CN113354688A - 6/6/6 tetradentate ring metal palladium (II) complex luminescent material based on azacarbazole-carbazole and application thereof - Google Patents
6/6/6 tetradentate ring metal palladium (II) complex luminescent material based on azacarbazole-carbazole and application thereof Download PDFInfo
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Abstract
The invention provides an 6/6/6 tetradentate ring metal palladium (II) complex luminescent material based on azacarbazole-carbazole and application thereof. The 6/6/6 tetradentate ring metal palladium (II) complex luminescent material based on azacarbazole-carbazole has a dual emission mechanism of phosphorescence and delayed fluorescence, wherein azacarbazole and pyridine moieties both serve as acceptors, carbazole-phenyl and carbazole-carbazole moieties serve as donors, and the excited state (S) passes through1) And triplet state (T)n) With a small energy gap (Δ E) between statesS1‑Tn) Two key processes of effective intersystem crossing (ISC) are realized by the natural transition orbit matched with the metal-assisted delayed fluorescence (MADF) emission, so that the emission spectrum is formedBlue shift occurs, which is beneficial to obtaining luminescent material with high triplet state energy from triplet state energy low molecules and realizing broader luminescent color.
Description
Technical Field
The invention relates to a luminescent material and application thereof, in particular to an 6/6/6 quadridentate ring metal palladium (II) complex luminescent material based on azacarbazole-carbazole and application thereof.
Background
OLEDs, i.e., Organic Light-Emitting diodes (OLEDs), also known as Organic electroluminescent displays, Organic Light-Emitting semiconductors, have many unique and outstanding advantages, such as compatibility with flexible substrates, low-cost manufacturing methods, and low power consumption, and also have high color quality, wide viewing angle, wide operating temperature range, and fast response, and have been widely considered as candidates for next-generation display and solid-state lighting technologies.
The OLED material is the core of OLED display technology and is the basis for realizing self-luminescence of the OLED. The fluorescent material can be mainly divided into a first generation fluorescent material, a second generation phosphorescent material and a third generation delayed fluorescent material (a thermally activated delayed fluorescent material and metal-assisted delayed fluorescence). Purely organic TADF materials employ bulky, helical or twisted molecules to link the donor and acceptor moieties. Due to T1→S0Has spin-forbidden properties, so no strong phosphorescence is observed at room temperature.
Compared with a pure organic delayed luminescent material, the delayed luminescent material with metal participation has more advantages. In recent years, Metal-assisted delayed Fluorescence (MADF) -based materials have been mainly used to make triplet excitons pass T first due to their dual emission mechanism of phosphorescence and delayed Fluorescence1→S1Up-conversion, and then from S1To S0Radiation transition of (2). In this process, Δ E is smallerST(usually 0.05-0.2eV) and long excited state lifetime are two key features for enhancing the delayed fluorescence emission process, and T can be effectively realized1→S1Up-conversion and suppression of non-radiative decay processes. In addition, metals can also contribute to their d-orbitals to efficiently achieve metal-to-ligand charge transfer (MLCT) processes, which may play a key role in delaying fluorescence processes. Therefore, the metal-assisted delayed fluorescent material has the characteristics of abundant excited state properties, controllability, heavy atom effect and the like, and has been widely concerned by researchers in recent years.
At present, palladium has a strong spin-orbit coupling (SOC) effect in a metal complex, because charge transfer can be generated between metal and a ligand in the metal complex, and the charge transfer singlet state is close to the charge transfer triplet state and the energy between the triplet state orbitals of the ligand, so that a metal-assisted delayed fluorescence process is realized. Therefore, the design and development of new metal-assisted delayed fluorescence materials are still the urgent problems to be solved for promoting the development of the OLED field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an 6/6/6 tetradentate ring metal palladium (II) complex luminescent material based on azacarbazole-carbazole and application thereof.
To achieve the above object of the invention: the invention provides an 6/6/6 fused tetracyclic metal palladium (II) complex luminescent material based on azacarbazole-carbazole, which is shown as a general formula (1):
wherein, Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9And Y10Each independently represents C or N;
a represents B, CH, CD, CRa、SiH、SiD、SiRa、GeH、GeD、GeRdP, P ═ O, As ═ O, Bi, or Bi ═ O;
Ra、Rb、Rcand RdEach independently is hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imine, sulfo, carboxyl, hydrazine, substituted silyl, a polymeric group, or a combination thereof;
R1、R2、R3、R4、R5、R6and R7Each independently represents hydrogen, deuterium, an alkyl group, an alkoxy group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a haloalkyl group, a halogen, a hydroxyl group, a mercapto group, a nitro group, a cyano group, an amino group, a carboxyl group, a sulfo group, a hydrazino group, a ureido group, an alkynyloxy group, an ester group, an amide group, a sulfonyl group, a sulfinyl group, a sulfonylamino group, a phosphorylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a silyl group, an alkylamino group, a bisalkylamino group, a monoarylamino group, a bisarylamino group, a ureylene group, an imino group, or a combination thereof, R1、R2、R3、R4、R5、R6And R7Two or more of which may be joined to form a fused ring, which may also be fused with other rings.
Further, the 6/6/6 pentacyclic tetradentate ring metal palladium (II) complex luminescent material based on azacarbazole-carbazole is shown as a general formula (2):
wherein, Y1、Y2、Y3、Y4、Y5、Y6And Y7Each independently represents C or N;
a represents O, S, S ═ O or O ═ S ═ O;
R1、R2、R3、R4、R5and R6Each independently represents hydrogen, deuterium, an alkyl group, an alkoxy group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a haloalkyl group, halogen, a hydroxyl group, a mercapto group, a nitro group, a cyano group, an amino group, a carboxyl group, a sulfo group, a hydrazino group, a ureido group, an alkynyloxy group, an ester group, an amide group, a sulfonyl group, a sulfinyl group, a sulfonylamino group, a phosphorylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a silyl group, an alkylamino group, a bisalkylamino group, a monoarylamino group, a bisarylamino group, a ureylene groupImino or a combination thereof, R1、R2、R3、R4、R5、R6And R7Two or more of which may be joined to form a fused ring, which may also be fused with other rings.
Further, the 6/6/6 pentacyclic tetradentate ring metal palladium (II) complex luminescent material based on azacarbazole-carbazole is a compound represented by the following structure, but is not limited to the compound:
further, the 6/6/6 pentacyclic tetradentate ring metal palladium (II) complex based on azacarbazole-carbazole is applied to an organic light-emitting element as a light-emitting material. The organic light emitting element is an organic light emitting diode, a light emitting diode or a light emitting electrochemical cell.
Further, the light-emitting element includes a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, the 6/6/6 pentacyclic and tetracyclic palladium (II) complex based on azacarbazole-carbazole.
The invention has the beneficial effects that: the 6/6/6 tetradentate ring metal palladium (II) complex luminescent material based on azacarbazole-carbazole has a dual emission mechanism of phosphorescence and delayed fluorescence, wherein azacarbazole and pyridine moieties both act as acceptors, carbazole-phenyl and carbazole-carbazole moieties act as donors, and the emission is carried out through an excited state (S)1) And triplet state (T)n) With a small energy gap (Δ E) between statesS1-Tn) (less than 0.3eV) and a natural transition orbit matched with the (less than 0.3eV) realize two key processes of effective intersystem crossing (ISC), realize metal-assisted delayed fluorescence (MADF) emission, enable an emission spectrum to generate blue shift, are beneficial to obtaining a luminescent material with high triplet state energy from triplet state energy low molecules, and realize wider emissionWide light emitting color.
Drawings
FIG. 1 is a graph showing emission spectra of Pd (ACzCz-1) and Pd (ACzCz-2) in 2-methyltetrahydrofuran at 77K;
FIG. 2 is a graph showing the emission spectra of Pd (ACzCz-1) and Pd (ACzCz-2) in a dichloromethane solution at room temperature;
FIG. 3 is a graph showing the emission spectra of Pd (ACzCz-1) and Pd (ACzCz-2) in polymethyl methacrylate (PMMA) at room temperature;
FIG. 4 is a graph showing the emission spectra of Pd (ACCZCz-1) in 2-methyltetrahydrofuran at 77K, in dichloromethane and in polymethyl methacrylate (PMMA);
FIG. 5 is a graph of the emission spectra of Pd (ACCZCz-2) in 2-methyltetrahydrofuran at 77K, in dichloromethane and in Polymethylmethacrylate (PMMA);
FIG. 6 is a diagram showing the optimized molecular structures, the front linear orbital levels and their distributions, and the Spin Density distribution maps of the lowest triplet states of Pd (ACzCz-1) and Pd (ACzCz-2) calculated by Density Functional Theory (DFT) and time-dependent Density functional theory (DT-DFT), in which HOMO or H is the highest occupied molecular orbital, LUMO or L is the highest occupied molecular orbital, Spin Density is the Spin Density, and T is the Spin Density distribution map of the lowest triplet state1Is the lowest triplet state;
FIG. 7 is a graph showing the optimization of the ground state of molecules (S)0) The structure is calculated to obtain Pd (ACzCz-1) and Pd (ACzCz-2) S1And T1Natural Transition Orbit (NTO) profile under state;
fig. 8 is a schematic structural view of an organic light emitting device.
Detailed Description
The present invention will be described in detail below. The following description of the constituent elements may be based on a representative embodiment or specific example of the present invention, but the present invention is not limited to such an embodiment or specific example.
The 6/6/6-fused tetracyclic palladium (II) metal complex luminescent material based on azacarbazole-carbazole comprises a compound having a structure represented by the following general formula (1) or (2).
Specific examples of the light-emitting material of the present invention represented by the following general formula (1) are illustrated below, however, the present invention is not construed to be limited thereto.
Unless otherwise indicated, all commercial reagents involved in the following experiments were purchased and used directly without further purification. The hydrogen spectrum and the carbon spectrum of the nuclear magnetic resonance are both in deuterated chloroform (CDCl)3) Or deuterated dimethyl sulfoxide (DMSO-d)6) The hydrogen spectrum is measured by a nuclear magnetic resonance spectrometer with 400 or 500 MHz, the carbon spectrum is measured by a nuclear magnetic resonance spectrometer with 100 or 125 MHz, and the chemical shift is based on Tetramethylsilane (TMS) or residual solvent. If CDCl is used3As solvents, the hydrogen spectrum and the carbon spectrum are respectively expressed in TMS (delta-0.00 ppm) and CDCl3(δ 77.00ppm) as an internal standard. If DMSO-d is used6As solvents, the hydrogen spectrum and the carbon spectrum are respectively expressed in TMS (delta 0.00ppm) and DMSO-d6(δ 39.52ppm) as an internal standard. The following abbreviations (or combinations) are used to interpret the hydrogen peaks: s is singlet, d is doublet, t is triplet, q is quartet, p is quintet, m is multiplet, br is broad. High resolution mass spectra were measured on an ESI-QTOF mass spectrometer from Applied Biosystems, the sample ionization mode being electrospray ionization.
The general formulas (1) and (2) are synthesized by the following steps:
example 1: the synthetic route of the luminescent material Pd (ACzCz-1) of the tetradentate ring metal palladium (II) complex is as follows:
(1) synthesis of ligand L (ACzCz-1): to a dry sealed tube with a magnetic rotor was added ACzCzH (200mg,0.6mmol,1.0 equiv.), 1-Br (300mg,1.2mmol,2 equiv.), tris (dibenzylideneallyl propane)Ketone) dipalladium (46mg,0.05mmol,8 mol%), 2- (di-tert-butylphosphine) biphenyl (30mg,0.1mmol,16 mol%) and sodium tert-butoxide (115mg,1.2mmol,2.0 eq.) then nitrogen was purged three times and toluene (12mL) was added under nitrogen. The mixture was stirred in an oil bath at 110 ℃ for 2 days, cooled to room temperature, and the solvent was distilled off under reduced pressure. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum ether/ethyl acetate 10:1-5:1 gave product L (ACzCz-1) as a white solid, 290mg, 96% yield.1H NMR(500MHz,DMSO-d6):δ6.94-6.96(m,1H),7.07(d,J＝7.5Hz,1H),7.24-7.26(m,1H),7.34-7.40(m,3H),7.45-7.50(m,3H),7.51-7.60(m,4H),7.67(t,J＝8.0Hz,1H),7.70-7.72(m,1H),7.73(d,J＝1.5Hz,1H),7.76-7.80(m,1H),8.33(d,J＝8.0Hz,1H),8.36-8.38(m,2H),8.50(d,J＝8.0Hz,1H),8.67(dd,J＝7.5,1.5Hz,1H)。13C NMR(125MHz,CDCl3):δ109.54,110.13,110.48,111.86,115.85,116.21,118.90,119.72,119.92,120.43,120.47,120.56,120.63,120.81,121.21,122.45,123.17,126.29,128.20,130.70,134.09,138.34,139.46,140.74,141.18,141.28,146.50,147.51,152.36,155.32,163.01。
(2) Synthesis of Pd (ACzCz-1): to a 100mL dry three-necked flask equipped with a magnetic rotor and condenser was added ligand L (ACzCz-1) (200mg,0.41mmol,1.0 equiv.), palladium acetate (101mg,0.45mmol,1.1 equiv.), tetra-n-butylammonium bromide (13mg,0.041mmol,0.1 equiv.) in that order, then nitrogen was purged three times and acetic acid (25mL) was added under nitrogen blanket. After bubbling nitrogen for 30 minutes, the reaction mixture was stirred for 8 hours at room temperature, then stirred at 100 ℃ for 2 days, cooled to room temperature, and the solvent was distilled off under reduced pressure. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum ether/dichloromethane ═ 3:1-2:1, yielding the product Pd (ACzCz-1) as a yellow solid, 35mg, yield 14%.1H NMR(500MHz,DMSO-d6):δ7.00(d,J＝8.0Hz,1H),7.22(t,J＝7.5Hz,1H),7.32(t,J＝7.5Hz,1H),7.45-7.51(m,3H),7.60-7.74(m,5H),8.08(d,J＝8.5Hz,1H),8.12-8.16(m,2H),8.22-8.27(m,2H),8.41-8.45(m,2H),8.94-8.95(m,1H),8.97-8.99(m,1H)。
Example 2: the synthetic route of the luminescent material Pd (ACzCz-2) of the tetradentate ring metal palladium (II) complex is as follows:
(1) synthesis of ligand L (ACzCz-2): to a dry sealed tube with a magnetic rotor was added ACzCzH (400mg,1.2mmol,1.0 equiv.), 2-Br (580mg,1.8mmol,1.5 equiv.), tris (dibenzylideneacetone) dipalladium (44mg,0.048mmol,4 mol%), 2- (di-tert-butylphosphine) biphenyl (29mg,0.096mmol,8 mol%) and sodium tert-butoxide (231mg,2.4mmol,2.0 equiv.) and then nitrogen was purged three times and toluene (12mL) was added under nitrogen blanket. The mixture was stirred in an oil bath at 110 ℃ for 2 days, cooled to room temperature, and the solvent was distilled off under reduced pressure. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum ether/ethyl acetate 10:1-5:1 gave product L (ACzCz-2) as a white solid, 400mg, 58% yield.1H NMR(500MHz,DMSO-d6):δ7.28-7.34(m,2H),7.38(t,J＝8.0Hz,2H),7.42-7.39(m,2H),7.50-7.53(m,4H),7.57(d,J＝8.5Hz,1H),7.63(d,J＝8.5Hz,1H),7.66(d,J＝8.5Hz,1H)7.83-7.86(m,2H),8.05-8.08(m,1H),8.11(d,J＝2.0Hz,1H),8.27(d,J＝7.5Hz,1H),8.30-8.33(m,2H),8.38(d,J＝8.0Hz,1H),8.48-8.52(m,2H),8.60-8.62(m,2H)。13C NMR(125MHz,CDCl3):δ109.33,110.13,110.42,111.15,115.81,116.21,118.88,119.53,120.12,120.15,120.30,120.39,120.49,120.65,120.79,121.16,121.26,121.31,121.47,122.89,122.96,123.74,126.20,126.55,126.85,128.16,134.04,135.25,138.59,140.20,140.22,140.63,140.63,141.96,142.12,146.41,149.71,151.33,152.28。
(2) Synthesis of Pd (ACzCz-2): : to a 100mL dry three-necked flask equipped with a magnetic rotor and a condenser, ligand L (ACzCz-2) (200mg,0.35mmol,1.0 equiv.), palladium acetate (88mg,0.39mmol,1.1 equiv.), tetra-n-butylammonium bromide (11mg,0.035mmol,0.1 equiv.) were added sequentially, then nitrogen was purged three times, and acetic acid (21mL) was added under nitrogen. After bubbling nitrogen for 30 minutes, the reaction mixture was stirred for 8 hours at room temperature, then stirred at 100 ℃ for 2 days, cooled to room temperature, and the solvent was distilled off under reduced pressure. Separating and purifying the obtained crude product by using a silica gel chromatographic column, eluting a eluent: petroleum ether/dichloromethane ═ 3:1-2:1, yielding the product Pd (ACzCz-2) as a yellow solid, 100mg, yield 42%.
1H NMR(500MHz,DMSO-d6) δ 7.34(t, J ═ 7.5Hz,1H),7.41(t, J ═ 7.0Hz,1H),7.46-7.55(m,5H),7.62-7.66(m,1H),7.80(d, J ═ 8.0Hz,1H),7.86(d, J ═ 8.5Hz,1H),7.94(d, J ═ 8.5Hz,1H),8.07-8.09(m,2H),8.12-8.15(m,3H),8.20(d, J ═ 8.0Hz,2H),8.30(d, J ═ 7.5Hz,1H),8.43(d, J ═ 7.5Hz,1H),8.55(dd, J ═ 5.0, 1.0, 7.5H), 7.97.19, 7.17H), and 1.17H). Electrochemical, photophysical tests and theoretical calculations show that:
absorption spectra were measured on an Agilent 8453 uv-vis spectrometer, steady state emission experiments and lifetime measurements were performed using a Horiba Jobin Yvon fluolog-3 spectrometer. Low temperature (77K) emission spectra and lifetimes were measured in 2-methyltetrahydrofuran (2-MeTHF) solution cooled with liquid nitrogen. The Pd (II) complex is theoretically calculated by using a Gaussian 09 software package, and the ground state (S) is optimized by using the Density Functional Theory (DFT)0) The geometry of the molecule was calculated by DFT using the B3LYP functional, wherein C, H, O and N atoms were grouped using the 6-31G (d) group and Pd atoms were grouped using the LANL2DZ group.
Experimental data and analysis:
as can be seen from the photoluminescence emission spectra and photophysical data of Pd (ACzCz-1) and Pd (ACzCz-2) in the attached figures 1, 2, 3 and Table 1 under different conditions, Pd (ACzCz-1) and Pd (ACzCz-2) can be used as a blue-to-green light emitting material, and the derivatives thereof can have a wider emission color from blue light to yellow light or even red light through the regulation and control of substituents in the ligands. As can be seen from FIGS. 4 and 5, the emission spectra of Pd (ACzCz-1) and Pd (ACzCz-2) in the dichloromethane solution and the polymethyl methacrylate film at room temperature are both smooth and fine-vibrational structure-free spectra (i.e., Gaussian-type spectra), and the emission spectra of Pd (ACzCz-1) and Pd (ACzCz-2) in PMMA at RT shows a significant blue shift, which is a characteristic of metal-assisted delayed fluorescence (MADF), compared with the corresponding emission spectra in 2-MeTHF at 77K.
Table 1: four-ring metal palladium (II) complex luminescent material photophysical property data list
Note: λ is the emission wavelength; tau isobsIs the excited state lifetime of the material; PMMA is polymethyl methacrylate.
Table 2: excited state energy level of quadridentate ring metal palladium (II) complex luminescent material
| T1[eV] | T2[eV] | S1[eV] | ΔES1-T1[eV] | ΔES1-T2[eV] | |
| Pd(ACzCz-1) | 2.704 | 2.741 | 2.761 | 0.057 | 0.020 |
| Pd(ACzCz-2) | 2.559 | 2.641 | 2.671 | 0.122 | 0.030 |
| Pt(ACzCz-1) | 2.547 | 2.577 | 2.595 | 0.048 | 0.018 |
| Pt(ACzCz-2) | 2.244 | 2.494 | 2.524 | 0.280 | 0.030 |
Note: t is1Is the lowest excited triplet state; t is2Is a second excited triplet state; s1Is the lowest excited singlet state; delta ES1-T1Is S1And T1The difference in energy levels between; delta ES1-T2Is S1And T2The difference in energy levels between.
As shown in the attached figure 6 and the table 2, 6/6/6-fused tetracyclic metal palladium (II) complex luminescent materials Pd (ACzCz-1) and Pd (ACzCz-2) based on azacarbazole-carbazole have small delta ES1-T1And Δ ES1-T20.057eV and 0.020eV, 0.020 and 0.030eV, respectively, and T1And T2Charge transfer type of state and S1Matching, inter-system cross-over (ISC) and T are efficiently achieved1→S1The intersystem crossing (RISC) pathway of (a), Pd (ACzCz-1) and Pd (ACzCz-2) exhibit both phosphorescence and metal-assisted delayed fluorescence (MADF) for the two reasons described above, matching the experimental data described above.
As can be seen from the natural orbital transition (NTO) analysis in FIG. 7, Pd (II) (ξ ═ 1412 cm)-1) Has an SOC constant of less than Pt (II) (ξ 4481 cm)-1) Result in T1In the following, the first and second parts of the material,3has less MLCT, therebyEnhanced3The LC characteristic. In FIG. 7, of Pd (ACzCz-1)3MLCT(πACz*→πCzPhdPt) Only 7.1%, mostly3LC(πACz*→πACz，πPhPy*→πPhPy) Whereas Pd (ACzCz-2) is only 4.2%3MLCT(πPyy*→πCzCzdPt) Most of them are also3LC (π Cz → π Cz). Thus, T1Reduced in state3MLCT characteristics thereby reducing T1→S0Radiation rate (k) of transitionr) And returning some excitons to S via inter-inversion cross-over (RISC)1State, finally decaying to S0State-generated metal-assisted delayed fluorescence (MADF), matched with the experimental data above.
In an organic light-emitting element, carriers are injected into a light-emitting material from both positive and negative electrodes, and the light-emitting material in an excited state is generated and emits light. The complex of the present invention represented by the general formula (1) can be used as a phosphorescent material for an excellent organic light-emitting device such as an organic photoluminescent device or an organic electroluminescent device. The organic photoluminescent element has a structure in which at least a light-emitting layer is formed over a substrate. The organic electroluminescent element has a structure in which at least an anode, a cathode, and an organic layer between the anode and the cathode are formed. The organic layer may be composed of only the light-emitting layer, or may have 1 or more organic layers other than the light-emitting layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer. The hole transport layer may be a hole injection transport layer having a hole injection function, and the electron transport layer may be an electron injection transport layer having an electron injection function. Fig. 8 shows a schematic structure of a specific organic light-emitting element. In fig. 8, 7 layers are shown from bottom to top, and a substrate, an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and a cathode are sequentially shown, where the light-emitting layer is a mixed layer in which a guest material is doped with a host material.
The phosphorescent light-emitting material is doped into a host material as a guest material to prepare a light-emitting layer which can be applied to OLED devices, and the structure is shown as follows:
ITO/HATCN (10nm)/TAPC (65 nm)/host Material Pd (ACzCz-2) (10 wt.%, 20nm)/TmPyPB (55nm)/LiF/Al
Wherein, the ITO is a transparent anode; HATCN is a hole injection layer, TAPC is a hole transport layer, the host materials are mCBP and 26mCPy, respectively, TmPyPB is an electron transport layer, LiF is an electron injection layer, and Al is a cathode. The number in parentheses in nanometers (nm) is the thickness of the film.
The molecular formula of the applied material in the device is as follows:
it should be noted that the structure is an example of an application of the light emitting material of the present invention, and does not constitute a limitation to the structure of a specific OLED device of the light emitting material of the present invention, and the phosphorescent light emitting material is not limited to the compounds shown in the examples.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice. For example, many of the substituent structures described herein may be substituted with other structures without departing from the spirit of the invention.
Claims (6)
1. An 6/6/6 tetradentate ring metal palladium (II) complex luminescent material based on azacarbazole-carbazole, which is characterized in that the chemical formula is shown as the general formula (1):
wherein, Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8、Y9And Y10Each independently represents C or N;
a represents B, CH, CD, CRa、SiH、SiD、SiRa、GeH、GeD、GeRdP, P ═ O, As ═ O, Bi, or Bi ═ O;
Ra、Rb、Rcand RdEach independently is hydrogen, deuterium, aryl, cycloalkyl, cycloalkenyl, heterocyclyl, heteroaryl, alkyl, alkenyl, alkynyl, halogen, hydroxy, mercapto, nitro, cyano, amino, mono-or dialkylamino, mono-or diarylamino, alkoxy, aryloxy, haloalkyl, ester, nitrile, isonitrile, heteroaryl, alkoxycarbonyl, amido, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, carbamoyl, alkylthio, sulfinyl, ureido, phosphoramido, imine, sulfo, carboxyl, hydrazine, substituted silyl, a polymeric group, or a combination thereof;
R1、R2、R3、R4、R5、R6and R7Each independently represents hydrogen, deuterium, an alkyl group, an alkoxy group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a haloalkyl group, a halogen, a hydroxyl group, a mercapto group, a nitro group, a cyano group, an amino group, a carboxyl group, a sulfo group, a hydrazino group, a ureido group, an alkynyloxy group, an ester group, an amide group, a sulfonyl group, a sulfinyl group, a sulfonylamino group, a phosphorylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a silyl group, an alkylamino group, a bisalkylamino group, a monoarylamino group, a bisarylamino group, a ureylene group, an imino group, or a combination thereof; r1、R2、R3、R4、R5、R6And R7Two or more of which are joined to form a fused ring, which may also be fused with other rings.
2. An 6/6/6 tetradentate ring metal palladium (II) complex luminescent material based on azacarbazole-carbazole, which is characterized in that the chemical formula is shown as a general formula (2):
wherein, Y1、Y2、Y3、Y4、Y5、Y6And Y7Each independently represents C or N;
a represents O, S, S ═ O or O ═ S ═ O;
R1、R2、R3、R4、R5and R6Each independently represents hydrogen, deuterium, an alkyl group, an alkoxy group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a haloalkyl group, a halogen, a hydroxyl group, a mercapto group, a nitro group, a cyano group, an amino group, a carboxyl group, a sulfo group, a hydrazino group, a ureido group, an alkynyloxy group, an ester group, an amide group, a sulfonyl group, a sulfinyl group, a sulfonylamino group, a phosphorylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, a silyl group, an alkylamino group, a bisalkylamino group, a monoarylamino group, a bisarylamino group, a1、R2、R3、R4、R5、R6And R7Two or more of which may be joined to form a fused ring, which may also be fused with other rings.
3. The azacarbazole-carbazole-based 6/6/6 tetradentate ring metallic palladium (II) complex light-emitting material according to claims 1 to 2, characterized in that its structural formula is selected from:
4. use of the 6/6/6 pentacyclic tetradentate ring metal palladium (II) complex based on azacarbazole-carbazole as described in any one of claims 1 to 3 as a luminescent material in an organic light-emitting element.
5. Use according to claim 4, wherein the organic light emitting element is an organic light emitting diode, a light emitting diode or a light emitting electrochemical cell.
6. The use according to claim 4, wherein the light-emitting element comprises a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, the organic layer comprising an azacarbazole-carbazole-based 6/6/6 pentacyclic metal palladium (II) complex.
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| US20160359125A1 (en) * | 2015-06-03 | 2016-12-08 | Arizona Board Of Regents On Behalf Of Arizona State University | Tetradentate and octahedral metal complexes containing naphthyridinocarbazole and its analogues |
| US20180212165A1 (en) * | 2017-01-23 | 2018-07-26 | Universal Display Corporation | Organic electroluminescent materials and devices |
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| WO2014031977A1 (en) * | 2012-08-24 | 2014-02-27 | Arizona Board Of Regents For And On Behalf Of Arizona State University | Metal compounds and methods and uses thereof |
| US20160359125A1 (en) * | 2015-06-03 | 2016-12-08 | Arizona Board Of Regents On Behalf Of Arizona State University | Tetradentate and octahedral metal complexes containing naphthyridinocarbazole and its analogues |
| US20180212165A1 (en) * | 2017-01-23 | 2018-07-26 | Universal Display Corporation | Organic electroluminescent materials and devices |
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