CN101161663B - Pyrazine ligand iridium complex and method for synthesizing same - Google Patents
Pyrazine ligand iridium complex and method for synthesizing same Download PDFInfo
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- CN101161663B CN101161663B CN2007101580610A CN200710158061A CN101161663B CN 101161663 B CN101161663 B CN 101161663B CN 2007101580610 A CN2007101580610 A CN 2007101580610A CN 200710158061 A CN200710158061 A CN 200710158061A CN 101161663 B CN101161663 B CN 101161663B
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Abstract
The present invention relates to a pyrazine-ligand iridium complex and the preparation method thereof, the technical proposal of which includes a pyrazine-ligand iridium complex with the structure shown by the formula on the right. The preparation includes the following procedures that: a) the pyrazine ligand is dissolved with glycol, into which N2 is inducted for 30 min, b) Iridium trichloride hydrate is added into the solution above, with calefaction with a microwave oven for 4-5 min, c)the mixture solution is cooled down under room temperature, and filtrated, the filter cake is rinsed withwater and then with anhydrous ethanol, d) thin layer chromatography is carried out, in which the crude product is extracted with silica gel adopted as the stationary phase and chloroform adopted as the lotion and, e) the intended product is obtained through vacuum drying under 40 DEG C. The present invention accomplishes the coordination between pyrazine ligand and metal iridium under radiation of micro waves to obtain a novel tri-loop iridium complex, which is a good phosphorescence material excellent in solubility when kept in an organic solvent, and has huge potentials and applicable prospect as an electro-phosphorescence material to improve the illuminant efficacy of parts of apparatus.
Description
Technical field: the present invention relates to a kind of title complex and synthetic method field thereof, particularly a kind of pyrazine class complex of iridium and synthetic method field thereof.
Background technology: the Tang of Kodak in 1987 and the nineteen ninety Burroughes of univ cambridge uk have released respectively since organic and high molecule electroluminescent material and the device, have started the upsurge of Organic Light Emitting Diode (hereinafter to be referred as OLED) research in global academia and industrial community.Compare with liquid-crystal display, advantages such as OLED has that response is fast, the visual angle wide, flexiblely show, low temperature resistant, antidetonation, compare with the cathode ray tube (CRT) technology, it has, and volume is little, in light weight, high-level efficiency, high brightness, low voltage direct drive, be easy to realize numerous advantages such as the panchromatic demonstration of big area.Organic Light Emitting Diode has made it become the most competitive technology in the third generation flat pannel display in the potential excellent performance in technique of display field.
The luminescent material that is used for OLED can be divided into two classes.One class is a fluorescent material, and a class is a phosphor material.Fluorescence luminescent material is because the simple singlet state exciton attenuation that relies on is luminous, and its electroluminescent maximum internal quantum efficiency is 25%.Phosphor material can pass through intersystem crossing, realizes having mixed singlet state and the luminous phosphorescent emissions of triplet state.In theory, the OLED internal quantum efficiency that utilizes phosphor material to make can reach 100%.
Recent study is found Ir
3+Title complex can produce intensive spin-orbit coupling, makes the triplet state transition of prohibiting originally become permission, and then can realize strong phosphorescent emissions.At present, three ring iridium complex phosphorescence device external quantum efficiencys reach about 15%.As Baldo etc. with phenylbenzene pyridine complex of iridium Ir (ppy)
3(II) be entrained among the material TAZ (I), obtained the phosphorescence device of external quantum efficiency for (15.4 ± 0.2) %.Tsuboyama etc. are with Ir (piq)
3(III) be doped among the CBP, obtained external quantum efficiency and reached 10.3% phosphorescence device.The efficient of phosphorescence device depends on numerous factors, and as the energy level between Subjective and Objective coupling, Subjective and Objective lifetime of excited state, object orbit coupling, electric charge injection and transmission and triplet state-triplet state (T-T) are buried in oblivion etc.The structure of organic ligand has very big-influence to luminous efficiency and emission wavelength in the metal complexes, therefore designs the metal complexes of synthesizing new, and is significant to the phosphor material of developing different glow colors.
Summary of the invention: the objective of the invention is for a synthetic class new have a phosphor material pyrazine ligand iridium complex than high luminous quantum efficiency.
Another object of the present invention provides a kind of synthetic method of pyrazine ligand iridium complex.
To achieve these goals, the technical solution used in the present invention is: a kind of pyrazine ligand iridium complex is characterized in that its structural formula is as follows:
Wherein ,-R is-H or-CH
3-X is-H or-F.
The synthetic method of pyrazine ligand iridium complex, its synthesis step is as follows:
A) pyrazine ligand is dissolved in the ethylene glycol, logical N
230min;
B) in above-mentioned solution, add the hydration iridous chloride, microwave-assisted heating 4～5min;
C) mixed solution room temperature cooling, suction filtration, filter residue is water, absolute ethanol washing successively;
D) tlc is that stationary phase, trichloromethane are the leacheate thick product of purifying with silica gel;
E), get target product 40 ℃ of following vacuum-dryings.
Wherein, the proportioning of each material is:
The mol ratio of pyrazine ligand and hydration iridous chloride is 50～100: 1;
The volume that the 1mmol pyrazine ligand adds ethylene glycol is about 1～3mL.
Described microwave-assisted heating, temperature is 75～85 ℃.
Reaction mechanism is: nucleophilic addition at first takes place in dibenzoyl and alkyl diamine, generates the dihydro pyrazine, under the tetrachlorobenzoquinone effect, oxidizing reaction takes place again, generates pyrazine ligand.
Pyrazine ligand in the medium of ethylene glycol, under protection of nitrogen gas, with iridous chloride generation coordination reaction, generates pyrazine ligand iridium complex.
Uv absorption spectra by contrast pyrazine part and pyrazine ligand iridium complex as can be seen, red shift all takes place in absorption peak accordingly.Can show thus and synthesize metal iridium complex.
By seeing among the fluorescence spectrum figure, bigger red shift has also taken place than pyrazine part emission peak in the pyrazine ligand iridium complex emission peak.Ir
3+Title complex is because the spin coupling of intensive track makes the singlet state exciton and the triplet exciton of its title complex mix.On the one hand, triplet exciton has the character of singlet state exciton, and the symmetry of triplet exciton is destroyed, and the phosphorescence cancellation is effectively suppressed; On the other hand, singlet has also had the character of some triplet state, and fall time is elongated, and fluorescence efficiency reduces, and this makes realizes that phosphorescence becomes possibility under the room temperature.Pyrazine ligand iridium complex luminous mainly is the phosphorescent emissions from the metal complexes triplet state.
The invention has the beneficial effects as follows: realized pyrazine ligand and the coordination of metal iridium under microwave exposure by the present invention, obtained a kind of novel tricyclic metal iridium complex.The solvability of this title complex in ordinary organic solvents is fine, is a kind of good phosphor material.By measuring fluorescence spectrum, as embodiment 2 synthetic Ir[DPP]
3Excitation wavelength is 332nm, and it is presented at the 572.9nm place stronger emission peak, is a kind of phosphor material of yellow-green colour preferably; As embodiment 5 synthetic Ir[MDPP]
3Title complex has emission peak at the 559nm place, is a kind of material of green phosphorescent preferably.With title complex Ir[DPP]
3Be entrained among the small molecule material TAZ with good electron transport property, do hole transmission layer with HMTPD, recording device is 65225cd/m in brightness
2The time maximum external quantum efficiency reached (16 ± 0.1) %.Showed pyrazine ligand iridium complex as the electrophosphorescent material in the great potential and the application prospect that improve aspect the device luminous efficiency.
Description of drawings:
Fig. 1 is Ir[DPP]
3 1H NMR spectrogram;
Fig. 2 is Ir[MDPP]
3 1H NMR spectrogram;
Fig. 3 is DPP and Ir[DPP]
3Uv absorption spectra; (wherein 1 is Ir[DPP]
32 is DPP)
Fig. 4 is DPP and Ir[DPP]
3Fluorescence spectrum figure; (wherein 1 is Ir[DPP]
32 is DPP)
Fig. 5 is MDPP and Ir[MDPP]
3Fluorescence spectrum figure; (wherein 3 is MDPP; 4 is Ir[MDPP]
3)
Embodiment:
Material: dibenzoyl (AR, Tianjin recovery fine chemistry industry institute)
Tetrachlorobenzoquinone (AR, Tianjin recovery fine chemistry industry institute)
Hydration iridous chloride (AR, Shanghai Yue Huagong of a specified duration company limited)
The accurate micro melting point apparatus of instrument: CXM-300
FLASH EA1112 elemental analyser
Varian Mercury-300 NMR spectrometer with superconducting magnet
Cary100-300 type fluorescence spectrophotometer
Perkin Elmer Lambda 25 ultraviolet spectrophotometers
Take by weighing the 10g dibenzoyl in the 100mL round-bottomed flask, add 3.84mL quadrol and 45mL dehydrated alcohol.Magnetic agitation, backflow 30min, stopped reaction.Faint yellow needle-like crystal is separated out in the room temperature cooling, uses the dehydrated alcohol recrystallization, and getting faint yellow needle-like crystal is 2,3-dihydro-5, and 6-diphenyl pyrazine (DPPH), vacuum-drying gets 5.33g, productive rate 48.6%.M.p162.5-163.5 ℃ (literature value 166-167 ℃).
Take by weighing 4.4g DPPH and 4.62g tetrachlorobenzoquinone in the 100mL round-bottomed flask, add 50mL dimethylbenzene.Magnetic agitation, backflow 7h stopped reaction.To react mixed liquid and be cooled to room temperature,, handle with sodium hydroxide solution then, use salt acid treatment organic phase again, the acid layer will be neutralized to neutrality, separate out khaki crystal, be 2,3-diphenyl pyrazine (DPP) with sodium hydroxide solution with the dilution of 40mL anhydrous diethyl ether.Vacuum-drying gets 3.89g, productive rate 87.6%.M.p.121.3～122.2 ℃ (123～124 ℃ of literature values).
The pyrazine part characterizes by measuring its fusing point; As shown in Figure 3, DPP shows at 224nm, 272nm and 286nm three absorption peaks are arranged on ultra-violet absorption spectrum.
Take by weighing 1.760g (7.580mmol) DPP in the 100mL there-necked flask, add 10mL ethylene glycol.Logical then nitrogen 30min is to remove the oxygen in the flask.Add 0.053g (0.152mmol) IrCl more rapidly
33H
2O.At N
2Under the protection, microwave heating (80 ℃) backflow 4min.The room temperature cooling, the precipitation suction filtration.Difference water, absolute ethanol washing.Tlc is a stationary phase with silica gel, and trichloromethane is for expanding agent purification crude product.Vacuum-drying gets orange red solid 0.036g, productive rate 51%.
Element test result (theoretical value): C:64.58% (65.07%); H:4.03% (3.75%); N:9.25% (9.49%).
As shown in Figure 1,
1HNMR analysis revealed, δ=9.1ppm are proton absorption peaks (3H) on a place pyrazine ring, and δ=8.0ppm is a proton absorption peak (3H) on the b place pyrazine ring; δ=7.8ppm is the absorption peak (6H) of proton on c place and the iridium coordinate phenyl ring; δ=7.5ppm be the d place not with iridium coordinate phenyl ring on proton absorption peak (9H); δ=6.1ppm, δ=6.5ppm, δ=6.6ppm, δ=6.9ppm are respectively e, f, g, the absorption peak (being 3H) of proton on the h place phenyl ring.
Confirm that by ultimate analysis and magnetic nuclear resonance method the compound that obtains is target product.
As shown in Figure 3, Ir[DPP]
3Ultra-violet absorption spectrum is presented at 227nm, and there are three place's absorption peaks at 283nm and 343nm place.
As shown in Figure 4, Ir[DPP]
3Excitation wavelength is 332nm in the fluorescence spectrum, and it is presented at the phosphorescent emissions that there is stronger metal complexes triplet state at the 572.9nm place.
Take by weighing 1.760g (7.580mmol) DPP in the 100mL there-necked flask, add 10mL ethylene glycol.Logical then nitrogen 30min is to remove the oxygen in the flask.Add 0.030g (0.085mmol) IrCl more rapidly
33H
2O.At N
2Under the protection, microwave heating (80 ℃), backflow 4min.The room temperature cooling, the precipitation suction filtration.Difference water, absolute ethanol washing.Tlc is a stationary phase with silica gel, and trichloromethane is for expanding agent purification crude product.Vacuum-drying gets orange red solid Ir[DPP]
30.035g, productive rate 47%.
Take by weighing the 10g dibenzoyl in the 100mL reaction flask, add the dehydrated alcohol of 45mL new system, under stirring at room with 4.89mL 1, the 2-propylene diamine slowly is added drop-wise in the above-mentioned reaction solution, back flow reaction 0.5h reaction mixture is cooled to room temperature then, and sedimentation and filtration is used the dehydrated alcohol recrystallization.Through absolute ethanol washing, it is 2-methyl-2 that vacuum-drying gets faint yellow solid, 3-dihydro-5,6-diphenyl pyrazine (MDPPH) 7.55g, productive rate 64.9%.m.p.121～122℃
Take by weighing 5.0g MDPPH, 5.29g tetrachlorobenzoquinone and measure 47mL dimethylbenzene in the 100mL reaction flask, stirring and refluxing reaction 7h is cooled to room temperature with reaction mixture, dilute with anhydrous diethyl ether, handle with sodium hydroxide solution then, use salt acid treatment organic phase again, the acid layer is neutralized to neutrality.It is product (MDPP) 4.08g that sedimentation and filtration, vacuum-drying get the lightpink solid, productive rate 82.3%.m.p.91～92℃。
Embodiment 5 5-methyl-2,3-diphenyl pyrazine complex of iridium (Ir[MDPP]
3) synthetic
Take by weighing 3.00g (12.18mmol) MDPPH in the 100mL there-necked flask, add 15mL ethylene glycol.Logical then nitrogen 30min is to remove the oxygen in the flask.Add 0.049g (0.14mmol) IrCl more rapidly
33H
2O.At N
2Under the protection, microwave heating (80 ℃), backflow 5min.The room temperature cooling, precipitation suction filtration, water, absolute ethanol washing respectively.Tlc is a stationary phase with silica gel, and trichloromethane is for expanding agent purification crude product.Vacuum-drying gets orange/yellow solid 0.068g, productive rate 52%.
As shown in Figure 2,
1HNMR analysis revealed, δ=9.0ppm are proton absorption peaks (3H) on a place pyrazine ring, and δ=2.3ppm is a methyl proton absorption peak (9H) on the b place pyrazine ring; δ=7.7ppm is the absorption peak (6H) of proton on c place and the iridium coordinate phenyl ring; δ=7.6ppm be the d place not with iridium coordinate phenyl ring on proton absorption peak (9H); δ=6.0ppm, δ=6.4ppm, δ=6.6ppm, δ=6.7ppm are respectively e, f, g, the absorption peak (being 3H) of proton on the h place phenyl ring.
As shown in Figure 5, Ir[MDPP]
3Excitation wavelength is 346nm in the fluorescence spectrum, and it is presented at the phosphorescent emissions that there is stronger metal complexes triplet state at the 559nm place.
Embodiment 6
Take by weighing 3.00g (12.18mmol) 5-methyl-2, the 3-diphenyl pyrazine adds 15mL ethylene glycol in the 100mL there-necked flask.Logical then nitrogen 30min is to remove the oxygen in the flask.Add 0.043g (0.12mmol) IrCl more rapidly
33H
2O.At N
2Under the protection, microwave heating (80 ℃), backflow 5min.The room temperature cooling, precipitation suction filtration, water, absolute ethanol washing respectively.Tlc is a stationary phase with silica gel, and trichloromethane is for expanding agent purification crude product.Vacuum-drying get orange/yellow solid (Ir[MDPP]
3) 0.053g, productive rate 50%.
Embodiment 74,4 '-two fluoro-2,3-diphenyl pyrazine (DPPF) synthetic
Take by weighing 2.4g 4,4 '-DfBP formyl in the 100mL reaction flask, add the dehydrated alcohol of 20mL new system, under room temperature, stirring, the 1.0mL quadrol slowly is added drop-wise in the above-mentioned reaction solution, then back flow reaction 0.5h.Reaction mixture is cooled to room temperature, and pouring into then and obtaining yellow crystals in the distilled water is 4,4 '-two fluoro-2,3-dihydro-5,6-diphenyl pyrazine (DPPFH) 2.04g, productive rate 78%.m.p.108～113℃。
Take by weighing 2.04g 4,4 '-two fluoro-2,3-dihydro-5,6-diphenyl pyrazine, 2.0g tetrachlorobenzoquinone and 25mL dimethylbenzene are in the 100mL reaction flask, and stirring and refluxing is reacted 7h.Reaction mixture is cooled to room temperature,, handles with sodium hydroxide solution then, the upper strata is told with the anhydrous diethyl ether dilution.With salt acid treatment organic phase, the acid layer is neutralized to neutrality.Sedimentation and filtration, vacuum-drying get the tawny solid and are product (DPPF) 1.68g, productive rate 82%.m.p.121～122℃。
Embodiment 8 title complexs [Ir (DPPF)
3] preparation
Take by weighing 0.966g (3.60mmol) 4,4 '-two fluoro-2,3-diphenyl pyrazine (DPPF) adds 10mL ethylene glycol in the 100mL there-necked flask.Logical then nitrogen 30min.Add 0.0169g (0.048mmol) IrCl more rapidly
33H
2O.At N
2Under the protection, microwave heating (80 ℃), backflow 5min.The room temperature cooling, suction filtration, water, absolute ethanol washing respectively.Tlc is a stationary phase with silica gel, and trichloromethane is for expanding agent purification crude product.Vacuum-drying gets brick-red solid 0.026g, productive rate 54%.
Claims (3)
1. the synthetic method of a pyrazine ligand iridium complex is characterized in that synthesis step is as follows:
A) pyrazine ligand is dissolved in the ethylene glycol, logical N
230min;
B) in above-mentioned solution, add the hydration iridous chloride, microwave-assisted heating 4～5min;
C) mixed solution room temperature cooling, suction filtration, filter residue is water, absolute ethanol washing successively;
D) tlc is that stationary phase, trichloromethane are the leacheate thick product of purifying with silica gel;
E), get target product 40 ℃ of following vacuum-dryings;
The structure of described target product pyrazine ligand iridium complex is as follows:
Wherein ,-R is-H or-CH
3-X is-H or-F.
2. the synthetic method of pyrazine ligand iridium complex according to claim 1, it is characterized in that: the proportioning of each material is:
The mol ratio of pyrazine ligand and hydration iridous chloride is 50～100: 1;
The volume that the 1mmol pyrazine ligand adds ethylene glycol is 1～3mL.
3. the synthetic method of pyrazine ligand iridium complex according to claim 1 is characterized in that: described microwave-assisted heating, temperature is 75～85 ℃.
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