CN102659847A - Organic iridium complex - Google Patents
Organic iridium complex Download PDFInfo
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- CN102659847A CN102659847A CN2012101116400A CN201210111640A CN102659847A CN 102659847 A CN102659847 A CN 102659847A CN 2012101116400 A CN2012101116400 A CN 2012101116400A CN 201210111640 A CN201210111640 A CN 201210111640A CN 102659847 A CN102659847 A CN 102659847A
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- ppz
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Abstract
The invention discloses an organic iridium complex of the following structural general formula, wherein X represents N-ethyl-3-carbazolyl or 9,9'-dihexyl-2-fluorenyl. The organic iridium complex of the invention can be used as an electroluminescent electron-blocking functional material and mainly used in organic electroluminescent devices.
Description
Technical field
Organic complex of iridium disclosed by the invention relates to a kind of functional materials of electroluminescent device, especially relates to the electronics barrier functionality layer material of electroluminescent device.
Background technology
The organic electroluminescent technology was through the development in twenties years; It has been recognized that the main path that improves OLED luminescent device efficient, except improving the efficient of luminescent material own, another important method changes device architecture exactly; Through in device, introducing the difference in functionality layer; Equilbrium carrier injects transmission, so that better be compounded to form exciton, improves the luminous efficiency of device.
Electronics barrier functionality layer is exactly a kind of functional layer of between the hole transmission layer of device and luminescent layer, introducing in the electroluminescent device, and this functional layer can stop from the negative electrode injected electrons effectively, makes it rest on luminescent layer, thereby improves the luminous efficiency of device.Need have lower lowest unoccupied molecular orbital (LUMO) energy level and the highest occupied orbital (HOMO) energy level suitable as the electronics blocking material with hole mobile material.Ir (ppz)
3Shown in its structural formula as I of typical electronic blocking material.The HOMO energy level of this material is 5.166ev, and lumo energy is merely 1.788ev.
People " Electrophosphorescent p-i-n Organic Light-Emitting Devices for Very-High-Efficiency Flat-Panel Displays " .Adv.Mater.2002 such as Martin Pfeiffer for example; 14,1633-1636 discloses a kind of relevant Ir (ppz)
3As having obtained pure color phosphorescence device in the electronic barrier layer application device, the quantum yield of this device is higher than the device that only uses hole mobile material NPB.Forrest in the same year " High Efficiency single Dopant White Electrophosphorescent Light Emitting Diodes " .New J.Chem; 2002; 26,1171-1178 also discloses a kind of Ir (ppz) that in phosphorescence doping device, uses
3, make the quantum yield of device and luminous intensity all obtain effective raising, obtained the highest at that time white light parts quantum yield 6.4% ± 0.6%.
Ferchet " Multifunction Crosslinkable Iridium Complexes as Hole Transporting/Electron Blocking and Emitting Materials for Solution-Processed Multilayer Organic Light-Emitting Diodes " .Aav.Funct.Mater.2009; 19; 1024-1031 discloses a series of ppz complex of iridium material, finds that this type of material has good cavity transmission ability and electronics blocking capability.Its structure is shown in II:
But it is still less as organic electroluminescent electronics barrier functionality material at present with organic complex of iridium kind.
Summary of the invention
Technical problem to be solved by this invention is to overcome the background technology deficiency, provides a kind of electronics barrier functionality material to use organic complex of iridium.
The general structure of organic complex of iridium of the present invention is as follows:
Wherein X is N-ethyl-3-carbazyl or 9,9 '-dihexyl-2-fluorenyl.
The preferred organic complex of iridium of the present invention is, when X is N-ethyl-3-carbazyl, its structural formula is as follows:
Another preferred organic complex of iridium of the present invention is, when X is 9, during 9 '-dihexyl-2-fluorenyl, its structural formula is as follows:
Synthetic route of the present invention is:
Three hydration iridous chlorides generate chlorine bridge dipolymer with containing the phenylpyrazole reaction, under the Anhydrous potassium carbonate effect, make the target title complex with the reaction of new system beta-diketo derivative then.Wherein X is N-ethyl-3-carbazyl or 9,9 '-dihexyl-2-fluorenyl.
Advantage of the present invention
Organic complex of iridium of the present invention can be used for electronics barrier functionality material, be a kind of organic electroluminescence device electronics barrier functionality material with organic complex of iridium kind, this organic complex of iridium has lower lumo energy, is respectively 1.859ev, 1.998ev; And appropriate H OMO energy level, be respectively 5.158ev, 5.227ev.
Embodiment
In conjunction with embodiment the present invention is done further explain.
Product performance test event and testing tool:
Absorption spectrum is measured with UNICO UV-4802 type twin-beam ultraviolet-visible pectrophotometer; Sample concentration in dichloromethane solution is 10
-5Mol/L, test is to carry out in 20 ℃～25 ℃ in temperature.
Chemical property adopts the CHI660D chem workstation to measure, with glass-carbon electrode as working electrode, with Ag/Ag
+Be reference electrode, anhydrous methylene chloride is that (concentration is 10 to solvent
-4Mol/L), tetrabutyl ammonium hexafluorophosphate (n-Bu
4NPF
6, 0.1M) being ionogen, scanning speed is 50mV/s.Energy level calculates according to following formula and calculates:
E
HOMO＝eE
Ag/AgCl-eE
oxon()E
Ag/AgCl＝4.70ev
E
g＝E
HOMO-E
LUMO
E
g＝hC/λ
on≈1240/λ
on
E wherein
HOMO, E
LUMORepresent HOMO, lumo energy respectively; E
Ag/AgClBe the silver electrode current potential; E
OxonOxidizing potential for test substances; E
gThe expression energy gap; λ
OnExpression energy of absorption edge wavelength.
Embodiment 1 two (N-phenylpyrazole) [1-(N-ethyl-3-carbazyl)-5,5-dimethyl--1,3-hexanedione] closes iridium [Ir (ppz)
2(tmdc)] synthetic
(1) (9-ethyl-3-carbazyl)-5,5-dimethyl--1,3-two hexanones (tmdcH) synthetic
Under the nitrogen protection, add 3-ethanoyl-N-ethyl carbazole 23.7g (0.1mol) in the 500ml there-necked flask successively, 3; 3 dimethyl butyrate acetoacetic ester 43.20g (0.3mol), dry toluene 200ml, sodium amide 15.6g (0.4mol); Be warming up to backflow, react 5 hours postcooling to room temperature.Add 100ml water, stir that slowly to use 10% Hydrogen chloride to be neutralized to pH value down be about 8.Separatory, extraction, to neutral, anhydrous magnesium sulfate drying spends the night with brine wash.Column chromatography is separated, and normal hexane/methylene dichloride is as the eluent gradient wash-out.Obtain faint yellow solid product 3.65g.
Structural characterization:
1H?NMR(CDCl
3/TMS)，δ：16.66(s，1H)，8.71(s，1H)，8.17(s，1H)，8.05(s，1H)，7.53-7.50(m，1H)，7.43(t，2H)，7.30(t，1H)，6.27(s，1H)，5.974(s，1H)，4.324(q，2H)，2.176(d，1H，J＝5.93)，1.380(t，3H)，0.733(s，9H)。
IR?v：(KBr，cm
-1)：3052，2963，2934，2871，1770，1591，1472，786，1383，1233。
MS(m/z)：335(M
+)。
(2) two (N-phenylpyrazoles) [1-(N-ethyl-3-carbazyl)-5,5-dimethyl--1,3-hexanedione] close iridium [Ir (ppz)
2(tmdc)] synthetic
Under the nitrogen protection, add 2.00g (5.638mmol) IrCl in the 250ml there-necked flask successively
33H
2O, 1.78g (12.404mmol) phenylpyrazole, 120ml ethylene glycol ethyl ether and 30ml water.Be heated with stirring to backflow, reacted 24 hours.Be cooled to room temperature, add 100ml water, filter, filter cake is with ethanol 30ml drip washing, and vacuum drying gets 2.42g green black colour chlorine bridge dipolymer [Ir (ppz)
2Cl]
2
Above-mentioned chlorine bridge dipolymer 1.21g (1.178mmol) is joined in the 250ml four-hole bottle; Nitrogen protection adds tmdcH 0.87g (2.591mmol), Anhydrous potassium carbonate 1.97g (10.600mol), 1 down; 2-ethylene dichloride 80ml; Back flow reaction 24 hours, the naturally cooling after-filtration, concentrate pale brown look solid.Column chromatography separating purification, eluent n-hexane/ethyl acetate gradient elution obtains yellow title complex Ir (ppz)
2(tmdc) 0.9g.
Structural characterization:
1H?NMR(CDCl
3/TMS)，δ：8.501(s，1H)，8.082-8.054(m，1H)，8.0.15(s，1H)，7.904(s，2H)，7.767(d，1H)，7.639(s，1H)，7.446(t，1H)，7.386(d，1H)，7.386-7.181(m，2H)，6.869(t，1H)，6.814(t，1H)，6.711-6.669(m，2H)，6.596(t，1H)，6.559(t，1H)，5.974(s，1H)，4.324(q，2H)，2.176(d，1H)，2.089(d，1H)，1.380(t，3H)，0.733(s，9H)。
MS(m/z)：811(M
+)
Ultimate analysis: C
40H
38IrN
5O
2
Calculated value: C 59.10%, H 4.68%, and N 8.62%;
Measured value: C 58.88%, H 4.66%, and N 8.40%.
The resulting material of the above-mentioned reaction of above data acknowledgement is that two (N-phenylpyrazoles) [1-(N-ethyl-3-carbazyl)-5,5-dimethyl--1,3-hexanedione] close iridium [Ir (ppz) really
2(tmdc)]
Embodiment 2 two (N-phenylpyrazole) [1-(9,9-dihexyl-2-fluorenyl)-5,5-dimethyl--1,3-hexanedione] closes iridium [Ir (ppz)
2(tmdf)] synthetic
(1) 1-(9,9-dihexyl-2-fluorenyl)-5,5-dimethyl--1,3-hexanedione (tmdfH) synthetic
Under the nitrogen protection, add 2-ethanoyl-9 in the there-necked flask successively, 9-dihexyl fluorenes 18.80g (0.05mol); 3,3-dimethyl butyrate acetoacetic ester 21.60g (0.15mol), dry toluene 180ml; Sodium amide 7.80g (0.2mol) is warming up to backflow, reacts 5 hours postcooling to room temperature.Add 100ml water, stir that slowly to use 10% Hydrogen chloride to be neutralized to pH value down be about 8.Separatory, extraction, to neutral, anhydrous magnesium sulfate drying spends the night with brine wash.Column chromatography is separated, and n-hexane/ethyl acetate is as the eluent gradient wash-out.Obtain light brown liquid 2.35g.
Structural characterization:
1H?NMR(CDCl
3/TMS)：δ：16.67(s，1H)，7.90-7.86(m，2H)，7.76-7.73(m，2H)，7.37-7.34(m，3H)，6.37(s，1H)，2.15(d，1H)，2.07(d，1H)，1.93-1.88(m，4H)，1.12-0.99(m，12H)，0.73-0.71(m，15H)，0.68-0.54(m，4H)。
IR?v(KBr，cm
-1)：3062，2955，2926，2854，1363，1800，1610，1581，1465，1449，739。
MS(m/z)：474(M
+)。
(2) two (N-phenylpyrazoles) [1-(9,9-dihexyl-2-fluorenyl)-5,5-dimethyl--1,3-hexanedione] close iridium [Ir (ppz)
2(tmdf)] synthetic
Chlorine bridge dipolymer [Ir (ppz)
2Cl]
2Synthesis step identical with the synthesis step of chlorine bridge dipolymer among the embodiment 1.
Above-mentioned chlorine bridge dipolymer 1.21g (1.178mmol) is joined in the 250ml four-hole bottle; Nitrogen protection adds tmdfH 1.228g (2.591mmol), Anhydrous potassium carbonate 1.97g (10.600mol), 1 down; 2-ethylene dichloride 80ml; Back flow reaction 24 hours, the naturally cooling after-filtration, concentrate pale brown look solid.Column chromatography separating purification, eluent n-hexane/ethyl acetate gradient elution obtains yellow title complex Ir (ppz)
2(tmdc) 1.08g.
Structural characterization:
1H-NMR(CDCl
3/TMS)δ：8.061(s，1H)，8.0146(s，1H)，7.760(s，1H)，7.722(s，1H)，7.672-7.654(m，1H)，7.632(q，2H)，7.555(d，1H)，7.282-7.309(m，3H)，7.179(q，1H)，7.119(q，1H)，6.855-6.815(m，2H)，6.669-6.694(m，2H)，6.615-6.570(m，2H)，6.425(d，2H)，6.314(m，1H)，5.822(s，1H)，2.156(d，1H)，2.070(d，1H)，1.928-1.883(m，4H)，1.121-1.066(m，4H)，1.032-0.992(m，8H)，0.784-0.727(m，15H)，0.5910-0.6119(m，4H)。
MS(m/z)：951(M
+)
Ultimate analysis: C51H59IrN4O2
Calculated value: C 64.34%, H 6.20%, and N 5.89%;
Measured value: C 64.57%, H 5.98%, and N 5.90%.
The resulting material of the above-mentioned reaction of above data acknowledgement is that two (N-phenylpyrazoles) [1-(9,9-dihexyl-2-fluorenyl)-5,5-dimethyl--1,3-hexanedione] close iridium [Ir (ppz) really
2(tmdf)].
Performance test
Embodiment 1,2 electroluminescent electronics barrier functionality material is as shown in the table with organic complex of iridium ability test result:
Table 1Ir (ppz)
2(tmdc) and Ir (ppz)
2(tmdf) performance data
Above data show that organic complex of iridium material related among the embodiment has the electronics blocking capability, its performance and Ir (ppz)
3Quite.
Claims (3)
1. organic complex of iridium, its general structure is as follows:
Wherein X is N-ethyl-3-carbazyl or 9,9 '-dihexyl-2-fluorenyl.
2. organic complex of iridium as claimed in claim 1 is characterized in that: its structural formula is as follows:
3. organic complex of iridium as claimed in claim 1 is characterized in that: its structural formula is as follows:
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002105055A (en) * | 2000-09-29 | 2002-04-10 | Fuji Photo Film Co Ltd | Method for manufacturing indium complex or its tautomer |
| US20040048101A1 (en) * | 2002-03-29 | 2004-03-11 | Thompson Mark E. | Organic light emitting devices with electron blocking layers |
| CN101531686A (en) * | 2009-04-15 | 2009-09-16 | 西安近代化学研究所 | Monomer for organic electrophosphorescent polymer |
| CN101531684A (en) * | 2009-04-15 | 2009-09-16 | 西安近代化学研究所 | Monomer for organic electrophosphorescent polymer |
-
2012
- 2012-04-17 CN CN201210111640.0A patent/CN102659847B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002105055A (en) * | 2000-09-29 | 2002-04-10 | Fuji Photo Film Co Ltd | Method for manufacturing indium complex or its tautomer |
| US20040048101A1 (en) * | 2002-03-29 | 2004-03-11 | Thompson Mark E. | Organic light emitting devices with electron blocking layers |
| CN101531686A (en) * | 2009-04-15 | 2009-09-16 | 西安近代化学研究所 | Monomer for organic electrophosphorescent polymer |
| CN101531684A (en) * | 2009-04-15 | 2009-09-16 | 西安近代化学研究所 | Monomer for organic electrophosphorescent polymer |
Non-Patent Citations (4)
| Title |
|---|
| VADIM I. ADAMOVICH等，: "New charge-carrier blocking materials for high efficiency OLEDs", 《ORGANIC ELECTRONICS》, 30 September 2003 (2003-09-30), pages 77 - 87 * |
| ZHIWEI LIU等,: "Photophysical Properties of Heteroleptic Iridium Complexes Containing Carbazole-Functionalized β-Diketonates", 《CHEMPHYSCHEM》, 7 March 2008 (2008-03-07), pages 634 - 640 * |
| 刘坚等,: "一种含载流子传输基的铱配合物:合成及深黄色电致磷光器件", 《无机化学学报》, 29 February 2012 (2012-02-29), pages 398 - 404 * |
| 谷新等,: "以苯基吡唑为主配体的Ir配合物电子结构和光谱性质的密度泛函理论研究", 《高等学校化学学报》, 31 July 2009 (2009-07-31), pages 1392 - 1396 * |
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