrode of device successively, and wherein the evaporation speed of Mg:Ag alloy layer is 2.0 ~ 3.0nm/s, and thickness is 100nm, and the evaporation speed of Ag layer is 0.3nm/s, and thickness is 100nm.
Prepare according to the method described above OLED-2 and OLED-3, change electron transport material, the performance of device refers to table 1:
Embodiment 33 fabricate devices OLED-4～OLED-6
Prepare according to the method described above OLED-4 ~ OLED-6, change electric transmission layer thickness, the performance of device refers to table 2:
As can be seen from the above table, the emission wavelength of material provided by the invention is positioned at near-infrared region, and its external quantum efficiency reaches 1.8%.The fluorescence quantum efficiency of material self is higher, reaches 0.015.
Embodiment 34 fabricate devices OLED-7～OLED-10
Prepare according to the method described above OLED-7 ~ OLED-10, change luminescent material, the performance of device refers to table 2:
As can be seen from the above table, the emission wavelength of material provided by the invention is positioned at near-infrared region, luminescence peak can red shift to 900nm; But due to energy gap rule, along with luminous red shift, the luminous efficiency of device declines to some extent.
Although describe the present invention in conjunction with the preferred embodiments, but the present invention is not limited to above-described embodiment and accompanying drawing, should be appreciated that under the guiding of the present invention's design, those skilled in the art can carry out various modifications and improvement, and claims have been summarized scope of the present invention.
Claims (4)
1. a class is as near-infrared luminous metal iridium complex, and its general structure is L
nirX
(3-n);
In this general formula, X is selected from methyl ethyl diketone, phenyl phenacyl ketone, dipivaloylmethane(DPVM) or pyridine carboxylic acid, and in general formula, n is selected from 1,2 or 3, and in general formula, L is selected from following structural formula L1, L2 or L3:
Structural formula L1
Structural formula L2
Structural formula L3
In said structure formula L1, L2 and L3, R
1-R
9the aromatic group that alkylamino, carbazyl, fluorine atom, trifluoromethyl and the carbonatoms that the alkoxyl group that the alkyl that is 1-10 independently selected from hydrogen atom, carbonatoms respectively, carbonatoms are 1-10, carbonatoms are 1-10 is 5-18; Ar represents that carbonatoms is the aryl of 5-18, the heterocyclic aryl that carbonatoms is 5-18.
2. compound according to claim 1, structural formula is as follows:
3. the application of the compound described in claim 1 or 2 in organic electroluminescence device.
4. an organic electroluminescence device, comprises negative electrode, anode and is positioned at the direct organic function layer of two electrodes, it is characterized in that, adopts a class as near-infrared luminous metal iridium complex in described organic function layer, and its general structure is L
nirX
(3-n);
In this general formula, X is selected from methyl ethyl diketone, phenyl phenacyl ketone, dipivaloylmethane(DPVM) or pyridine carboxylic acid; In general formula, n is selected from 1,2 or 3; In general formula, L is selected from following structural formula L1, L2 or L3:
Structural formula L1
Structural formula L2
Structural formula L3
In said structure formula L1, L2 and L3, the aromatic group that alkylamino, carbazyl, fluorine atom, trifluoromethyl and the carbonatoms that the alkoxyl group that the alkyl that R1-R9 is 1-10 independently selected from hydrogen atom, carbonatoms respectively, carbonatoms are 1-10, carbonatoms are 1-10 is 5-18; Ar represents that carbonatoms is the aryl of 5-18, the heterocyclic aryl that carbonatoms is 5-18.
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