CN109734750A - Platinum complex and preparation method thereof for organic electroluminescence device - Google Patents
Platinum complex and preparation method thereof for organic electroluminescence device Download PDFInfo
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Abstract
The platinum complex and preparation method thereof that the invention discloses a kind of for organic electroluminescence device.Different steric groups, including carbonyl, spiro structure, carbazole group, then Pt (DMSO) Cl with synthesis are modified on basic ligand2Coordination, generates platinum metal complex, and general structure is expressed from the next.Platinum complex has both the light radiation characteristic and good dissolubility of higher thermal stability, high-quality, can prepare electroluminescent device by solwution method, reduce the cost of manufacture of device.The preparation method of platinum complex is simple, and reaction condition is mild, and it is easy to isolate and purify, and yield is high.It is 2.8V that luminescent device as guest materials preparation, which opens bright voltage, and light emission luminance is up to 15408.6cd/m2, current efficiency is up to 16.0cd/A, and electroluminescent spectrum excitation purity is preferable, single emission peak is presented, without miscellaneous peak.
Description
Technical field
The present invention relates to platinum complexes and preparation method thereof more particularly to a kind of platinum for organic electroluminescence device to match
Close object and preparation method thereof.
Background technique
Organic electroluminescence device is widely used in the neck such as FPD, solid-state lighting as a kind of novel display technology
Domain.Heavy metal complex, such as complex of iridium, platinum complex can be simultaneously due to the coupling between track and spin
Triplet excitons and singlet exciton are collected, realize 100% interior quantum yield, it is considered to be effectively prepare organic electroluminescence
The material of luminescent device, such as Organic Light Emitting Diode (Organic light-emitting diode, OLED).
Platinum complex is different according to the composition of the main ligand of its molecule, is divided into three classes: phenylpyridine class C^N ligand, phenyl miaow
The effect of azole C^N ligand and phenyl bipyridine N^N class ligand, main ligand plays adjusting complex transmitting color, simultaneously also
There are thermal stability, the photoelectrochemical behaviour of complex, assistant ligand has levulinic ketone, divides for adjusting
The dissolubility and film forming ability of son.Platinum complex belongs to tetravalence coordination, and the complex of formation is plane quadrilateral structure, this
Structure is easy to happen intermolecular π-π interaction and the interatomic interaction of Pt metal-Pt, so as to cause fluorescence
Quenching, at the same time, but also light radiation process more complicatedization, emission spectrum excitation purity is not high, and often multiple bands of a spectrum are mixed
It closes, the transition radiation including electronics from ligand to central atom transition radiation and electronics on ligand or between ligand.In addition, hair
Spectrum is penetrated to change with doping concentration, or change with operation voltage and platinum complex industrial application faces one ask
Topic.In addition, the easy aggregation of platinum complex molecule forms excimer and makes light radiation low efficiency；Device spectral is not yet simultaneously
Stablize, gradually excimer emission peak occurs in Long wavelength region with the raising of doping concentration.
On the one hand, in order to reduce platinum complex fluorescent quenching the phenomenon that, steric group is often introduced on ligand；Another party
Face introduces rigid structure group in ligand, to enhance the thermal stability of platinum complex.Although this method can be to a certain extent
Fluorescent quenching and enhancing thermal stability are reduced, however the solubility property of platinum complex is deteriorated, and is unfavorable for passing through platinum complex molten
Liquid legal system has organic electroluminescence devices, and the performance that dissolubility prepares small molecule OLED device for solwution method has very greatly
Influence.
Summary of the invention
Goal of the invention: in view of the above problems, the invention proposes have both high thermal stability, high-quality light radiation characteristic with
And the platinum complex of good solubility.It is a further object of the present invention to provide the preparation method of the platinum complex and organic
Application in light emitting diode.
Technical solution: the platinum complex of the present invention for organic electroluminescence device has following chemical structure,
That is R1=carbonyl, fluorenyl, double N- alkyl carbazole bases；
R2=methyl, ethyl, propyl.
Preferred R2For ethyl.
The method of the present invention for preparing above-mentioned platinum complex, comprising the following steps:
(1) under nitrogen protection, Platinous Potassium Chloride is dissolved in dimethyl sulfoxide and water, reaction is stirred at room temperature, is stood, is taken out
Filter, washing, obtains Pt (DMSO)2Cl2；
(2) under nitrogen protection, by Ligands and Pt (DMSO)2Cl2It is added in 2-methyl cellosolve, the first stage is first permanent
It is temperature reaction a period of time, cooling, sodium acetate and the first ligand are added, second stage continues isothermal reaction for a period of time, cold
But, methylene chloride extracts, and chromatographed column, and obtained platinum complex；Wherein, first ligand is 3,3 '-two Trifluoromethyl-1 H,
1 ' H- [5,5 ']-joins pyrazoles, and the Ligands are 4,5- carboline -9- ketone, 4A'4B', 8A'9a' tetrahydro spiral shell [cyclopentadiene
And [2,1-B:3,4-B'] two pyridine 5,9' fluorenes] or bis- (9- ethyl -9H- carbazole -4- the base) -5H- cyclopentas of 5,5- [2,
1-B:3,4-B'] two pyridines any one.
Wherein, the temperature of first stage isothermal reaction is 119~125 DEG C in the step (2), and the reaction time is 2~3h；
The temperature of second stage isothermal reaction is 130~135 DEG C, and the reaction time is 7~8h；The eluant, eluent for chromatographing column is dichloromethane
The mixture of alkane or petroleum ether and methylene chloride.
The system of bis- two pyridines of (9- ethyl -9H- carbazole -4- base) -5H- cyclopenta [2,1-B:3,4-B'] of 5,5-
Standby is that under nitrogen protection, 4,5- carboline -9- ketone and N- ethyl carbazole are dissolved in methylene chloride, dropwise addition Eton reagent, 90
~110 DEG C, the reaction time is 10~14h, cooling, adjusts pH value of solution to neutrality, and methylene chloride extraction chromatographed what column obtained, layer
Analysing eluant, eluent used in column is methylene chloride.
Due to heavy metal effect, platinum metal complex has stronger Effect of Spin-orbit Coupling, can generate phosphorescent radiation,
Therefore with the light radiation characteristic of higher quality.Conventional method can be reduced fluorescent quenching by introducing steric group, introduce rigidity
Group enhances the thermal stability of platinum complex, but the dissolubility of platinum complex is bad.With bisglyoxaline-spiro fluorene platinum complex
(SPFPy) for Pt, Ligands are spiro fluorene structure, which has very strong rigidity, and the heat that platinum complex can be enhanced is steady
It is qualitative；Peripheral trifluoromethyl and spiro fluorene ring form steric hindrance structure, it is possible to reduce fluorescent quenching；Meanwhile trifluoromethyl group
It also can increase dissolubility, spiro structure steric group reduces intermolecular aggregation, can also enhance dissolubility.Therefore between group
Interaction, so that platinum complex is while thermal stability with higher and light radiation characteristic, dissolution also with higher
Property.
The utility model has the advantages that compared with prior art, remarkable advantage of the invention is: (1) it is steady to have both higher heat for platinum complex
Qualitative, high-quality light radiation characteristic and good dissolubility can prepare electroluminescent device by solwution method, reduce device
The cost of manufacture of part；(2) photo-quantum efficiency of platinum complex is higher by 9.98%~21.55%, and fluorescence lifetime is shorter by 0.8~3.9
μs；(3) preparation method of platinum complex is simple, and reaction condition is mild, and it is easy to isolate and purify, and yield is high；(4) it is used as main body material
It is 2.8V that the luminescent device of material preparation, which opens bright voltage, and light emission luminance is up to 15408.6cd/m2, current efficiency is up to
16.0cd/A, electroluminescent spectrum excitation purity is preferable, single emission peak is presented, without miscellaneous peak.
Detailed description of the invention
Fig. 1 is the tomograph of (SPFPy) Pt complex, and wherein a is complex single molecule structure schematic diagram, and b is to match
Close the dimeric structure schematic diagram of object；
Fig. 2 is the solution uv absorption spectra of (FONPy) Pt, (SPFPy) Pt, (ECzPy) Pt complex；
Fig. 3 is the PMMA film shape fluorescence spectra of (FONPy) Pt, (SPFPy) Pt, (ECzPy) Pt complex；
Fig. 4 is the powdered fluorescence spectra of (FONPy) Pt, (SPFPy) Pt, (ECzPy) Pt complex；
Fig. 5 is the fluorescence spectra of (FONPy) Pt, (SPFPy) Pt, (ECzPy) Pt complex in acetonitrile solution；
Fig. 6 is the fluorescence lifetime figure of (FONPy) Pt, (SPFPy) Pt, (ECzPy) Pt complex；
Fig. 7 is the cyclic voltammetry curve figure of (FONPy) Pt, (SPFPy) Pt, (ECzPy) Pt complex；
Fig. 8 is the electroluminescent light spectrogram of (ECzPy) Pt device；
Fig. 9 is the voltage~current density characteristics curve graph of (ECzPy) Pt device；
Figure 10 is the brightness~voltage characteristic curve of (ECzPy) Pt device；
Figure 11 is the efficiency~luminosity response of (ECzPy) Pt device.
Specific embodiment
The present invention is further illustrated with reference to the accompanying drawings and examples.
1, the synthesis and characterization of platinum complex
Embodiment 1
(FONPy) preparation of Pt complex:
(1) under nitrogen protection, Platinous Potassium Chloride K is weighed2(PtCl4) (1.65g, 3.9mmol) be added in reaction flask, to anti-
Answer bottle that the dimethyl sulfoxide DMSO (7.5mL) and deionized water (2mL) of re-distillation is added, 25 DEG C are stirred 1h at room temperature, stirring
Terminate, reaction flask is placed into 12h in refrigerator, filter, water washing obtains two-dimethyl sulfoxide of yellow needles product-dichloride
Platinum Pt (DMSO)2Cl2, drying, weighing obtains 1.38g product, and calculating yield is 79.5%.
(2) under nitrogen protection, Ligands 4,5- carboline -9- ketone (0.3g, 1.5mmol) and step (1) gained are weighed
Pt (DMSO)2Cl2(0.6g, 1.5mmol) is added in reaction flask, and 2-methyl cellosolve (15mL) is added into reaction flask, and 125
2h is reacted at DEG C, solution becomes green by yellow, is cooled to room temperature, and is added sodium acetate NaAc (0.9g, 6.0mmol) and first
Ligand 3,3 '-two Trifluoromethyl-1 H, 1 ' H- [5,5 ']-join pyrazoles, hereinafter referred to as CF3BPZ (0.45g, 1.5mmol), 130
8h is reacted at DEG C, is cooled to room temperature after reaction, and methylene chloride extraction is added, is spin-dried for, by the stone of 1:1 volume ratio mixing
Oily ether and methylene chloride obtain yellow powder product bisglyoxaline-Fluorenone platinum complex (i.e. as eluant, eluent Chromatographic purification
(FONPy) Pt complex), dry, weighing obtains 0.45g product, and calculating yield is 51%.1HNMR(400MHz, CDCl3)δ
10.70 (d, J=5.3Hz, 1H), 7.95 (d, J=7.8Hz, 1H), 7.84 (t, J=8.0Hz, 1H), 7.57-7.49 (m,
3H), 6.29 (d, J=9.3Hz, 2H)；19FNMR(376MHz,CDCl3) δ -60.38 (d, J=3.4 Hz, 6F)；HRMS((+)-
ESI): m/z=736.1016 (calcd.646.0390for [C19H9F6N6Pt][M+H]+)。
Embodiment 2
(SPFPy) preparation of Pt complex:
(1)Pt(DMSO)2Cl2Preparation process with the step (1) in embodiment 1, this will not be repeated here.
(2) under nitrogen protection, Ligands 4A'4B', 8A'9a' tetrahydro spiral shell [cyclopenta [2,1-B:3,4- are weighed
B'] two pyridines 5,9' fluorenes], hereinafter referred to as (SPFPy) Pt ligand (0.45g, 1.5mmol) and step (1) resulting Pt
(DMSO)2Cl2(0.6g, 1.5mmol) is added in reaction flask, and 2-methyl cellosolve (15mL) is added into reaction flask, at 122 DEG C
2h is reacted, solution becomes green by yellow, is cooled to room temperature, and NaAc (1.2g, 9.0mmol) and the first ligand CF is added3BPZ
(0.45g, 1.5mmol) reacts 8h at 132 DEG C, is cooled to room temperature after reaction, and methylene chloride extraction is added, is spin-dried for, with
Methylene chloride is as eluant, eluent Chromatographic purification, and obtaining yellow powder product bisglyoxaline-spiro fluorene platinum complex, (i.e. (SPFPy) Pt matches
Close object), dry, weighing obtains 0.3g product, and calculating yield is 48%.1HNMR(400MHz, CDCl3) δ 9.88 (dd, J=
4.0,2.4Hz, 2H), 7.95 (d, J=7.6Hz, 2H), 7.54 (dd, J=6.0,3.7Hz, 6H), 7.29 (d, J=1.1Hz,
1H), 7.25 (d, J=1.1Hz, 1H), 6.86 (d, J=7.6Hz, 2H), 6.49 (s, 2H)；19F NMR(376MHz,CDCl3)
δ-60.58(s,6F)；HRMS ((+)-ESI): m/z=782.1011 (calcd. 782.1067for [C31H17F6N6Pt][M+H
]+)。
Embodiment 3
(ECzPy) preparation of Pt complex:
(1)Pt(DMSO)2Cl2Preparation process with the step (1) in embodiment 1, this will not be repeated here.
(2) under nitrogen protection, weigh 4,5- carboline -9- ketone (3g, 15.4mmol) and N- ethyl carbazole (7.25g,
It 24.6mmol) is added in reaction flask, dichloromethane solvent (100ml) dissolution is added into reaction flask, Eton reagent dropwise is arrived
In reaction flask, 13h is reacted at 101 DEG C, is cooled to room temperature, sodium bicarbonate aqueous solution is added to be adjusted to neutrality, dichloromethane is then added
Alkane extraction, is spin-dried for, using methylene chloride as eluant, eluent Chromatographic purification, obtains white powder product 5, the bis- (9- ethyl -9H- clicks of 5-
Azoles -4- base) two pyridine of -5H- cyclopenta [2,1-B:3,4-B'], hereinafter referred to as carbazole ligand ECzFN, dry, weighing
7.2g product is obtained, calculating yield is 81%.1HNMR(400MHz,DMSO-d6) δ 8.70 (s, 2H), 8.14 (d, J=7.6Hz,
2H), 7.93 (d, J=8.0Hz, 4H), 7.52 (dd, J=16.9,8.6Hz, 4H), 7.41 (d, J=17.3Hz, 4H), 7.29
(d, J=8.3Hz, 2H), 7.06 (s, 2H), 4.37 (d, J=7.1Hz, 4H), 1.26 (s, 6H).
(3) under nitrogen protection, carbazole ligand ECzFN (0.9g, 1.5mmol) and step (1) resulting Pt are weighed
(DMSO)2Cl2(0.6g, 1.5mmol) is added in reaction flask, and 2-methyl cellosolve (15ml) is added into reaction flask, at 119 DEG C
3h is reacted, solution becomes green by yellow, is cooled to room temperature, and NaAc (1.2g, 9.0mmol) and the first ligand CF is added3BPZ
(0.45g, 1.5mmol) reacts 7h at 135 DEG C, is cooled to room temperature after reaction, and methylene chloride extraction is added, is spin-dried for, with
By the petroleum ether and methylene chloride of 1:1 volume ratio mixing as eluant, eluent Chromatographic purification, red powder product bisglyoxaline-is obtained
Carbazole fluorenyl platinum complex (i.e. (ECzPy) Pt complex), dry, weighing obtain 0.4g product, and calculating yield is 58%.1HNMR(400MHz,CDCl3) δ 9.51 (s, 2H), 8.14-7.89 (m, 6H), 7.54-7.31 (m, 8H), 7.20 (t, J=
7.4Hz, 2H), 6.13 (s, 2H), 4.38 (d, J=6.9Hz, 4H), 1.45 (t, J=7.0Hz, 6H)；19FNMR(376MHz,
CDCl3)δ-60.03(s,6F)；HRMS ((+)-ESI): m/z=1018.2306 (calcd.1018.2380for
[C47H32F6N8Pt][M+H]+)。
2, the solid-state mono-crystalline structures characteristic of platinum complex
Embodiment 4
As shown in Figure 1, being in the accumulation mode in monocrystalline state for (SPFPy) Pt complex, X-ray single crystal diffraction is analyzed
Test result shows the atomic species in the crystalline state three-dimensional structure of material, quantity and is actually consistent.(SPFPy) Pt complex
Basic 5,5 '-connection of ligand pyrazoles (5- (1H-FNrazol-5-yl) -1H-FNrazole) and the not coplanar (figure of central atom Pt
1a), Ligands are spiro fluorene structure, which has very strong rigidity, two fluorenes ring unit is arranged in approximate 90 degree, this
Kind mode has effectively interrupted the conjugation between molecular cell；N atom is coordinated in a manner of almost plane with center Pt atom, figure
1b is the tomograph of (SPFPy) Pt dimer, and as can be seen from the figure second bipyridyl and platinum be not in spiro structure
It is coplanar, effectively inhibit the intermolecular accumulation of metal platinum.It is intermolecular to take T-shaped accumulation mode, between the Pt atom of center
There are weak interactions, are present in structure cell in the form of dimer；Peripheral CF3Group and spiro fluorene ring form steric hindrance knot
Structure, this accumulation mode effectively shield intermolecular interaction, are conducive to the concentration quenching effect for inhibiting complex,
Improve device photoelectric transformation efficiency.
(FONPy) accumulation mode of Pt and (ECzPy) Pt complex is similar to (SPFPy) Pt, and this will not be repeated here.
3, the Photophysics of platinum complex
Embodiment 5
Fig. 2 gives the solution ultra-violet absorption spectrum of (FONPy) Pt, (SPFPy) Pt, (ECzPy) Pt complex.It will
(FONPy) Pt, (SPFPy) Pt, (ECzPy) Pt complex are configured to 10 respectively-5The methylene chloride weak solution of mol/L, pipettes one
(FONPy) Pt, (SPFPy) Pt, (ECzPy) Pt complex solution of volume are determined in fluorescence cuvette, test its UV absorption
Spectrum.As shown in Figure 2, since the main ligand of three kinds of metal platinum complexes is similar, absorption spectrum waveform is roughly the same.?
Strong absorption within the scope of 250nm-330nm belongs on ligand1The transition absorption peak of π-π *；Within the scope of 330 nm-425nm
With absorption peak, in this intensity absorption peak belong to singlet state metal that spin allows to ligand charge transfer (1MLCT)；?
Weak absorbing peak wavelength within the scope of 450nm-550nm is followed successively by (FONPy) Pt, (SPFPy) Pt, (ECzPy) Pt from short to long, should
The absorption peak of range can belong to the triplet metal of spin forbidden to ligand charge transfer (3MLCT)。
Embodiment 6
Fig. 3 gives the PMMA film shape fluorescence spectrum of (FONPy) Pt, (SPFPy) Pt, (ECzPy) Pt complex.By three
Kind platinum complex is doped into polymetylmethacrylate with 1% mass concentration is made film, then surveys its fluorescence light
Spectrum.From figure 3, it can be seen that luminosity curve is all substance curve, (FONPy) Pt, (SPFPy) Pt, (ECzPy) Pt complex
Emission maximum be respectively 567nm, 515.5nm and 549nm.It is made after PMMA film and occurs that part is aerobic to be quenched, therefore the wave that shines
Length is affected.(SPFPy) spiro structure in Pt complex has very strong rigidity, so that the disconnected conjugation of complex, and
(ECzPy) charge transfer transition is generated in the double carbazole groups modified on Pt complex, energy reduces, and wavelength becomes larger.It introduces
Spiro structure and carbazole group can inhibit intermolecular stacking, greatly increase the spacing between Pt-Pt, to reduce triplet
Metal-metal to ligand charge shift (3MMLCT) phenomenon increases wavelength.
Embodiment 7
Fig. 4 gives the powdered fluorescence spectrum of (FONPy) Pt, (SPFPy) Pt He (ECzPy) Pt complex.By three kinds
Complex is spin-dried for powder, surveys the fluorescence spectrum of powdered complex.Figure 4, it is seen that Pt complex shows single-shot
Peak is penetrated, luminescent spectrum covers green light-yellow light-red light region, and emission maximum is respectively 524nm, 548nm and 620 nm.Compared to
The transmitting of PMMA doping film, a degree of red shift has occurred in bulk powder shape fluorescence emission spectra, this is because in PMMA
The aerobic of part occurs when membranaceous to be quenched, therefore the relatively powdered Shi Genggao of energy, wavelength is shorter, and occurs when powdered
Red shift occurs so that wavelength is elongated for aggregation.
Embodiment 8
Fig. 5 gives (FONPy) Pt, (SPFPy) Pt, (ECzPy) Pt complex fluorescence spectra in acetonitrile solution, leads to
Crossing water/acetonitrile mixed solvent of configuration different moisture content, (0%, 10% in figure, 20%, 30%...90% refers to the mixing of water/acetonitrile
Volume fraction shared by water in solvent), same amount of complex is added and is dissolved, its fluorescence spectrum is tested, verifies
Assemble luminescence enhancement (AIEE) activity.With the addition of dampening, Pt complex is gradually precipitated out, and solution becomes liquid-solid two-phase mixture
System, Pt system complex show typical aggregation inducing enhancing luminescent effect, and red shift occurs in emission spectrum.Three kinds of metal platinums are matched
Close object (FONPy) Pt, (SPFPy) Pt, (ECzPy) Pt fluorescence radiation wavelength be respectively 529nm, 518nm, 613.5nm.Phase
Solid-state PMMA film is emitted, red shift has occurred in all wavelength of fluorescence, this is because complex generates aggregation, so that wave
Long to increase, the higher state of aggregation of concentration shines and is more obvious.
Embodiment 9
Fig. 6 gives the fluorescence lifetime figure of (FONPy) Pt, (SPFPy) Pt He (ECzPy) Pt complex.Three kinds of complexs
Quantum efficiency be respectively 9.98%, 18.64%, 21.55%, fluorescence lifetime is respectively 3.9 μ s, 1.7 μ s, 0.8 μ s.
(ECzPy) service life of fluorescence lifetime ratio (SPFPy) Pt complex of Pt complex is short, illustrates that the rigid structure of spiro structure is opposite
More preferable in carbazole group performance flexible, complex structure is more stable, is more applicable for device preparation.
4, the chemical property of platinum complex
Embodiment 10
Complex HOMO/LUMO energy level plays a decisive role to device and the selection of each functional material, the device junction of level-density parameter
Structure can be injected and be transmitted in order to electron hole, improve device efficiency.For the energy level for measuring complex, using cyclic voltammetry,
Oxidation process uses tetrahydrofuran, and reduction process uses methylene chloride, Ag+/AgNO3For solution as reference electrode, ferrocene is molten
As standard solution, (concentration is greater than 10 to liquid-3Mol).Fig. 7 gives (FONPy) Pt, (SPFPy) Pt, (ECzPy) Pt and matches
The cyclic voltammetry curve of object is closed, specific Photophysical Behaviors parameter is listed in Table 1 below.It can be seen from figure 7 that all Pt complexs
Good electrochemical oxidation-the reduction peak of invertibity is shown, secondary electron reduction successively occurs, and rise with the variation of ligand
Beginning peak position moves.For (ECzPy) Pt, corresponding HOMO, LUMO energy level be respectively (- 4.962eV ,-
2.612eV) and (- 5.678eV, -3.328eV)；And two HOMO, the lumo energies of spiro fluorene complex (SPFPy) Pt are respectively
(- 5.229eV, -2.989eV) and (- 5.581eV, -3.341eV), by changing modification group, the HOMO energy of Pt complex
Grade, spectrum band gap are regulated, to change transmitting color.The higher HOMO energy level of three kinds of platinum complexes is conducive to hole injection,
Lower lumo energy is conducive to electron injection, so as to prepare the device of low operating voltage.
Table 1 (FONPy) Pt, (SPFPy) Pt, (ECzPy) Pt complex Photophysical Behaviors
5, the production of organic electroluminescence device
Embodiment 11
Fig. 8~11 are red device characterization result.By (ECzPy) Pt complex as material of main part, device performance is characterized.
Prepared device architecture are as follows: ITO/PEDOT:PSS/TAPC:TCTA:PVK:OXD-7:wt% (ECzPy) Pt/TPBI (35
Nm)/Ca:Ag, wherein ITO (oxidation cigarette tin) indicates the anode of device, PEDOT:PSS (poly- (3,4- ethyl dioxy thiophene): poly-
Styrene sulfonate) indicate that hole transmission layer, TAPC:TCTA:PVK:OXD-7:wt% (ECzPy) Pt indicate luminescent layer, TPBI
Indicate that electron transfer layer, Ca:Ag indicate the cathode of device, TAPC:TCTA:PVK:OXD-7 is as the main body material in luminescent layer
Material, wherein TAPC:TCTA:PVK:OXD-7=18:18:5:9, adjust (ECzPy) Pt doping concentration (5%, 10%, 15%,
20%, 30%).First by ITO substrate methylene chloride ultrasound 20min, then cleaned with detergent, then successively with ultrapure water,
Acetone, EtOH Sonicate 20min, last 80 DEG C of drying.Substrate after cleaning successively spin coating PEDOT:PSS and luminescent layer, when spin coating
Between be 30s, anneal 120 DEG C, 20min.Electron transfer layer TPBI and electrode Ca:Ag is deposited later.
When the doping concentration of (ECzPy) Pt in luminescent layer is 10%, as shown in figure 8, electroluminescent light spectral purity is preferable,
Single emission peak is presented, maximum emission peak position is 608nm, belongs to typical red emission device；Shown in Figure 10, maximum brightness
Reach 15408.6cd/m2, opening bright voltage is 2.8V；Shown in Figure 11, maximum current efficiency reaches 16.0cd/A, shows that the platinum is matched
Object is closed to have a good application prospect in OLED.
Claims (9)
1. a kind of platinum complex for organic electroluminescence device, which is characterized in that there is following chemical structure,
Wherein,
R1=carbonyl, fluorenyl, double N- alkyl carbazole bases；
R2=methyl, ethyl, propyl.
2. platinum complex according to claim 1, which is characterized in that R2=ethyl.
3. a kind of method for preparing platinum complex as claimed in claim 1 or 2, which comprises the following steps:
(1) under nitrogen protection, Platinous Potassium Chloride is dissolved in dimethyl sulfoxide and water, reaction is stirred at room temperature, is stood, filters, washes
It washs, obtains Pt (DMSO)2Cl2；
(2) under nitrogen protection, by Ligands and Pt (DMSO)2Cl2It is added in 2-methyl cellosolve, first stage elder generation's constant temperature is anti-
It answers, it is cooling, sodium acetate and the first ligand are added, second stage continues isothermal reaction, and cooling, extraction chromatographed column, and obtained platinum
Complex；Wherein, first ligand is 3,3 '-two Trifluoromethyl-1 H, 1 ' H- [5,5 ']-connection pyrazoles, and the Ligands are
4,5- carboline -9- ketone, 4A'4B', 8A'9a' tetrahydro spiral shell [two pyridine 5,9' fluorenes of cyclopenta [2,1-B:3,4-B']] or 5,
Any one of bis- two pyridines of (9- ethyl -9H- carbazole -4- base) -5H- cyclopenta [2,1-B:3,4-B'] of 5-.
4. the preparation method of platinum complex according to claim 3, which is characterized in that the bis- (9- ethyl -9H- of 5,5-
Carbazole -4- base) -5H- cyclopenta [2,1-B:3,4-B'] two the preparation of pyridine be under nitrogen protection, by 4,5- phenodiazine
Fluorenes -9- ketone and N- ethyl carbazole are dissolved in methylene chloride, and Eton reagent is added dropwise, and isothermal reaction is cooling, tune pH value of solution to neutrality,
Extraction, chromatographed column and obtained.
5. the preparation method of platinum complex according to claim 3, which is characterized in that the first stage in the step (2)
The temperature of isothermal reaction is 119~125 DEG C, and the reaction time is 2~3h；The temperature of second stage isothermal reaction is 130~135
DEG C, the reaction time is 7~8h.
6. the preparation method of platinum complex according to claim 3, which is characterized in that chromatographed column in the step (2)
Eluant, eluent be methylene chloride or petroleum ether and methylene chloride mixture.
7. the preparation method of platinum complex according to claim 4, which is characterized in that the isothermal reaction temperature be 90~
110 DEG C, the reaction time is 10~14h.
8. the preparation method of platinum complex according to claim 4, which is characterized in that chromatographing eluant, eluent used in column is two
Chloromethanes.
9. the preparation method of platinum complex according to claim 3 or 4, which is characterized in that extractant used is dichloromethane
Alkane.
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| CN114573639A (en) * | 2020-11-30 | 2022-06-03 | 广东阿格蕾雅光电材料有限公司 | Platinum complexes of carbazole-containing ONCN tetradentate ligands |
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| CN114573639A (en) * | 2020-11-30 | 2022-06-03 | 广东阿格蕾雅光电材料有限公司 | Platinum complexes of carbazole-containing ONCN tetradentate ligands |
| CN114573639B (en) * | 2020-11-30 | 2023-12-12 | 广东阿格蕾雅光电材料有限公司 | Platinum complex of ONCN tetradentate ligand containing carbazole |
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