CN113121604A - Red organic electrophosphorescent platinum complex and application thereof in OLED (organic light emitting diode) device - Google Patents
Red organic electrophosphorescent platinum complex and application thereof in OLED (organic light emitting diode) device Download PDFInfo
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- CN113121604A CN113121604A CN201911390064.6A CN201911390064A CN113121604A CN 113121604 A CN113121604 A CN 113121604A CN 201911390064 A CN201911390064 A CN 201911390064A CN 113121604 A CN113121604 A CN 113121604A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 32
- 239000010410 layer Substances 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 21
- -1 dimethylfluorenyl group Chemical group 0.000 claims description 12
- 125000006413 ring segment Chemical group 0.000 claims description 12
- 125000001072 heteroaryl group Chemical group 0.000 claims description 8
- 239000002346 layers by function Substances 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 4
- 125000006267 biphenyl group Chemical group 0.000 claims description 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 4
- 229910052805 deuterium Inorganic materials 0.000 claims description 4
- 125000002541 furyl group Chemical group 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 59
- 230000000694 effects Effects 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 3
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- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 description 2
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 2
- XFJBGINZIMNZBW-CRAIPNDOSA-N 5-chloro-2-[4-[(1r,2s)-2-[2-(5-methylsulfonylpyridin-2-yl)oxyethyl]cyclopropyl]piperidin-1-yl]pyrimidine Chemical compound N1=CC(S(=O)(=O)C)=CC=C1OCC[C@H]1[C@@H](C2CCN(CC2)C=2N=CC(Cl)=CN=2)C1 XFJBGINZIMNZBW-CRAIPNDOSA-N 0.000 description 2
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- VMFMUJZRXZXYAH-UHFFFAOYSA-N n-[5-[[5-chloro-4-[2-[2-(dimethylamino)-2-oxoacetyl]anilino]pyrimidin-2-yl]amino]-4-methoxy-2-(4-methylpiperazin-1-yl)phenyl]prop-2-enamide Chemical compound C=CC(=O)NC=1C=C(NC=2N=C(NC=3C(=CC=CC=3)C(=O)C(=O)N(C)C)C(Cl)=CN=2)C(OC)=CC=1N1CCN(C)CC1 VMFMUJZRXZXYAH-UHFFFAOYSA-N 0.000 description 2
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- VFMUXPQZKOKPOF-UHFFFAOYSA-N 2,3,7,8,12,13,17,18-octaethyl-21,23-dihydroporphyrin platinum Chemical compound [Pt].CCc1c(CC)c2cc3[nH]c(cc4nc(cc5[nH]c(cc1n2)c(CC)c5CC)c(CC)c4CC)c(CC)c3CC VFMUXPQZKOKPOF-UHFFFAOYSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
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- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
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- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
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- 230000004580 weight loss Effects 0.000 description 1
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
The invention discloses a red organic electrophosphorescent platinum complex and application thereof in an OLED device, belonging to the technical field of semiconductors. The structure of the red organic electrophosphorescent platinum complex is shown as a general formula (1):
the invention also discloses application of the red organic electrophosphorescent platinum complex in an OLED device. The red organic electrophosphorescent platinum complex takes metal platinum as a structural core, has higher luminous efficiency, lower triplet state service life, narrower spectral half-peak width and good material stability, and is used as a luminous layerThe doped material is applied to an OLED device, and can improve the luminous efficiency and prolong the service life of the device. The red organic electrophosphorescent platinum complex has good application effect in OLED luminescent devices and good industrialization prospect.
Description
Technical Field
The invention relates to the technical field of semiconductors, in particular to a red organic electrophosphorescent platinum complex and application thereof in an OLED device.
Background
The research on the improvement of the performance of the OLED light emitting device includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the OLED photoelectric functional material are needed to create the functional material of the OLED with higher performance.
Organic electroluminescent materials fall into two broad categories: organic electroluminescent materials and organic electroluminescent phosphorescent materials. Wherein the organic electroluminescence is the result of radiative deactivation of singlet excitons. In the organic electroluminescent process, triplet excitons and singlet excitons are generated simultaneously, the ratio of the generation of the singlet excitons to the generation of the triplet excitons is usually 1:3, while according to the forbidden effect of quantum statistics, the triplet excitons are subject to important non-radiative decay, have little contribution to luminescence, and only the singlet excitons emit luminescence by radiation,
the fundamental reason that the luminous efficiency is difficult to improve for the OLED device is that the light emitting process is the light emission of singlet excitons, so that the maximum internal quantum efficiency of the light emitting device is only 25 percent, and the maximum external quantum efficiency of the light emitting device is about 5 percent at most.
How to utilize singlet state and triplet state to emit light at the same time to improve the luminous efficiency becomes an important research subject in the OLED field, the phosphorescent material is used for replacing fluorescent material to realize the basic method of phosphorescent emission, in order to improve the yield of phosphorescent quantum of triplet excited state, heavy metal atoms are usually introduced into the phosphorescent material to improve the spin-orbit coupling of excited state molecules, shorten the phosphorescent service life, change the transition from the latest excited triplet state of the original spin forbidden resistance to the singlet ground state into the allowable transition, and greatly improve the luminous efficiency of the material. The Forrest group dopes octaethylporphyrin platinum (PtOEP) in a small molecular host material 8-hydroxyquinoline aluminum to manufacture a red electrophosphorescent device, the external quantum efficiency reaches 4%, so the research on electrophosphorescence is greatly concerned, but the service life of the existing organic electrophosphorescent complex is not ideal and needs to be further improved.
Disclosure of Invention
One of the objects of the present invention is to provide a red organic electrophosphorescent platinum complex. When the red organic electrophosphorescent platinum complex is used as a doping material of a light-emitting layer of an OLED light-emitting device, the current efficiency and the external quantum efficiency of the device are both greatly improved, and the service life of the device is obviously prolonged.
The technical scheme for solving the technical problems is as follows: a red organic electrophosphorescent platinum complex has a general structure shown in general formula (1):
general formula (1)
In the general formula (1), X, X0And X1Each independently represents a single bond, -O-, -S-, -C (R)7)(R8) -or-N (R)9)-；
a. b and c represent 0 or 1, and a + b + c is more than or equal to 1;
R1-R6each independently represents a structure represented by the general formula (2) or the general formula (3), and R1-R6May also be represented by a hydrogen atom, said R1-R6At least one of the structures is represented by the general formula (2);
in the general formula (2), X2And X3Each independently represents a single bond, -O-, -S-, -C (R)10)(R11) -or-N (R)12) -, and not simultaneously represent a single bond;
zi is independently represented by nitrogen atom or C-Ai, wherein i is represented by 1 to 31; ai is selected from hydrogen atom, halogen, cyano, C1-10Alkyl of (C)2-20Substituted or unsubstituted aryl having 6 to 30 ring atoms, substituted or unsubstituted heteroaryl having 5 to 30 ring atoms, wherein two or more Ai's adjacent thereto may be bonded to each other to form a ring;
R7-R12independently selected from C1-10Substituted or unsubstituted aryl having 6 to 30 ring atoms, substituted or unsubstituted heteroaryl having 5 to 30 ring atoms;
the general formula (2) and the general formula (3) are respectively and independently bonded with the adjacent sites marked by the letters in the general formula (1) in a ring-bond mode through two adjacent sites marked by the letters; zi (i ═ 1-23) at adjacent sites is represented as a C atom;
the substituent for substituting the above-mentioned substitutable group is optionally selected from deuterium, halogen, cyano, C1-20Alkyl of (C)2-20Alkenyl of (a), aryl having 6 to 30 ring atoms, heteroaryl containing 5-30 ring atoms;
the heteroatom in the heteroaryl is any one or more selected from N, O or S.
Further, in the general formula (1), R7-R12Each independently represents any one of a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dimethylfluorenyl group, and a substituted or unsubstituted dimethylazazinyl group; ai represents any one of a hydrogen atom, a halogen group, a cyano group, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dimethylfluorenyl group, and a substituted or unsubstituted dimethylazazinyl group; wherein two or more Ai's adjacent can be bonded to each other to form a ring;
the substituent for substituting the above-mentioned substitutable group is optionally selected from deuterium, halogen, cyano, methyl, ethyl, isopropyl, tert-butyl.
Further, the platinum complex is selected from compounds shown as a general formula (1-2) or a general formula (1-3):
further, the platinum complex is selected from compounds represented by general formulas (1-4) to (1-8):
further, said R1-R5At least one of the structures is represented by a general formula (2) or a general formula (3).
Further, X1Is represented by a single bond.
Further, the specific structural formula of the platinum complex is preferably:
the second objective of the present invention is to provide an organic electroluminescent device. The compound has good application effect in an OLED luminescent device, can effectively improve the luminescent efficiency and the service life of the OLED device, and has good application effect and industrialization prospect.
The technical scheme for solving the technical problems is as follows: an organic electroluminescent device comprises a cathode, an anode and an organic functional layer, wherein the organic functional layer is positioned between the anode and the cathode, and the organic functional layer contains the red organic electrophosphorescent platinum complex.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the functional layer containing the organic electroluminescent material is a light-emitting layer.
It is a further object of the present invention to provide an illumination or display device. The organic electroluminescent device can be applied to display elements, so that the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged, and the OLED luminescent device has a good application effect and a good industrialization prospect.
The technical scheme for solving the technical problems is as follows: a lighting or display element comprising an organic electroluminescent device as described above.
The beneficial technical effects of the invention are as follows:
when the red organic electrophosphorescent platinum complex is used as a luminescent layer doping material of an OLED luminescent device, compared with the traditional doped phosphorescent material, the organic electroluminescent material has higher luminous efficiency, lower triplet state service life, narrower spectral half-peak width and good material stability. The metal platinum-containing organic electroluminescent material is applied to OLED devices as a luminescent layer doping material, the luminous efficiency of the devices is greatly improved, the service life of the devices is obviously prolonged, and the metal platinum-containing organic electroluminescent material has unexpected technical effects.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device of the present invention;
in the figure: 1. a substrate layer, 2, an anode layer, 3, a hole injection layer, 4, a hole transport layer, 5, a light emitting layer, 6, an electron transport layer, 7, an electron injection layer, 8 and a cathode electrode layer.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below.
All the raw materials in the following examples were purchased from cigarette Taiwangrun Fine chemical Co., Ltd.
EXAMPLE 1 Synthesis of Compound A1
The chemical reaction route is as follows:
adding 0.01mol of raw material D-1, 0.012mol of raw material C-1 and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 5 multiplied by 10-5molPd2(dba)3，5×10-5mol P(t-Bu)3Heating 0.03mol of potassium tert-butoxide to 105 ℃, carrying out reflux reaction for 24 hours, and sampling a point plate to show that no bromide is left and the reaction is complete; naturally cooling to room temperature, filtering, rotatably evaporating the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain the target product with the HPLC purity of 99.83 percent and the yield of 81.1 percent. Elemental analysis Structure (molecular formula C)59H48N6): theoretical value C, 84.26; h, 5.75; n, 9.99; test values C, 84.27; h, 5.77; and N, 9.98. LC-MS: theoretical value: 840.39, found: 840.41.
the intermediate A-1 is synthesized from the raw material C-1 and the raw material D-1, the preparation method of other intermediate A is similar to that of the intermediate A-1, and the specific structures of the raw material C, the raw material D and the intermediate A used in the invention are shown in Table 1.
TABLE 1
EXAMPLE 2 Synthesis of Compound 1
In a 200ml three-necked flask, 0.01mol of intermediate A-1 and 0.015mol of PtCl were placed2(DMSO)2And 0.02mol of sodium carbonate were added to 50mL of 1, 2-dimethoxyethane, and the mixture was heated under reflux at 130 ℃ for 24 hours to complete the reaction, cooled to room temperature naturally, added with 70mL of water, extracted with dichloromethane, and the organic phase was collected and purified by silica gel column to obtain Compound 1. HPLC purity 99.3%, yield 55.4%. Elemental analysis (formula C)59H46N6Pt): theoretical value C, 68.53; h, 4.48; n, 8.13; pt, 18.86; test values are: c, 68.55; h, 4.50; n, 8.14; pt, 18.87. LC-MS: theoretical value is 1033.34, found 1033.36.
EXAMPLE 3 Synthesis of Compound 5
The synthesis of compound 4 was identical to that of example 2, except thatConsists in replacing intermediate A-1 with intermediate A-2. HPLC purity 99.2%, yield 58.4%. Elemental analysis (formula C)59H46N6Pt): theoretical value C, 68.53; h, 4.48; n, 8.13; pt, 18.86; test values are: c, 68.54; h, 4.49; n, 8.15; pt, 18.87. LC-MS: theoretical value is 1033.34, found 1033.37.
EXAMPLE 4 Synthesis of Compound 4
The synthesis of compound 5 was identical to that of example 2, except that intermediate a-1 was replaced with intermediate a-3. HPLC purity 98.7%, yield 56.9%. Elemental analysis (formula C)59H46N6Pt): theoretical value C, 68.53; h, 4.48; n, 8.13; pt, 18.86; test values are: c, 68.56; h, 4.51; n, 8.16; pt, 18.88. LC-MS: theoretical value is 1033.34, found 1033.35.
EXAMPLE 5 Synthesis of Compound 7
The synthesis of compound 7 was identical to that of example 2, except that intermediate a-1 was replaced with intermediate a-4. HPLC purity 99.6%, yield 60.1%. Elemental analysis (formula C)50H35N5OPt): theoretical value C, 65.49; h, 3.85; n, 7.64; pt, 21.28; test values are: c, 65.51; h, 3.87; n, 7.65; pt, 21.28. LC-MS: theoretical value is 916.25, found 916.27.
EXAMPLE 6 Synthesis of Compound 11
The synthesis of compound 11 was identical to that of example 2, except that intermediate a-1 was replaced with intermediate a-5. HPLC purity 98.6%, yield 57.8%. Elemental analysis (molecular formula)C50H35N5OPt): theoretical value C, 65.49; h, 3.85; n, 7.64; pt, 21.28; test values are: c, 65.51; h, 3.87; n, 7.65; pt, 21.27. LC-MS: theoretical value is 916.25, found 916.26.
EXAMPLE 7 Synthesis of Compound 15
The synthesis of compound 15 was identical to that of example 2, except that intermediate a-1 was replaced with intermediate a-6. HPLC purity 99.4%, yield 55.7%. Elemental analysis (formula C)53H41N5Pt): theoretical value C, 67.50; h, 4.38; n, 7.43; pt, 20.69; test values are: c, 67.52; h, 4.39; n, 7.44; pt, 20.68. LC-MS: theoretical value is 943.03, found 943.05.
EXAMPLE 8 Synthesis of Compound 21
The procedure for the synthesis of compound 21 was identical to that of example 2, except that intermediate A-1 was replaced with intermediate A-7. HPLC purity 99.3%, yield 59.3%. Elemental analysis (formula C)59H46N6OPt): theoretical value C, 67.48; h, 4.42; n, 8.00; pt,18.58 test value: c, 67.48; h, 4.42; n, 8.00; pt, 18.58. LC-MS: theoretical value is 1049.34, found 1049.38.
EXAMPLE 9 Synthesis of Compound 25
The synthesis of compound 25 was identical to that of example 2, except that intermediate a-1 was replaced with intermediate a-8. HPLC purity 99.4%, yield 58.2%. Elemental analysis (formula C)50H35N5O2Pt): theoretical value C, 64.37; h, 3.78; n, 7.51; the amount of Pt is not particularly limited,20.91 test value: c, 64.37; h, 3.78; n, 7.51; pt, 20.91. LC-MS: theoretical value is 932.24, found 932.26.
EXAMPLE 10 Synthesis of Compound 30
The procedure for the synthesis of compound 30 was identical to that of example 2, except that intermediate A-1 was replaced with intermediate A-9. HPLC purity 99.1%, yield 63.7%. Elemental analysis (formula C)53H41N5OPt): theoretical value C, 66.38; h, 4.31; n, 7.30; pt,20.34 test value: c, 66.39; h, 4.33; n, 7.32; pt, 20.35. LC-MS: theoretical value is 932.24, found 932.26.
EXAMPLE 11 Synthesis of Compound 35
The procedure for the synthesis of compound 35 was identical to that of example 2, except that intermediate A-1 was replaced with intermediate A-10. HPLC purity 98.4%, yield 60.5%. Elemental analysis (formula C)62H52N6Pt): theoretical value C, 69.19; h, 4.87; n, 7.81; pt,18.13 test value: c, 69.21; h, 4.88; n, 7.83; pt, 18.15. LC-MS: theoretical value is 1075.39, found 1075.41.
EXAMPLE 12 Synthesis of Compound 52
The procedure for the synthesis of compound 52 was identical to that of example 2, except that intermediate A-1 was replaced with intermediate A-11. HPLC purity 99.0%, yield 58.5%. Elemental analysis (formula C)59H46N6Pt): theoretical value C, 68.53; h, 4.48; n, 8.13; pt,18.86 test value: c, 68.55; h, 4.51; n, 8.14; pt, 18.85. LC-MS: a theoretical value of 1033.34 and an actual value of 1033.37。
EXAMPLE 13 Synthesis of Compound 53
The procedure for the synthesis of compound 53 was identical to that of example 2, except that intermediate A-1 was replaced with intermediate A-12. HPLC purity 99.3%, yield 57.4%. Elemental analysis (formula C)59H46N6Pt): theoretical value C, 68.53; h, 4.48; n, 8.13; pt,18.86 test value: c, 68.54; h, 4.50; n, 8.13; pt, 18.87. LC-MS: theoretical value is 1033.34, found 1033.35.
EXAMPLE 14 Synthesis of Compound 58
The procedure for the synthesis of compound 58 was identical to that of example 2, except that intermediate A-1 was replaced with intermediate A-13. HPLC purity 99.3%, yield 57.4%. Elemental analysis (formula C)50H35N5OPt): theoretical value C, 65.49; h, 3.85; n, 7.64; pt,21.28 test value: c, 65.52; h, 3.87; n, 7.63; pt, 21.27. LC-MS: theoretical value is 916.25, found 916.34.
EXAMPLE 15 Synthesis of Compound 66
The procedure for the synthesis of compound 66 was identical to that of example 2, except that intermediate A-1 was replaced with intermediate A-14. HPLC purity 99.4%, yield 56.1%. Elemental analysis (formula C)53H41N5Pt): theoretical value C, 67.50; h, 4.38; n, 7.43; pt,20.69 test value: c, 67.51; h, 4.40; n, 7.44; pt, 20.69. LC-MS: theoretical value is 943.30, found 943.29.
EXAMPLE 16 Synthesis of Compound 74
The procedure for the synthesis of compound 74 was identical to that of example 2, except that intermediate A-1 was replaced with intermediate A-15. HPLC purity 99.2%, yield 53.5%. Elemental analysis (formula C)50H35N5O2Pt): theoretical value C, 64.37; h, 3.78; n, 7.51; pt,20.91 test value: c, 64.38; h, 3.79; n, 7.50; pt, 20.92. LC-MS: theoretical value is 932.24, found 932.25.
The nmr hydrogen spectra data of the compounds of the examples of the invention are shown in table 2:
TABLE 2
The organic compound of the present invention is used in a light-emitting device as a doping material for a light-emitting layer. The compounds of the present invention were tested for various aspects of HOMO/LUMO energy levels, glass transition temperatures (Tg), decomposition temperatures (Td), etc., as shown in Table 3 below: all standard data and device structures, data references are modified from labels in VS 312. Reference is made to the literature TLEC-025.
TABLE 3
Note: the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the thermogravimetric temperature Td is a temperature at which 1% of the weight loss is observed in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan, and the nitrogen flow rate is 20 mL/min; the highest occupied molecular orbital HOMO energy level is tested by an ionization energy testing system (AC-3) under an atmospheric environment, and the test value is an absolute value. The LUMO energy level is the absolute value of the energy at the longest wavelength (Eg) of the ultraviolet absorption spectrum of a material minus the HOMO energy level. The cyclic voltammetry test adopts CS350H electrochemical workstation of Costet instruments Co., Ltd, tetrabutyl hexafluorophosphate is used as electrolyte and is dissolved into dichloromethane solution; the scanning speed is 100 mv/s.
As can be seen from the data in the table, compared with the conventional red light doping material TLEC-025, the compound of the invention has higher glass transition temperature and decomposition temperature; and has good reversible redox characteristics. The luminescent layer is used as a doping material of the luminescent layer, and can inhibit the crystallization and the film phase separation of the material; meanwhile, the decomposition of the material under high brightness can be inhibited, and the service life of the device is prolonged. In addition, the compound has a lower HOMO energy level, and is doped in a host material as a doping material, so that generation of carrier traps is inhibited, energy transfer efficiency of a host and an object is improved, and luminous efficiency of a device is improved.
To further illustrate the excellent properties of the materials of the present invention, a comparison was made between the fluorescence quantum efficiency (PLYQ) (doped in the host CBP with a doping concentration of 6% of the total mass, full width at half maximum (FWHM), lowest triplet state (T1) lifetime and thermal stability of the materials.
The detailed results are shown in table 4 below:
all standard data and device structures, data references are modified from labels in VS 312. Reference is made to the literature TLEC-025.
TABLE 4
Note: testing by adopting a Fluorolog-3 series fluorescence spectrometer of Horiba under the condition that the triplet state energy level is in a thin film state; the fluorescence quantum efficiency is that the material is co-evaporated on a high-transmittance quartz glass sheet through double sources, the concentration of the doped material is 6 percent of the total mass, the film thickness is 60nm, and a Horiba Fluorolog-3 series fluorescence spectrometer (integrating sphere) is adopted for testing; the full width at half maximum (FWHM) of the spectrum is that the material is co-evaporated on a high-transmittance quartz glass sheet through double sources, the concentration of the doped material is 6 percent of the total mass, the film thickness is 60nm, and the material is tested by adopting a Fluorolog-3 series fluorescence spectrometer of Horiba; the triplet state lifetime τ was tested using a Fluorolog-3 series fluorescence spectrometer from Horiba; the thermal stability is the temperature at which the material is heated in a vacuum (10-4pa) to 1% decomposition of the material.
As can be seen from Table 4, the compound of the invention has higher fluorescence quantum efficiency as a doping material, and the fluorescence quantum efficiency of part of the materials is close to 100%, which shows that the compound of the invention has higher triplet state radiation rate and lower triplet state non-radiation rate; meanwhile, the spectrum FWHM of the material is narrow, so that the color gamut of the device can be effectively improved, and the luminous efficiency of the device is improved; the triplet state life of the material is 1-3.5 us, the triplet state-triplet state quenching effect can be effectively inhibited, the luminous efficiency of a device is improved, and the service life of the device is prolonged.
And finally, the evaporation decomposition temperature of the material is higher, so that the evaporation decomposition of the material can be inhibited, and the service life of the device is effectively prolonged.
Spin orbit coupling coefficient (SOC), radiation rate and non-radiation rate of the triplet-ground state (T1-S0) of the material were calculated as shown in table 5 below:
all standard data and device structures, data references are modified from labels in VS 312. Reference is made to the literature TLEC-025.
TABLE 5
From the above table, it can be seen that the compound of the present application has a large SOC coefficient, and the triplet state is easily transited to the ground state by the spin-orbit coupling effect, and emits phosphorescence. Meanwhile, the luminescent material has higher radiation rate and lower non-radiation rate, thereby ensuring that the luminescent material can improve the luminous efficiency when being used as a luminescent layer doping material.
The OLED device is manufactured, the driving voltage, the efficiency and the service life of the OLED device are tested, and the material is comprehensively evaluated.
Preparation of the organic electroluminescent device of the present invention
The effect of the synthesized compound of the present invention as a doping material for a light emitting layer in a device is explained in detail by device examples 1 to 23 and device comparative example 1 below. Device examples 2-23 and device comparative example 1 compared with device example 1, the manufacturing process of the device is completely the same, and the same substrate material and electrode material are adopted, and the film thickness of the electrode material is kept consistent. Except that the doping material of the light emitting layer was changed. The structural composition of the resulting device of each example is shown in table 6. The test results of the resulting devices are shown in table 7.
Device example 1
Cleaning an ITO anode layer 2 on a transparent glass substrate layer 1, respectively ultrasonically cleaning the ITO anode layer 2 with deionized water, acetone and ethanol for 30 minutes, and then treating the ITO anode layer 2 in a plasma cleaner for 2 minutes; drying an ITO glass substrate, spin-coating PEDOT (PSS) with the thickness of 30nm by a wet method, taking the layer as a hole injection layer 3, drying, placing in a vacuum cavity, and keeping the vacuum degree to be less than 1 multiplied by 10- 6Torr, depositing α -NPD with a film thickness of 40nm on the hole injection layer 3 as a hole transport layer 4; further, a 35nm light-emitting layer 5 was evaporated, wherein the light-emitting layer included a host material Bebq2 and a guest dopant material of the compound 1 of the present invention, the dopant material was 6% by mass, the specific material was selected as shown in table 5, and the rate control was performed by a film thickness meter according to the mass percentages of the host material and the dopant dye; further evaporating a TPBI layer of organic material with the thickness of 35nm on the light-emitting layer 5 to form an electron transport layer 6; vacuum evaporating LiF with the thickness of 1nm on the electron transport layer 6, wherein the layer is an electron injection layer 7; vacuum evaporating cathode Al (100nm) on electron injection layer 7 as cathodeA pole layer 8. Example 1 relates to the prior material structure as shown below:
examples 2 to 23 and comparative example 1 were completely identical to example 1 except that the doping material of the light emitting layer was changed.
The device structures of examples 1-23 and comparative example 1 are shown in table 6 below: all standard data and device structures, data references are modified from labels in VS 312. Reference is made to the literature TLEC-025.
TABLE 6
After the OLED light emitting device was completed as described above, the anode and cathode were connected by a known driving circuit, and the driving voltage, current efficiency, and lifetime of the device were measured.
All standard data and device structures, data references are modified from labels in VS 312. Reference is made to the literature TLEC-025.
TABLE 7
External quantum efficiencyFor a device luminance of 1000cd/m2Test values in the case tested using the IVL (current-voltage-brightness) test system (frarda scientific instruments ltd, su); LT80 refers to a device luminance of 1000cd/m2The time taken for the luminance of the device to decay to 80% in the case; the life test system is an EAS-62C type OLED device life tester of Japan System research company.
From the results in table 7, it can be seen that the compound of the present invention can be applied to the fabrication of an OLED light emitting device, and compared to comparative example 1, the current efficiency, external quantum efficiency and device lifetime of the device are greatly improved at the same current density.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A red organic electrophosphorescent platinum complex is characterized in that: the general structure of the platinum complex is shown as a general formula (1):
in the general formula (1), X, X0And X1Each independently represents a single bond, -O-, -S-, -C (R)7)(R8) -or-N (R)9)-；
a. b and c represent 0 or 1, and a + b + c is more than or equal to 1;
R1-R6each independently represents a structure represented by the general formula (2) or the general formula (3), and R1-R6May also be represented by a hydrogen atom, said R1-R6At least one of the structures is represented by the general formula (2);
in the general formula (2), X2And X3Each independently represents a single bond, -O-, -S-, -C (R)10)(R11) -or-N (R)12) -, and not simultaneously represent a single bond;
Zieach independently being represented by a nitrogen atom or C-AiWherein i represents 1 to 31; a. theiSelected from hydrogen, halogen, cyano, C1-10Alkyl of (C)2-20Substituted or unsubstituted aryl having 6 to 30 ring atoms, substituted or unsubstituted heteroaryl having 5 to 30 ring atoms, wherein two or more A's are adjacentiMay be bonded to each other to form a ring;
R7-R12independently selected from C1-10Substituted or unsubstituted aryl having 6 to 30 ring atoms, substituted or unsubstituted heteroaryl having 5 to 30 ring atoms;
the general formula (2) and the general formula (3) are respectively and independently bonded with the adjacent sites marked by the letters in the general formula (1) in a ring-bond mode through two adjacent sites marked by the letters; z at adjacent sitesi(i ═ 1 to 23) represents a C atom;
the substituent for substituting the above-mentioned substitutable group is optionally selected from deuterium, halogen, cyano, C1-20Alkyl of (C)2-20Alkenyl of (a), aryl having 6 to 30 ring atoms, heteroaryl containing 5-30 ring atoms;
the heteroatom in the heteroaryl is any one or more selected from N, O or S.
2. The platinum complex according to claim 1, characterized in that: in the general formula (1), R7-R12Each independently represents any one of a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dimethylfluorenyl group, and a substituted or unsubstituted dimethylazazinyl group;
Airepresented by hydrogen atom, halogen, cyano, methyl, ethyl, isopropyl, tert-butyl, substituted orAny one of an unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dimethylfluorenyl group, and a substituted or unsubstituted dimethylazazinyl group; wherein two or more A are adjacentiMay be bonded to each other to form a ring;
the substituent for substituting the above-mentioned substitutable group is optionally selected from deuterium, halogen, cyano, methyl, ethyl, isopropyl, tert-butyl.
3. The platinum complex according to claim 1, characterized in that: the platinum complex is selected from compounds shown as a general formula (1-2) or a general formula (1-3):
4. the platinum complex according to claim 1, wherein the platinum complex is selected from the group consisting of compounds represented by general formulae (1-4) to (1-8):
5. the platinum complex according to any one of claims 1 to 4, wherein R is1-R5At least one of the structures is represented by a general formula (2) or a general formula (3).
6. The platinum complex of claim 5, wherein X is1Is represented by a single bond.
7. The platinum complex according to claim 1, wherein the platinum complex is any one of the following structures:
8. an organic electroluminescent device comprising a cathode, an anode and an organic functional layer, said organic functional layer being located between said cathode and anode, characterized in that: the organic functional layer comprises the platinum complex according to any one of claims 1 to 7.
9. The organic electroluminescent device according to claim 8, wherein the organic functional layer comprises a light-emitting layer, characterized in that: the light-emitting layer contains the platinum complex according to any one of claims 1 to 7.
10. An illumination or display element, characterized in that: comprising an organic electroluminescent device as claimed in any one of claims 8 to 9.
Priority Applications (1)
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| CN109970801A (en) * | 2017-12-27 | 2019-07-05 | 江苏三月光电科技有限公司 | A kind of complex and its application containing metal iridium |
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