WO2018107841A1 - 一种磷光PtAg2配合物及其制备方法和用途 - Google Patents

一种磷光PtAg2配合物及其制备方法和用途 Download PDF

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WO2018107841A1
WO2018107841A1 PCT/CN2017/102504 CN2017102504W WO2018107841A1 WO 2018107841 A1 WO2018107841 A1 WO 2018107841A1 CN 2017102504 W CN2017102504 W CN 2017102504W WO 2018107841 A1 WO2018107841 A1 WO 2018107841A1
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formula
complex
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phosphorescent
alkyl
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陈忠宁
舒辉星
王金云
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Fujian Institute of Research on the Structure of Matter of CAS
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Fujian Institute of Research on the Structure of Matter of CAS
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Priority to KR1020197018716A priority patent/KR102527776B1/ko
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Definitions

  • the invention belongs to the field of organic electroluminescence and can be applied to the field of color flat panel display and illumination. Specifically, it relates to a PtAg 2 (meso-/rac-dpmppe) heterotrinuclear metal organic alkyne complex for preparing an organic light emitting diode.
  • PtAg 2 meso-/rac-dpmppe
  • Organic electroluminescence is a phenomenon in which organic light-emitting diodes (OLEDs) directly convert electrical energy into light energy under the action of a low DC voltage of 3-12V. It has a very wide application in the field of flat panel display and illumination. Compared with traditional lighting and display technology, organic electroluminescence has many advantages such as full color display, wide viewing angle, high definition, fast response, low power consumption, low temperature resistance, etc.; and organic light-emitting device has simple structure, ultra-light, ultra-thin Excellent characteristics such as flexible folding.
  • OLEDs organic light-emitting diodes
  • the core of the organic light-emitting diode is a light-emitting film material.
  • most of the phosphorescent materials used in commercial organic electroluminescent devices are electrically neutral ring metal ruthenium (III) complexes, which are doped into an organic host material to form a light-emitting layer. Its biggest advantage is that it is convenient for vacuum thermal evaporation to produce an ideal thin film luminescent layer.
  • the equipment required for vacuum evaporation is expensive, and in particular, the process for preparing an organic doped luminescent film layer is complicated, which greatly limits the industrial development and commercial application of the organic light emitting diode in large-area full-color display.
  • ionic phosphorescent organometallic compounds with high quantum efficiency as a luminescent material is a viable alternative.
  • electro-neutral compounds ionic phosphorescent metal complexes are simpler, cheaper, more stable, and soluble in organic solvents. They are suitable for large-area solution spin coating or inkjet printing to form films. Device preparation costs.
  • Another object of the present invention is to provide a luminescent material containing the above ionic phosphorescent metal complex and use these luminescent materials to prepare a high performance organic light emitting diode.
  • R may be the same or different and are independently selected from the group consisting of alkyl, aryl, heteroaryl, heteroaryl aryl,
  • R' may be the same or different and are independently selected from the group consisting of an alkyl group, an aryl group, and a heteroaryl group;
  • alkyl, aryl, heteroaryl group may be substituted by one or more substituents selected from the group consisting of alkyl, alkenyl, alkynyl, alkoxy, amino, halogen, haloalkyl, Aryl;
  • X is selected from halogen
  • a m-, A n- is a monovalent or divalent anion, m or n is 1, 2, for example the anion ClO 4 -, PF 6 -, SbF 6 -, BF 4 -, SiF 6 2- and the like.
  • ⁇ stands for bridging.
  • the complex of formula (I) is a racemic structure and the complex of formula (II) is a meso structure.
  • the stereostructure of the phosphorescent metal complex of formula (I) or formula (II) is as follows:
  • the alkyl group means a straight or branched alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
  • the alkenyl group represents a linear or branched alkenyl group having 2 to 6 carbon atoms, for example, ethylene, propylene, butylene or the like.
  • the alkynyl group represents a linear or branched alkynyl group having 2 to 6 carbon atoms, for example, acetylene, propyne, butyne or the like.
  • the aryl group means a monocyclic, polycyclic aromatic group having 6 to 20 carbon atoms, and representative aryl groups include a phenyl group, a naphthyl group and the like.
  • the heteroaryl group means a monocyclic or polycyclic heteroaromatic group having 1 to 20 carbon atoms and comprising at least 1, preferably 1 to 4, hetero atoms selected from N, S, O, representative Heteroaryl groups include: pyrrolyl, pyridyl, pyrimidinyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, oxazolyl, quinolyl, quinazolinyl, fluorenyl, phenothiazine Base.
  • the A m- or A n- is preferably ClO 4 - , PF 6 - , SiF 6 2- or the like, and m/n is 1, 2.
  • the R is preferably an aryl group, a carbazolyl group, a phenothiazine group or a carbazolylaryl group.
  • the aryl, oxazolyl, phenothiazine group may be optionally substituted by one or more substituents selected from the group consisting of alkyl, alkoxy, amino, halogen, haloalkyl, aryl;
  • R' is preferably an aryl group, a nitrogen-containing heterocyclic ring (for example, a carbazolyl group), and the aryl group or the nitrogen-containing heterocyclic ring may be optionally substituted by one or more substituents selected from the group consisting of an alkyl group and an alkane.
  • R is phenyl, alkyl-phenyl, haloalkyl-phenyl, carbazolyl-phenyl, oxazolyl, alkyl-carbazolyl, phenyl-carbazolyl, phenothiazine Alkyl-phenothiazine; R' is phenyl, alkylphenyl, oxazolyl, alkyl-carbazolyl, phenyl-carbazolyl.
  • the specific structure of the ionic phosphorescent metal complex is preferably as follows:
  • the invention also provides a preparation method of the phosphorescent complex of the formula (I), comprising the following steps: 1) rac-(PPh 2 CH 2 PPhCH 2 -) 2 and Pt(PPh 3 ) 2 (C ⁇ CR 2 is reacted in a solvent to obtain an intermediate; 2) the intermediate obtained in the step 1) is further reacted with [Ag(tht)](A n- ) and PR' 3 in a solvent to obtain the formula (I) ) Phosphorescent complexes.
  • the tht tetrahydrothiophene
  • the A n- , R, R′, and X are as defined above.
  • the invention also provides a preparation method of the phosphorescent complex of the formula (II), comprising the steps of: A) meso-(PPh 2 CH 2 PPhCH 2 -) 2 and Pt(PPh 3 ) 2 (C ⁇ CR 2 ) reacting in a solvent to obtain an intermediate; B) reacting PR' 3 , n Bu 4 NX, [Ag(tht)] (A m- ) with the intermediate obtained in the step A) in a solvent to obtain Said (II) phosphorescent complex.
  • the tht tetrahydrothiophene
  • the A m- , R, R′, and X are as defined above.
  • the solvent is preferably a halogenated hydrocarbon such as dichloromethane.
  • the intermediate obtained by the reaction is concentrated and recrystallized.
  • the solvent is preferably a halogenated hydrocarbon such as dichloromethane.
  • PR' 3 and n Bu 4 NX are first mixed, and then the mixed solution and [Ag(tht)] (A m- ) are added to the middle obtained by dissolving the above step A). In the solution of the body.
  • the molar ratio of 3 is from 1 to 1.5:1 to 1.5:2 to 3:2 to 3, preferably the molar ratio is 1:1:2:2; meso-(PPh 2 CH 2 PPhCH 2 -) 2 :Pt(PPh 3 2 (C ⁇ CR) 2 : [Ag(tht)](A m- ): n Bu 4 NX: PR' 3 molar ratio is 1 to 1.5:1 to 1.5:2 to 3:1 to 1.5:1 ⁇ 1.5, preferably the molar ratio is 1:1:2:1:1.
  • the reactions are all carried out at room temperature.
  • it is purified by silica gel column chromatography.
  • the phosphorescent complex of the formula (I) or the formula (II) according to the invention has strong phosphorescence emission in both solid and film, and the phosphorescence quantum yield is higher than 50% in the film; and the color distribution of the emitted light is wide. From sky blue to orange red. Therefore, it can be used as a light-emitting layer dopant for the preparation of an organic light-emitting diode.
  • the invention also provides the use of the phosphorescent complex for organic light emitting diodes.
  • the present invention provides an organic light emitting diode comprising a light emitting layer, wherein the light emitting layer contains the phosphorescent complex of the formula (I) or (II) according to the present invention.
  • the phosphorescent complex of the formula (I) according to the present invention preferably accounts for 3-20% by weight, more preferably 5-10%, of all materials, and further preferably, the present invention
  • the phosphorescent complex of the formula (I) is doped into the host material as a light-emitting layer in a weight percentage of 6%;
  • the phosphorescent complex of the formula (II) according to the invention preferably accounts for 5-25% by weight of all materials (% by weight) More preferably, it is 8-15%, and further preferably, the phosphorescent complex of the formula (II) according to the present invention is doped into the host material as a light-emitting layer at a weight percentage of 10%.
  • the structure of the organic light emitting diode can be various structures known in the art.
  • the anode layer, the hole injection layer, optionally the hole transport layer, the light-emitting layer, the electron transport layer, the electron injection layer, and the cathode layer are included.
  • the organic light emitting diode further includes a substrate (eg, a glass substrate).
  • the hole transport layer may be CuSCN, CuI, CuBr.
  • the light-emitting layer contains the phosphorescent complex of the present invention, and a substance having a hole transporting property and/or a substance having an electron transporting property.
  • the substance having a hole transporting property may be 2,6-DCZPPY (2,6-bis(3-(9-carbazole)phenyl)pyridine), mCP (1,3-bis(9-carbazolyl) a kind of benzene), CBP (4,4'-bis(9-carbazole)-1,1'-biphenyl), or TCTA (tris(4-(9-carbazole)phenyl)amine) Or a variety.
  • the substance having electron transporting property may be OXD-7 (1,3-bis(5-(4-(tert-butyl)phenyl)-1,3,4-oxadiazol-2-yl)benzene);
  • the electron transport layer may be BmPyPB(3,3",5,5"-tetrakis(3-pyridyl)-1,1':3',1"-terphenyl), TPBi (1,3,5-three) (1-phenyl-1H-benzo[d]imidazol-2-yl)benzene), BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) or OXD One or more of -7; the electron injecting layer is LiF, and the cathode is Al.
  • the device structure containing the phosphorescent complex of the formula (I) is preferably: ITO/PEDOT: PSS (50 nm) / CuSCN (30 nm) / 70.5% 2, 6-DCZPPY: 23.5% OXD-7: 6% Wt
  • Formula (I) complex (50 nm) / BmPyPB (50 nm) / LiF (1 nm) / Al (100 nm), or ITO / PEDOT: PSS (50 nm) / 70.5% mCP: 23.5% OXD-7: 6% Wt
  • the complex of the formula (I) of the present invention (50 nm) / BmPyPB (50 nm) / LiF (1 nm) / Al (100 nm);
  • the device structure containing the phosphorescent complex of the formula (II) is preferably: ITO / PEDOT: PSS ( 50 nm) / CuSCN (30 nm) / 90% 2,
  • ITO is an indium tin oxide conductive film
  • PEDOT:PSS is poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid)
  • 2,6-DCZPPY is (2,6-di(3-) (9-carbazolyl)phenyl)pyridine)
  • mCP is (1,3-bis(9-carbazolyl)benzene)
  • OXD-7 is 1,3-bis(5-(4-(tert-butyl) Phenyl)-1,3,4-oxadiazol-2-yl)benzene
  • BmPyPB is (3,3",5,5"-tetrakis(3-pyridyl)-1,1':3', 1"-terphenyl).
  • the invention also provides a method for preparing the organic light emitting diode, comprising: 1) preparing a hole injection layer in an organic light emitting diode on a anode by a solution method; 2) optionally preparing an organic light emitting diode by a solution method; a hole transport layer; 3) preparing a light-emitting layer doped with the phosphorescent complex of the present invention by a solution method; 4) preparing an electron transport layer, an electron injection layer, and a cathode layer by a vacuum thermal evaporation method in this order.
  • the method comprises: first preparing a hole injection layer using water-soluble PEDOT:PSS; secondly, using a diethyl sulfide solution of cuprous cyanide cyanide Preparing a hole transport layer; using 2,6-DCZPPY having hole transporting property and OXD-7 having electron transporting property as a mixed host material, and doping with the phosphorescent complex of the formula (I) according to the present invention to prepare luminescence a Bmpypb electron transport layer, a LiF electron injection layer, and an Al cathode layer are sequentially prepared by a vacuum thermal evaporation method; for the phosphorescent complex of the formula (II), the method comprises: first using a water-soluble PEDOT:PSS Preparing a hole injection layer; secondly, preparing a hole transport layer by using a solution of copper thiocyanate in diethyl sulfide; and further utilizing the phosphorescence of the
  • a PEDOT:PSS hole injection layer, a 2,6-DCZPPY:OXD-7 or a 2,6-DCZPPY doped luminescent layer is respectively prepared by a solution spin coating method, and a BmPyPB electron transport layer is used.
  • the film was prepared by vacuum thermal evaporation using a LiF electron injection layer.
  • the organic light emitting diode prepared from the phosphorescent complex of the present invention has excellent performance and has high electro-optical conversion efficiency.
  • the invention further provides for the use of the organic light emitting diode, which can be used in the field of flat panel display and everyday illumination.
  • the present invention has the following advantages:
  • the phosphorescent complex of the present invention has strong phosphorescence emission in both solid and film, and the quantum efficiency of thin film phosphorescence is higher than 50% or even as high as 90%;
  • the present invention utilizes a phosphorescent Pt-Ag heterometallic complex for the first time to assemble an organic light-emitting device as a light-emitting material, and the organic light-emitting diode prepared by using the phosphorescent complex of the present invention as a light-emitting layer dopant has high electroluminescence external quantum conversion efficiency;
  • the present invention utilizes an orthogonal solution method to prepare a hole injection layer and a light-emitting layer of an organic light-emitting diode, which can greatly reduce device fabrication costs;
  • the ligand of the phosphorescent complex of the present invention has an internal/external racemic different configuration, and the electroluminescence changes from sky blue to orange red, and the luminous efficiency of each color is high.
  • Figure 1 is a schematic view of the structure of the device and the chemical structure of the organic material.
  • dpmppe represents (PPh 2 CH 2 PPhCH 2 -) 2
  • carb represents carbazolyl
  • PhBu t -4 represents 4-tert-butyl-phenyl
  • 9-Ph-carb-3 represents 9-benzene.
  • Base-carbazol-3-yl 9-Et-carb-3 represents 9-ethylcarbazol-3-yl
  • PhCF 3 -4 represents 4-trifluoromethyl-phenyl
  • 9-(4-Ph) -carb represents 9-(4-phenyl)-carbazolyl
  • 10-Et-PTZ-3 represents 10-ethylphenothiazine-3-yl
  • tht is tetrahydrothiophene.
  • Example 1 Complex [PtAg 2 (rac-dpmppe) (C ⁇ CC 6 H 4 Bu t -4) 2 ⁇ PhP(9-Ph-carb-3) 2 ⁇ 2 ](ClO 4 ) 2 (rac- 1) Preparation
  • Example 2 Preparation of complex [PtAg 2 (rac-dpmppe) ⁇ (C ⁇ C-4) C 6 H 4 -carb-9 ⁇ 2 (PPh 3 ) 2 ](ClO 4 ) 2 (rac-2)
  • the preparation method is basically the same as that in Example 1, except that Pt(PPh 3 ) 2 ⁇ (C ⁇ C-4)C 6 H 4 -carb-9 ⁇ 2 is used instead of Pt(PPh 3 ) 2 (C ⁇ CC 6 H 4 Bu t -4) 2 , PPh 3 replaces PhP(9-Ph-carb-3) 2 . Yield: 71%. Calcd for C 116 H 92 Ag 2 Cl 2 N 2 O 8 P 6 Pt: C, 60.33; H, 4.02; N, 1.21. Measured: C, 60.12; H, 4.02; N, 1.15. Spray mass spectrum m/z (%): 1055.1713 (100%, [M-2ClO 4 ] 2+ ).
  • Example 3 Preparation of complex [PtAg 2 (rac-dpmppe) ⁇ C ⁇ C-(9-Ph-carb-3) ⁇ 2 (PPh 3 ) 2 ](ClO 4 ) 2 (rac-3)
  • the preparation method is basically the same as that in Example 1, except that Pt(PPh 3 ) 2 (C ⁇ C-(9-Ph-carb-3)) 2 is used instead of Pt(PPh 3 ) 2 (C ⁇ CC 6 H 4 ). Bu t -4) 2 , PPh 3 replaces PhP(9-Ph-carb-3) 2 . Yield: 71%. Calcd for C 116 H 92 Ag 2 Cl 2 N 2 O 8 P 6 Pt: C, 60.33; H, 4.02; N, 1.21. Measured: C, 60.10; H, 4.05; N, 1.16. Spray mass spectrum m/z (%): 1055.1717 (100%, [M-2ClO 4 ] 2+ ).
  • the preparation method is basically the same as that in Example 1, except that Pt(PPh 3 ) 2 ⁇ C ⁇ C-(9-Ph-carb-3) ⁇ 2 is used instead of Pt(PPh 3 ) 2 (C ⁇ CC 6 H 4 ).
  • -Bu t -4) 2 P(9-Et-carb-3) 3 replaces PhP(9-Ph-carb-3) 2 .
  • Elemental analysis (C 164 H 134 Ag 2 Cl 2 N 8 O 8 P 6 Pt): C, 65.39; H, 4.48; N, 3.72. Measured: C, 65.14; H, 4.53; N, 3.53.
  • the preparation method is basically the same as that in Example 1, except that Pt(PPh 3 ) 2 ⁇ C ⁇ C-(9-Et-carb-3) ⁇ 2 is used instead of Pt(PPh 3 ) 2 (C ⁇ CC 6 H 4 ).
  • Bu t -4) 2 , P(9-Et-carb-3) 3 replaces PhP(9-Ph-carb-3) 2 .
  • Elemental analysis (C 156 H 134 Ag 2 Cl 2 N 8 O 8 P 6 Pt) Calcd: C, 64.25; H, 4.63 ; N, 3.84 measured values: C, 64.02; H, 4.65 ; N, 3.58 electrically.
  • Example 6 Complex [PtAg 2 (rac-dpmppe) ⁇ C ⁇ C-(10-Et-PTZ-3) ⁇ 2 ⁇ P(9-Et-carb-3) 3 ⁇ 2 ](ClO 4 ) 2 Preparation of (rac-6).
  • the preparation method is basically the same as that in Example 1, except that Pt(PPh 3 ) 2 ⁇ C ⁇ C-(10-Et-PTZ-3) ⁇ 2 is used instead of Pt(PPh 3 ) 2 (C ⁇ CC 6 H 4 ).
  • Bu t -4) 2 , P(9-Et-carb-3) 3 replaces PhP(9-Ph-carb-3) 2 .
  • Elemental analysis (C 156 H 134 Ag 2 Cl 2 N 8 O 8 P 6 PtS 2 ): C, 62.86; H, 4.53; N, 3.76. Measured: C, 62.62; H, 4.57; N, 3.59.
  • Example 7 [Cl PtAg 2 (meso -dpmppe) (C ⁇ CC 6 H 4 CF 3 -4) 2 (PPh 3)] (ClO 4) (meso-7) with the preparations.
  • Example 8 Preparation of complex [PtAg 2 (meso-dpmppe) (C ⁇ CC 6 H 4 Bu t -4) 2 (PPh 3 )Cl](ClO 4 ) (meso-8).
  • the preparation method is basically the same as that in Example 7, except that Pt(PPh 3 ) 2 (C ⁇ CC 6 H 4 Bu t -4) 2 is used instead of Pt(PPh 3 ) 2 (C ⁇ CC 6 H 4 CF 3 - 4) 2 .
  • Elemental analysis C 82 H 79 Ag 2 Cl 2 O 4 P 5 Pt: C, 55.80; H, 4.51. Measured: C, 56.02; H, 4.74.
  • Infrared spectrum (KBr, cm -1 ): 2092w (C ⁇ C), 1093s (ClO 4 - ).
  • Example 9 Complex [PtAg 2 (meso-dpmppe) (C ⁇ CC 6 H 4 Bu t -4) 2 ⁇ P(9-Et-carb-3) 3 ⁇ Cl](ClO 4 )(meso-9 Preparation of).
  • the preparation method is basically the same as that in Example 7, except that Pt(PPh 3 ) 2 (C ⁇ CC 6 H 4 Bu t -4) 2 is used instead of Pt(PPh 3 ) 2 (C ⁇ CC 6 H 4 CF 3 - 4) 2 , P(9-Et-carb-3) 3 replaces PPh 3 .
  • Elemental analysis (C 106 H 100 Ag 2 Cl 2 N 3 O 4 P 5 Pt): C, 60.15; H, 4.76; N, 1.99. Measured: C, 60.32; H, 4.73; N, 1.88.
  • Example 10 Complex [PtAg 2 (meso-dpmppe) (C ⁇ CC 6 H 4 Bu t -4) 2 ⁇ P(9-Et-carb-3) 3 ⁇ I](ClO 4 )(meso-10 Preparation of).
  • the preparation method is basically the same as that in Example 7, except that Pt(PPh 3 ) 2 (C ⁇ CC 6 H 4 Bu t -4) 2 is used instead of Pt(PPh 3 ) 2 (C ⁇ CC 6 H 4 CF 3 - 4) 2 , P(9-Et-carb-3) 3 replaces PPh 3 , n Bu 4 NI instead of n Bu 4 NCl. Yield: 72%. Elemental analysis (C 106 H 100 Ag 2 ClIN 3 O 4 P 5 Pt) Calcd: C, 57.66; H, 4.56 ; N, 1.90 measured values:. C, 57.57; H, 4.60; N, 1.83 electrospray mass spectrometry.
  • Example 11 Complex [PtAg 2 (meso-dpmppe) (C ⁇ C-(10-Et-PTZ-3)) 2 ⁇ P(9-Et-carb-3) 3 ⁇ ( ⁇ -I)]( Preparation of ClO 4 ) (meso-11).
  • the preparation method is basically the same as that in Example 7, except that Pt(PPh 3 ) 2 ⁇ C ⁇ C-(10-Et-PTZ-3) ⁇ 2 is used instead of Pt(PPh 3 ) 2 (C ⁇ CC 6 H 4 ).
  • Calcd for C 114 H 98 Ag 2 ClIN 5 O 4 P 5 PtS 2 C, 57.19; H, 4.13; N, 2.93. Measured: C, 57.42; H, 4.33; N, 2.84.
  • the complexes rac-1, rac-4, rac-5, rac-6 prepared in Examples 1, 4, 5, and 6 were tested on a Edinburgh FLS920 fluorescence spectrometer in solid powder and 70.5% 2,6-DCZPPY: 23.5.
  • %OXD-7 6% of the complex rac-1, 4, 5, or 6 (by weight) film of the present invention and the complex meso-11 prepared in Example 11 in solid powder and 90% 2,6-DCZPPY : 10% of the excitation spectrum, emission spectrum, luminescence lifetime and luminescence quantum yield in the meso-11 (weight ratio) film of the present invention.
  • the luminescence quantum yield of the solid powder sample was measured using an integrating sphere having a diameter of 142 mm.
  • the solid state emission wavelength and quantum yield of the complex rac-1, rac-4, rac-5, rac-6, or meso-11 were 500 nm and 15.1% (rac-1), 566 nm, and 37.1%, respectively (rac- 4), 580 nm and 30.4% (rac-5), 662 nm and 1.7% (rac-6), 600 nm and 8.1% (meso-11);
  • Example 13 Preparation and electroluminescence performance testing of organic light emitting diode devices
  • the device structure is: ITO/PEDOT: PSS (50 nm) / CuSCN ( 30 nm) / 90% 2, 6-DCZPPY: 10% of the complex of the present invention meso-11 (50 nm) / Bmpypb (50 nm) / LiF (1 nm) / Al (100 nm).
  • the ITO substrate was first washed with deionized water, acetone, and isopropanol, and then treated with UV-ozone for 15 minutes.
  • the filtered PEDOT:PSS aqueous solution was spin-coated on an ITO substrate at 4,800 rpm on a spin coater, and dried at 140 ° C for 20 minutes to obtain a 50 nm-thick hole injection layer.
  • a solution of CuSCN in diethyl sulfide (10 mg/mL) was spin-coated at a rate of 4,800 rpm to a PEDOT:PSS hole injection layer, and after drying at 120 ° C for 30 minutes, a hole transport layer having a thickness of 30 nm was obtained.
  • the filtered concentration was 7.0 mg/mL of 70.5% 2,6-DCZPPY: 23.5% XD-7: 6% of the complex of the present invention rac-1, rac-4, rac-5, or rac. -6 (% by weight) or 5.5 mg/mL of 90% 2,6-DCZPPY: 10% of the complex meso-11 (% by weight) of the dichloromethane solution was spin-coated to PEDOT at 2100 rpm: A light-emitting layer having a thickness of 50 nm was formed on the PSS film.
  • the ITO substrate was placed in a vacuum chamber having a vacuum of not less than 4 ⁇ 10 -4 Pa, and a 50 nm thick Bmpypb, a 1 nm thick LiF electron injection layer, and a 100 nm thick Al were sequentially thermally deposited as device cathodes.
  • Electroluminescence performance parameters include electroluminescence wavelength ( ⁇ EL ), ignition voltage (V on ), maximum luminance (L max ), maximum current efficiency (CE max ), maximum power efficiency (PE max ), maximum external quantum efficiency (EQE max ) is listed in Table 1.

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Abstract

本发明涉及一种具有消旋结构的离子型磷光金属配合物及其制备方法和用途，所述配合物的结构为：[PtAg2{rac-(PPh2CH2PPhCH2-)2}(C≡CR)2(PR'3)2]2+An- 2/n或[PtAg2{meso-(PPh2CH2PPhCH2-)2}(C≡CR)2(PR'3)(μ-X)]+ mAm-，其中，R可相同或不同，独立地选自：烷基、芳基、杂芳基、杂芳基芳基，R'可相同或不同，独立地选自：烷基、芳基、杂芳基；所述的烷基、芳基、杂芳基均可被一个或多个取代基取代，所述取代基选自烷基、烯基、炔基、烷氧基、氨基、卤素、卤烷基、芳基；X选自卤素；Am-、An-为一价或二价阴离子，m或n为1、2。本发明还涉及一种有机发光二极管及其制备方法和用途，以本发明所述的磷光金属配合物为发光层掺杂体，制备得到的有机发光二极管，具有高性能的有机电致发光，可应用于平板显示。

Description

一种磷光PtAg2配合物及其制备方法和用途 技术领域
本发明属于有机电致发光领域，可应用于彩色平板显示和照明领域。具体涉及一种PtAg2(meso-/rac-dpmppe)异三核金属有机炔配合物用于制备有机发光二极管。
背景技术
有机电致发光是有机发光二极管(OLED)在3-12V低直流电压作用下将电能直接转化为光能的发光现象，它在平板显示和照明领域具有非常广阔的应用。与传统照明和显示技术相比，有机电致发光具有全彩色显示、广视角、高清晰、快速响应、低功耗、耐低温等诸多优点；而且有机发光器件具有结构简单、超轻、超薄、柔性可折叠等优异特性。
有机发光二极管的核心是发光薄膜材料，目前商用有机电致发光器件所用的磷光材料绝大多数是电中性环金属铱(III)配合物，将其掺杂于有机主体材料中组成发光层，其最大优势是便于真空热蒸镀制作理想的薄膜发光层。然而，真空蒸镀所需的设备昂贵，特别是制备有机掺杂发光薄膜层工艺复杂，极大地限制了有机发光二极管在大面积全色显示的产业发展和商业应用。为了突破这个技术瓶颈，选择量子效率高的离子型磷光金属有机化合物作为发光材料是一条可行的替代途径。与电中性化合物相比，离子型磷光金属配合物制备更简单、廉价，稳定性更好，而且易溶于有机溶剂，适合于大面积溶液旋涂或喷墨打印成膜，能够大幅度降低器件制备成本。
发明内容
本发明的目的是提供一种具有内消旋(meso-)或外消旋(rac-)的离子型 磷光PtAg2配合物及其制备方法和用途。
本发明的另一目的是提供一种含有上述离子型磷光金属配合物的发光材料并利用这些发光材料制备高性能的有机发光二极管。
本发明的目的通过如下方式实现：
一种具有消旋结构的离子型磷光金属配合物，其结构为如下式(I)或式(II)所示：
[PtAg2{rac-(PPh2CH2PPhCH2-)2}(C≡CR)2(PR'3)2]2+An- 2/n；          (I)
或
[PtAg2{meso-(PPh2CH2PPhCH2-)2}(C≡CR)2(PR'3)(μ-X)]+ mAm-     (II)
其中，
R可相同或不同，独立地选自：烷基、芳基、杂芳基、杂芳基芳基，
R'可相同或不同，独立地选自：烷基、芳基、杂芳基；
所述的烷基、芳基、杂芳基均可被一个或多个取代基取代，所述取代基选自烷基、烯基、炔基、烷氧基、氨基、卤素、卤烷基、芳基；
X选自卤素；
Am-、An-为一价或二价阴离子，m或n为1、2，所述阴离子例如为ClO4 -、PF6 -、SbF6 -、BF4 -、SiF6 2-等。μ代表桥联。
根据本发明，所述式(I)配合物为外消旋结构，所述式(II)配合物为内消旋结构。
根据本发明，所述式(I)、或式(II)磷光金属配合物的立体结构如下：
Figure PCTCN2017102504-appb-000001
本发明中，所述的烷基是指碳原子数为1-10，优选1-6的直链或支链烷基， 例如，甲基、乙基、丙基、丁基、异丁基、叔丁基等。
所述的烯基代表碳原子数为2-6的直链或支链烯基，例如，乙烯、丙烯、丁烯等。
所述的炔基代表碳原子数为2-6的直链或支链炔基，例如，乙炔、丙炔、丁炔等。
所述的芳基是指具有6-20个碳原子的单环、多环芳族基团，代表性的芳基包括：苯基、萘基等。
所述的杂芳基是指具有1-20个碳原子、并且包含至少1个，优选1-4个选自N、S、O杂原子的单环或多环杂芳族基团，代表性的杂芳基包括：吡咯基、吡啶基、嘧啶基、咪唑基、噻唑基、噁唑基、噁二唑基、咔唑基、喹啉基、喹唑啉基、吲哚基、吩噻嗪基等。
根据本发明，所述Am-或An-优选为ClO4 -、PF6 -、SiF6 2-等，m/n为1、2。
根据本发明，所述R优选为芳基、咔唑基、吩噻嗪基、咔唑基芳基。所述芳基、咔唑基、吩噻嗪基可任选被一个或多个取代基取代，所述取代基选自烷基、烷氧基、氨基、卤素、卤烷基、芳基；所述R'优选为芳基、含氮杂环(例如咔唑基)，所述芳基、含氮杂环可任选被一个或多个取代基取代，所述取代基选自烷基、烷氧基、氨基、卤素、卤烷基、芳基。进一步优选的，R为苯基、烷基-苯基、卤烷基-苯基、咔唑基-苯基、咔唑基、烷基-咔唑基、苯基-咔唑基、吩噻嗪基、烷基-吩噻嗪基；R'为苯基、烷基苯基、咔唑基、烷基-咔唑基、苯基-咔唑基。
根据本发明，所述离子型磷光金属配合物具体的结构优选如下：
Figure PCTCN2017102504-appb-000002
本发明还提供了一种所述式(I)磷光配合物的制备方法，包括如下步骤：1)将rac-(PPh2CH2PPhCH2-)2和Pt(PPh3)2(C≡CR)2在溶剂中反应，得到中间体；2)再将步骤1)中得到的中间体与[Ag(tht)](An-)和PR'3在溶剂中反应，得到所述式(I)磷光配合物。其中，所述tht(tetrahydrothiophene)为四氢噻吩，所述An-、R、R'、X如上所定义。
本发明还提供了一种所述式(II)磷光配合物的制备方法，包括如下步骤：A)将meso-(PPh2CH2PPhCH2-)2和Pt(PPh3)2(C≡CR)2在溶剂中反应，得到中间体；B)将PR'3、nBu4NX、[Ag(tht)](Am-)与步骤A)中得到的中间体在溶剂中反应，得到所述式(II)磷光配合物。其中，所述tht(tetrahydrothiophene) 为四氢噻吩，所述Am-、R、R'、X如上所定义。
根据本发明，所述步骤1)、步骤A)中，所述溶剂优选为卤代烃，例如二氯甲烷。优选的，将反应得到的中间体进行浓缩重结晶。
根据本发明，所述步骤2)、步骤B)中，所述溶剂优选为卤代烃，例如二氯甲烷。优选的，所述步骤B)中，先将PR'3和nBu4NX混合，再将该混合溶液及[Ag(tht)](Am-)加入溶有上述步骤A)中得到的中间体的溶液中。
根据本发明，在所述方法中，rac-(PPh2CH2PPhCH2-)2：Pt(PPh3)2(C≡CR)2：[Ag(tht)](An-):PR'3的摩尔比为1～1.5:1～1.5:2～3:2～3，优选摩尔比为1:1:2:2；meso-(PPh2CH2PPhCH2-)2：Pt(PPh3)2(C≡CR)2：[Ag(tht)](Am-):nBu4NX:PR'3的摩尔比为1～1.5:1～1.5:2～3:1～1.5:1～1.5，优选摩尔比为1:1:2:1:1。
根据本发明，所述反应均在室温下进行。优选的，反应结束后，用硅胶柱色谱分离提纯。
本发明所述的式(I)或式(II)磷光配合物在固体和薄膜中均具有较强磷光发射，其磷光量子产率在薄膜中高于50％；并且其发射光颜色分布较宽，从天蓝到橙红。故其可以作为发光层掺杂体，用于有机发光二极管的制备。
本发明还提供了所述磷光配合物的用途，其用于有机发光二极管。
进一步的，本发明还提供了一种有机发光二极管，包括发光层，其中，所述发光层中含有本发明所述的式(I)或式(II)磷光配合物。
根据本发明，在所述发光层中，本发明所述的式(I)磷光配合物优选占所有材料的3-20％(重量百分比)，更优选5-10％，进一步优选的，本发明所述的式(I)磷光配合物以6％的重量百分比掺杂到主体材料中作为发光层；本发明所述的式(II)磷光配合物优选占所有材料的5-25％(重量百分比)，更优选8-15％，进一步优选的，本发明所述的式(II)磷光配合物以10％的重量百分比掺杂到主体材料中作为发光层。
根据本发明，所述有机发光二极管的结构可以为现有技术中已知的各种结构。优选的包括：阳极层、空穴注入层、任选地空穴传输层、发光层、电子传输层、电子注入层、阴极层。所述有机发光二极管还进一步包括基板(例如玻璃基板)。所述阳极可为铟锡氧化物，所述空穴注入层可为PEDOT:PSS (PEDOT:PSS＝聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸))。所述空穴传输层可为CuSCN、CuI、CuBr。所述发光层含有本发明所述的磷光配合物，以及具有空穴传输特性的物质和/或具有电子传输特性的物质。其中，具有空穴传输特性的物质可以为2,6-DCZPPY(2,6-二(3-(9-咔唑)苯基)吡啶)、mCP(1,3-双(9-咔唑基)苯)、CBP(4,4'-二(9-咔唑)-1,1'-联苯)、或TCTA(三(4-(9-咔唑)苯基)胺)中的一种或多种。具有电子传输特性的物质可以为OXD-7(1,3-双(5-(4-(叔丁基)苯基)-1,3,4-噁二唑-2-基)苯)；所述电子传输层可为BmPyPB(3,3”,5,5”-四(3-吡啶基)-1,1':3',1”-三联苯)、TPBi(1,3,5-三(1-苯基-1H-苯并[d]咪唑-2-基)苯)、BCP(2,9-二甲基-4,7-二苯基-1,10-菲珞啉)或OXD-7中的一种或多种；所述电子注入层为LiF，所述阴极为Al。
根据本发明,含有所述式(I)磷光配合物的器件结构优选为：ITO/PEDOT:PSS(50nm)/CuSCN(30nm)/70.5％2,6-DCZPPY:23.5％OXD-7:6％wt本发明式(I)配合物(50nm)/BmPyPB(50nm)/LiF(1nm)/Al(100nm)，或者ITO/PEDOT:PSS(50nm)/70.5％mCP:23.5％OXD-7:6％wt本发明式(I)配合物(50nm)/BmPyPB(50nm)/LiF(1nm)/Al(100nm)；含有所述式(II)磷光配合物的器件结构优选为：ITO/PEDOT:PSS(50nm)/CuSCN(30nm)/90％2,6-DCZPPY:10％wt本发明式(II)配合物(50nm)/BmPyPB(50nm)/LiF(1nm)/Al(100nm)，或者ITO/PEDOT:PSS(50nm)/90％mCP:10％wt本发明式(II)配合物(50nm)/BmPyPB(50nm)/LiF(1nm)/Al(100nm)。其中ITO为氧化铟锡导电薄膜，PEDOT:PSS为聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)，2,6-DCZPPY为(2,6-二(3-(9-咔唑基)苯基)吡啶)、mCP为(1,3-双(9-咔唑基)苯)，OXD-7为1,3-双(5-(4-(叔丁基)苯基)-1,3,4-噁二唑-2-基)苯，BmPyPB为(3,3”,5,5”-四(3-吡啶基)-1,1':3',1”-三联苯)。
本发明还提供了一种制备所述有机发光二极管的方法，包括：1)采用溶液法在阳极上制备有机发光二极管中的空穴注入层；2)任选地采用溶液法制备有机发光二极管中的空穴传输层；3)采用溶液法制备掺杂有本发明的磷光配合物的发光层；4)再依次利用真空热蒸镀方法制备电子传输层、电子注入层、以及阴极层。
在一个优选的实施方式中，对于所述式(I)磷光配合物，所述方法包括：首先利用水溶性PEDOT:PSS制备空穴注入层；其次利用硫氰化亚铜的二乙硫醚溶液制备空穴传输层；再利用具有空穴传输特性的2,6-DCZPPY和具有电子传输特性的OXD-7为混合主体材料，与本发明所述的式(I)磷光配合物掺杂制备发光层；再依次利用真空热蒸镀方法制备Bmpypb电子传输层、LiF电子注入层、以及Al阴极层；对于所述的式(II)磷光配合物，所述方法包括：首先利用水溶性PEDOT:PSS制备空穴注入层；其次利用硫氰化亚铜的二乙硫醚溶液制备空穴传输层；再利用具有空穴传输特性的2,6-DCZPPY与本发明所述的式(II)磷光配合物掺杂制备发光层；再依次利用真空热蒸镀方法制备Bmpypb电子传输层、LiF电子注入层、以及Al阴极层。
根据本发明，在所述方法中，PEDOT:PSS空穴注入层、2,6-DCZPPY：OXD-7或者2,6-DCZPPY掺杂发光层分别利用溶液旋涂法制备薄膜，BmPyPB电子传输层和LiF电子注入层采用真空热蒸镀法制备薄膜。
由本发明的磷光配合物制备的有机发光二极管具有优异的性能，其具有较高的电-光转换效率。
本发明进一步提供了所述有机发光二极管的用途，其可以用于平板显示和日常照明领域中。
与现有技术相比，本发明具有如下优点：
1)本发明的磷光配合物在固体和薄膜中均具有很强的磷光发射，薄膜磷光量子效率高于50％甚至高达90％；
2)本发明首次利用磷光Pt-Ag异金属配合物为发光材料组装有机发光器件，用本发明磷光配合物为发光层掺杂体制备的有机发光二极管具有高的电致发光外量子转换效率；
3)本发明利用正交溶液法制备有机发光二极管的空穴注入层和发光层，能够大幅度降低器件制备成本；
4)本发明所述的磷光配合物的配体具有内/外消旋不同构型，且电致发光从天蓝到橙红变化，各颜色的发光效率均较高。
附图说明：
图1为器件结构示意图及有机材料化学结构图。
具体实施方式：
为了使本发明的发明目的、技术方案和技术效果更加清晰，以下结合附图和实施例对本发明进行进一步详细说明。应当理解的是，本说明书中描述的实施例只是为了解释本发明，而非限定本发明。
在以下实施例中，dpmppe代表(PPh2CH2PPhCH2-)2，carb代表咔唑基，PhBut-4代表4-叔丁基-苯基，9-Ph-carb-3代表9-苯基-咔唑-3-基，9-Et-carb-3代表9-乙基咔唑-3-基，PhCF3-4代表4-三氟甲基-苯基，9-(4-Ph)-carb代表9-(4-苯基)-咔唑基，10-Et-PTZ-3代表10-乙基吩噻嗪-3-基，tht为四氢噻吩。
实施例1：配合物[PtAg2(rac-dpmppe)(C≡CC6H4But-4)2{PhP(9-Ph-carb-3)2}2](ClO4)2(rac-1)的制备
向20mL溶解了Pt(PPh3)2(C≡CC6H4But-4)2(80.6mg,0.078mmol)的二氯甲烷溶液中加入rac-dpmppe(50mg,0.078mmol)。搅拌30分钟后，浓缩，加入20mL正己烷，析出淡黄色固体，为中间体,产率90％(80.8mg)。向20mL溶解了上述中间体的二氯甲烷溶液中加入Ag(tht)ClO4(41.4mg,0.14mmol)及PhP(9-Ph-carb-3)2(82.9mg,0.14mmol)，反应液在室温下搅拌1小时后变为浅绿色。利用硅胶柱色谱纯化产物，使用CH2Cl2-MeCN(8:1)为洗脱液收集浅绿色产物。产率：70％。元素分析(C148H122Ag2Cl2N4O8P6Pt)计算值:C,64.59；H,4.47；N,2.04.测量值:C,64.40；H,4.55；N,1.96.电喷雾质谱m/z(％):1276.2909(100)[M-2ClO4]2+.核磁共振氢谱(CDCl3,ppm):8.20-8.14(dd,4H,J1＝16Hz，J2＝12Hz),8.08-8.04(dd,4H,J1＝12Hz,J2＝8Hz),7.73-7.59(m,12H),7.53-7.35(m,36H),7.27-7.11(m,20H),6.95-6.88(m,12H),6.69-6.67(d,4H,J＝8Hz),6.59-6.57(d,4H,J＝8Hz),4.29(m,2H),3.02-2.93(3,2H),2.63-2.46(m,2H),0.97(s,18H),0.54(m,2H).核磁共振磷谱(CDCl3,ppm):46.0(d,2P,JP-P＝78Hz,JPt-P＝2448Hz),13.8(m,2P,JP-Ag＝526Hz),1.8(m,2P,JP-Ag＝526Hz,JP-P＝52Hz)..红外光谱(KBr,cm-1):2081w(C≡C),1099s(ClO4 -)。
实施例2：配合物[PtAg2(rac-dpmppe){(C≡C-4)C6H4-carb-9}2(PPh3)2](ClO4)2(rac-2)的制备
制备方法与实施例1中方法基本相同，仅是使用Pt(PPh3)2{(C≡C-4)C6H4-carb-9}2替代Pt(PPh3)2(C≡CC6H4But-4)2，PPh3替代PhP(9-Ph-carb-3)2。产率:71％。元素分析(C116H92Ag2Cl2N2O8P6Pt)计算值:C,60.33；H,4.02；N,1.21.测量值:C,60.12；H,4.02；N,1.15.电喷雾质谱m/z(％):1055.1713(100％,[M-2ClO4]2+).核磁共振氢谱(CDCl3,ppm):8.21-8.13(m,8H),7.59-7.54(m,14H),7.48-7.14(m,18H),7.34-7.24(m,22H),7.20-7.12(m,14H),7.02-6.98(m,4H),6.86-6.85(d,4H,J＝7Hz),4.59(m,2H),3.15-3.06(m,2H),2.73-2.59(m,2H),0.61(m,2H).核磁共振磷谱(CDCl3,ppm):47.0(d,2P,JP-P＝76Hz,JPt-P＝2375Hz),11.8(m,2P,JP-Ag＝506Hz),3.4(m,2P,JP-Ag＝410Hz,JP-P＝45Hz)..红外光谱(KBr,cm-1):2091w(C≡C),1099s(ClO4 -).
实施例3：配合物[PtAg2(rac-dpmppe){C≡C-(9-Ph-carb-3)}2(PPh3)2](ClO4)2(rac-3)的制备
制备方法与实施例1中方法基本相同，仅是使用Pt(PPh3)2(C≡C-(9-Ph-carb-3))2替代Pt(PPh3)2(C≡CC6H4But-4)2，PPh3替代PhP(9-Ph-carb-3)2。产率:71％。元素分析(C116H92Ag2Cl2N2O8P6Pt)计算值:C,60.33；H,4.02；N,1.21.测量值:C,60.10；H,4.05；N,1.16.电喷雾质谱m/z(％):1055.1717(100％,[M-2ClO4]2+).核磁共振氢谱(CDCl3,ppm):8.17-8.12(dd,4H,J1＝12Hz,J2＝8Hz),7.67-7.63(t,4H,J＝8Hz),7.54-7.46(m,22H),7.43-7.40(m,8H),7.37-7.31(m,10H),7.29-7.18(m,10H),7.13-7.03(m,20H),6.95-6.92(m,4H),6.83-6.81(d,2H),4.45(m,2H),3.18-3.09(m,2H),2.69-2.50(m,2H),0.59(m,2H).核磁共振磷谱(CDCl3,ppm):46.3(d,2P,JP-P＝75Hz,JPt-P＝2384Hz),11.9(m,2P,JP-Ag＝510Hz),2.4(m,2P,JP-Ag＝398Hz,JP-P＝51Hz)..红外光谱(KBr,cm-1):2075w(C≡C),1093s(ClO4 -).
实施例4：配合物
[PtAg2(rac-dpmppe)(C≡C-(9-Ph-carb-3))2{P(9-Et-carb-3)3}2](ClO4)2(rac-4)的制备。
制备方法与实施例1中方法基本相同，仅是使用Pt(PPh3)2{C≡C-(9-Ph-carb-3)}2替代Pt(PPh3)2(C≡CC6H4-But-4)2，P(9-Et-carb-3)3替代PhP(9-Ph-carb-3)2。产率:71％。元素分析(C164H134Ag2Cl2N8O8P6Pt)计算值:C,65.39；H,4.48；N,3.72.测量值:C,65.14；H,4.53；N,3.53.电喷雾质谱m/z(％):1406.8446[M-2ClO4]2+.核磁共振氢谱(CDCl3,ppm):8.27-8.22(dd,4H,J1＝12Hz,J2＝8Hz),8.20-8.17(d,6H,J＝12Hz),8.04-7.99(dd,6H,J1＝12Hz,J2＝8Hz),7.71(s,2H),7.50-7.40(m,16H),7.37-7.32(m,12H),7.27-7.25(m,10H),7.17-7.14(m,6H),7.07-7.03(t,2H,J＝7Hz),7.0-6.90(m,12H),6.88-6.77(m,16H),6.73-6.66(m,4H),4.4(m,2H),3.88-3.83(q,12H,J＝7Hz),3.27-3.18(m,2H),2.62-2.44(m,2H),1.0-0.97(d,18H,J＝7Hz),0.72(m,2H).核磁共振磷谱(CDCl3,ppm):46.5(d,2P,JP-P＝78Hz,JPt-P＝2380Hz),15.3(m,2P,JP-Ag＝534Hz),0.8(m,2P,JP-Ag＝378Hz,JP-P＝53Hz).红外光谱(KBr,cm-1):2081w(C≡C),1093s(ClO4 -)。
实施例5：配合物
[PtAg2(rac-dpmppe){C≡C-(9-Et-carb-3)}2{P(9-Et-carb-3)3}2](ClO4)2(rac-5)的制备。
制备方法与实施例1中方法基本相同，仅是使用Pt(PPh3)2{C≡C-(9-Et-carb-3)}2替代Pt(PPh3)2(C≡CC6H4But-4)2，P(9-Et-carb-3)3替代PhP(9-Ph-carb-3)2。产率:72％。元素分析(C156H134Ag2Cl2N8O8P6Pt)计算值:C,64.25；H,4.63；N,3.84.测量值:C,64.02；H,4.65；N,3.58.电喷雾质谱m/z(％):1358.3459(100％)[M-2ClO4]2+.核磁共振氢谱(CDCl3,ppm):8.25-8.16(m,8H),8.01(m,6H),7.73-7.68(m,10H),7.44-7.27(m,28H),7.18-7.02(m,10H),6.94-6.82(m,22H),6.70-6.64(m,4H),4.33(m,2H),4.05-3.99(q,4H,J＝7Hz),3.85-3.79(q,12H,J＝7Hz),3.26-3.22(m,2H), 2.64-2.51(m,2H),1.29-1.15(t,6H,J＝7Hz),1.11-0.97(t,18H,J＝7Hz),0.71(m,2H).核磁共振磷谱(CDCl3,ppm):46.2(d,2P,JP-P＝78Hz,JPt-P＝2376Hz),15.3(m,2P,JP-Ag＝524Hz),0.6(m,2P,JP-Ag＝369Hz,JP-P＝52Hz).红外光谱(KBr,cm-1)(KBr,cm-1):2073w(C≡C),1093s(ClO4 -)。
实施例6：配合物[PtAg2(rac-dpmppe){C≡C-(10-Et-PTZ-3)}2{P(9-Et-carb-3)3}2](ClO4)2(rac-6)的制备。
制备方法与实施例1中方法基本相同，仅是使用Pt(PPh3)2{C≡C-(10-Et-PTZ-3)}2替代Pt(PPh3)2(C≡CC6H4But-4)2，P(9-Et-carb-3)3替代PhP(9-Ph-carb-3)2。产率:73％。元素分析(C156H134Ag2Cl2N8O8P6PtS2)计算值:C,62.86；H,4.53；N,3.76.测量值:C,62.62；H,4.57；N,3.59.电喷雾质谱m/z(％):1390.8150(100％)[M-2ClO4]2+.核磁共振氢谱(CDCl3,ppm):8.16-8.13(m,8H),8.01-7.96(dd,6H,J＝8Hz),7.58-7.55(m,6H),7.42-7.38(m,12H),7.34-7.30(m,8H),7.15-6.99(m,22H),6.90-6.86(m,14H),6.69-6.67(d,2H,J＝8Hz),6.54-6.52(d,2H,J＝8Hz),6.35-6.32(m,4H),5.92-5.90(d,2H,J＝8Hz),4.23(m,2H),4.05-3.99(q,12H,J＝7Hz),3.45-3.39(q,4H,J＝7Hz),3.06-2.97(m,2H),2.64-2.45(m,2H),1.18-1.14(t,18H,J＝7Hz),1.06-1.02(t,6H,J＝7Hz),0.59(m,2H).核磁共振磷谱(CDCl3,ppm):46.5(d,2P,JP-P＝78Hz,JPt-P＝2376Hz),15.2(m,2P,JP-Ag＝536Hz),1.5(m,2P,JP-Ag＝381Hz,JP-P＝54Hz).红外光谱(KBr,cm-1):2081w(C≡C),1093s(ClO4 -)。
实施例7：配合物[PtAg2(meso-dpmppe)(C≡CC6H4CF3-4)2(PPh3)Cl](ClO4)(meso-7)的制备。
向20mL溶解了Pt(PPh3)2(C≡CC6H4CF3-4)2(82.5mg,0.078mmol)的二氯甲烷溶液中加入meso-dpmppe(50mg,0.078mmol)。搅拌30分钟后，浓缩，加入20mL正己烷，析出淡黄色固体，为中间体,产率90％(82.4mg)。先混合PPh3(18.3mg,0.07mmol)和nBu4NCl(19.5mg,0.07mmol)，将该混合溶液及 Ag(tht)ClO4(41.4mg,0.14mmol)加入溶有上述中间体的二氯甲烷溶液，反应液在室温下搅拌1小时后变为浅蓝色。利用硅胶柱色谱纯化产物，使用CH2Cl2-MeCN(15:1)为洗脱液收集黄色产物。产率：75％。元素分析(C76H61Ag2Cl2F6O4P5Pt)计算值:C,51.03；H,3.44.测量值:C,51.21；H,3.60.电喷雾质谱m/z(％)：1688.0808(100％,[M-ClO4]+).核磁共振氢谱(CDCl3,ppm):8.03-7.96(m,8H),7.59-7.36(m,22H),7.33-7.29(t,4H,J＝7Hz),7.25-7.17(m,11H),6.92-6.89(m,4H),6.65-6.62(m,4H),3.86(m,2H),3.37(m,2H),2.28-2.11(m,4H).核磁共振磷谱(CDCl3,ppm):47.6(dd,2P,JP-P＝30Hz,JPt-P＝2412Hz),7.6(m,1P,JP-Ag＝579Hz),-8.9(m,2P,JP-Ag＝422Hz,JP-P＝59Hz).红外光谱(KBr,cm-1):2092w(C≡C),1104s(ClO4 -).
实施例8：配合物[PtAg2(meso-dpmppe)(C≡CC6H4But-4)2(PPh3)Cl](ClO4)(meso-8)的制备。
制备方法与实施例7中方法基本相同，仅是使用Pt(PPh3)2(C≡CC6H4But-4)2替代Pt(PPh3)2(C≡CC6H4CF3-4)2。产率:74％。元素分析(C82H79Ag2Cl2O4P5Pt)计算值:C,55.80；H,4.51.测量值:C,56.02；H,4.74.电喷雾质谱m/z(％)：1665.2304(100％,[M-ClO4]+).核磁共振氢谱(CDCl3,ppm):8.03-7.97(m,8H),7.53-7.50(m,7H),7.41-7.31(m,20H),7.24-7.16(m,12H),6.71-6.59(m,8H),3.81(m,2H),3.46(m,2H),2.18-2.01(m,4H),1.45(s,18H).核磁共振磷谱(CDCl3,ppm):47.1(q,2P,JP-P＝30Hz,JPt-P＝2409Hz),7.2(m,1P,JP-Ag＝565Hz),-9.5(m,2P,JP-Ag＝417Hz,JP-P＝58Hz).红外光谱(KBr,cm-1):2092w(C≡C),1093s(ClO4 -).
实施例9：配合物[PtAg2(meso-dpmppe)(C≡CC6H4But-4)2{P(9-Et-carb-3)3}Cl](ClO4)(meso-9)的制备。
制备方法与实施例7中方法基本相同，仅是使用Pt(PPh3)2(C≡CC6H4But-4)2替代Pt(PPh3)2(C≡CC6H4CF3-4)2，P(9-Et-carb-3)3替代PPh3。产率:74％。元素 分析(C106H100Ag2Cl2N3O4P5Pt)计算值:C,60.15；H,4.76；N,1.99.测量值:C,60.32；H,4.73；N,1.88.电喷雾质谱m/z(％)：2016.4011(100％,[M-ClO4]+).核磁共振氢谱(CDCl3,ppm):8.48-8.45(d,2H,J＝12Hz),8.08-8.04(dd,4H,J1＝12Hz,J2＝8Hz),7.94-7.92(d,2H,J＝8Hz),7.89(m,4H),7.53-7.41(m,26H),7.25-7.15(m,13H),6.61-6.59(m,4H),6.40-6.38(m,4H),4.41-4.37(q,6H,J＝7Hz),3.76(m,2H),3.49(m,2H),2.24-2.05(m,4H),1.49-1.47(t,9H,J＝7Hz),0.76(s,18H).核磁共振磷谱(CDCl3,ppm):47.5(q,2P,JP-P＝29Hz,JPt-P＝2394Hz),10.4(m,1P,JP-Ag＝601Hz),-9.3(m,2P,JP-Ag＝417Hz,JP-P＝56Hz).红外光谱(KBr,cm-1):2110w(C≡C),1093s(ClO4 -).
实施例10：配合物[PtAg2(meso-dpmppe)(C≡CC6H4But-4)2{P(9-Et-carb-3)3}I](ClO4)(meso-10)的制备。
制备方法与实施例7中方法基本相同，仅是使用Pt(PPh3)2(C≡CC6H4But-4)2替代Pt(PPh3)2(C≡CC6H4CF3-4)2，P(9-Et-carb-3)3替代PPh3，nBu4NI替代nBu4NCl。产率:72％。元素分析(C106H100Ag2ClIN3O4P5Pt)计算值:C,57.66；H,4.56；N,1.90.测量值:C,57.57；H,4.60；N,1.83.电喷雾质谱m/z(％):2108.3387(100％,[M-ClO4]+).核磁共振氢谱(CDCl3,ppm):8.51-8.48(d,2H,J＝12Hz),8.11-8.07(dd,4H,J1＝12Hz,J2＝8Hz),7.98-7.96(d,2H,J＝8Hz),7.82(m,4H),7.54-7.40(m,26H),7.29-7.16(m,13H),6.54-6.52(m,4H),6.37-6.35(m,4H),4.39-4.35(q,6H,J＝7Hz),3.71(m,2H),3.52(m,2H),2.25-2.05(m,4H),1.49-1.47(t,9H,J＝7Hz),0.72(s,18H).核磁共振磷谱(CDCl3,ppm):48.5(q,2P,JP-P＝30Hz,JPt-P＝2391Hz),9.0(m,1P,JP-Ag＝547Hz),-11.7(m,2P,JP-Ag＝386Hz,JP-P＝59Hz).红外光谱(KBr,cm-1):2104w(C≡C),1093s(ClO4 -)。
实施例11：配合物[PtAg2(meso-dpmppe)(C≡C-(10-Et-PTZ-3))2{P(9-Et-carb-3)3}(μ-I)](ClO4)(meso-11)的制备。
制备方法与实施例7中方法基本相同，仅是使用 Pt(PPh3)2{C≡C-(10-Et-PTZ-3)}2替代Pt(PPh3)2(C≡CC6H4CF3-4)2，P(9-Et-carb-3)3替代PPh3，nBu4NI替代nBu4NCl。产率：75％。元素分析(C114H98Ag2ClIN5O4P5PtS2)计算值:C,57.19；H,4.13；N,2.93.测量值:C,57.42；H,4.33；N,2.84.电喷雾质谱m/z(％):2294.2671(100％，[M-ClO4]+).核磁共振氢谱(CDCl3,ppm):8.54-8.51(d,2H,J＝12Hz),8.09-8.04(dd,4H,J1＝12Hz,J2＝8Hz),7.95-7.93(d,2H,J＝8Hz),7.80(m,4H),7.59-7.29(m,29H),7.18-7.01(m,12H),6.75(m,4H),6.51-6.49(d,2H,J＝8Hz),6.41-6.39(d,2H,J＝8Hz),6.22(s,2H),5.63-5.61(d,2H,J＝8Hz),4.45-4.27(q,6H,J＝7Hz),3.71(m,2H),3.46(m,2H),3.14-3.08(q,4H,J＝6Hz),2.28-2.03(m,4H),1.44-1.40(t,9H,J＝7Hz),0.86-0.81(t,6H,J＝6Hz).核磁共振磷谱(CDCl3,ppm):48.6(q,2P,JP-P＝29Hz,JPt-P＝2391Hz),9.1(m,1P,JP-Ag＝548Hz),-11.4(m,2P,JP-Ag＝384Hz,JP-P＝60Hz).红外光谱(KBr,cm-1):2101w(C≡C),1094s(ClO4 -)。
实施例12：光致发光性能测试
在Edinburgh FLS920荧光光谱仪上分别测试实施例1、4、5、6中制备的配合物rac-1、rac-4、rac-5、rac-6在固体粉末及70.5％2,6-DCZPPY:23.5％OXD-7:6％本发明配合物rac-1、4、5、或6(重量比)薄膜中和实施例11中制备的配合物meso-11在固体粉末及90％2,6-DCZPPY:10％本发明配合物meso-11(重量比)薄膜中的激发光谱、发射光谱、发光寿命和发光量子产率。利用直径为142mm的积分球测定固体粉末样品的发光量子产率。
配合物rac-1、rac-4、rac-5、rac-6、或meso-11的固体状态发射波长和量子产率分别为500nm和15.1％(rac-1)，566nm和37.1％(rac-4)，580nm和30.4％(rac-5)，662nm和1.7％(rac-6)，600nm和8.1％(meso-11)；
配合物rac-1、rac-4、rac-5、或rac-6在70.5％2,6-DCZPPY:23.5％OXD-7:6％本发明配合物rac-1、4、5、或6(重量比)薄膜中的发射波长和量子产率分别为487nm和52.2％(rac-1)，527nm和90.5％(rac-4)，535nm和77.0％(rac-5)，616nm和56.8％(rac-6)；配合物meso-11在90％2,6-DCZPPY:10％本发明配合物meso-11(重量比)薄膜中的发射波长和量子产率分别为570nm和 52.2％(meso-11)。
实施例13：有机发光二极管器件制备与电致发光性能测试
分别利用实施例1、4、5、6中制备的磷光配合物rac-1、rac-4、rac-5、或rac-6为发光材料以6％的重量百分比掺杂到2,6-DCZPPY(70.5％):OXD-7(23.5％)混合主体材料中作为发光层制备有机发光二极管，器件结构为：ITO/PEDOT:PSS(50nm)/CuSCN(30nm)/70.5％2,6-DCZPPY:23.5％OXD-7:6％本发明配合物rac-1、4、5、或6(50nm)/Bmpypb(50nm)/LiF(1nm)/Al(100nm)；实施例11中制备的磷光配合物meso-11为发光材料以10％的重量百分比掺杂到2,6-DCZPPY(90％)主体材料中作为发光层制备有机发光二极管，器件结构为：ITO/PEDOT:PSS(50nm)/CuSCN(30nm)/90％2,6-DCZPPY:10％本发明配合物meso-11(50nm)/Bmpypb(50nm)/LiF(1nm)/Al(100nm)。
首先分别利用去离子水、丙酮、异丙醇清洗ITO基底，再采用UV-臭氧处理15分钟。将过滤后的PEDOT:PSS水溶液在旋涂仪上以4800转/分钟的转速旋涂到ITO基底上，在140℃干燥20分钟后得到50nm厚度的空穴注入层。然后将CuSCN的二乙基硫醚溶液(10mg/mL)以4800转/分钟的转速旋涂到PEDOT:PSS空穴注入层，在120℃干燥30分钟后得到30nm厚度的空穴传输层。其次利用旋涂仪将过滤后的浓度为5.5mg/mL的70.5％2,6-DCZPPY:23.5％XD-7:6％本发明配合物rac-1、rac-4、rac-5、或rac-6(重量百分比)或者5.5mg/mL的90％2,6-DCZPPY:10％本发明配合物meso-11(重量百分比)的二氯甲烷溶液以2100转/分钟的转速旋涂到PEDOT:PSS薄膜上形成50nm厚度的发光层。随后，将ITO基底置于真空度不低于4×10-4Pa的真空腔中，依次热蒸镀50nm厚的Bmpypb、1nm厚的LiF电子注入层、以及100nm厚度的Al为器件阴极。
发光二极管器件性能测试在室温干燥的空气环境中进行。电致发光性能参数包括电致发光波长(λEL)，启亮电压(Von)，最大亮度(Lmax)，最大电流效率(CEmax)，最大功率效率(PEmax)，最大外量子效率(EQEmax)列于表1。
表1.本发明磷光配合物rac-1、rac-4、rac-5、rac-6、或meso-11电致发光器件性能数据
Figure PCTCN2017102504-appb-000003
a)亮度为1cd/m2的启亮电压，b)最大亮度，c)最大电流效率，d)最大功率效率，e)最大外量子效率，f)CIE为色度坐标。

Claims (10)

  1. 一种离子型磷光金属配合物，其结构为如下式(I)或式(II)所示：
    [PtAg2{rac-(PPh2CH2PPhCH2-)2}(C≡CR)2(PR'3)2]2+An- 2/n；  (I)
    或
    [PtAg2{meso-(PPh2CH2PPhCH2-)2}(C≡CR)2(PR'3)(μ-X)]+ mAm-  (II)
    其中，
    R可相同或不同，独立地选自：烷基、芳基、杂芳基、杂芳基芳基；
    R'可相同或不同，独立地选自：烷基、芳基、杂芳基；
    所述的烷基、芳基、杂芳基均可被一个或多个取代基取代，所述取代基选自烷基、烯基、炔基、烷氧基、氨基、卤素、卤烷基、芳基；
    X选自卤素；
    Am-、An-为一价或二价阴离子，m或n为1、或2，所述阴离子例如为ClO4 -、PF6 -、SbF6 -、BF4 -、SiF6 2-，μ代表桥联。
  2. 根据权利要求1所述的磷光金属配合物，其中，所述式(I)、或式(II)磷光金属配合物的立体结构如下：
    Figure PCTCN2017102504-appb-100001
  3. 根据权利要求1或2所述的磷光金属配合物，其中，所述R为芳基、咔唑基、吩噻嗪基、咔唑基芳基；所述芳基、咔唑基、吩噻嗪基可任选被一个或多个取代基取代，所述取代基选自烷基、烷氧基、氨基、卤素、卤烷基、芳基；所述R'为芳基、含氮杂环，所述芳基、含氮杂环可任选被一个或多个取代基取代，所述取代基选自烷基、烷氧基、氨基、卤素、卤烷基、芳基；
    进一步优选的，R为苯基、烷基-苯基、卤烷基-苯基、咔唑基-苯基、咔唑基、烷基-咔唑基、苯基-咔唑基、吩噻嗪基、烷基-吩噻嗪基；R'为苯基、烷基 苯基、咔唑基、烷基-咔唑基、苯基-咔唑基。
  4. 根据权利要求1或2所述的磷光金属配合物，其中，所述金属配合物具体为如下11个配合物：
    Figure PCTCN2017102504-appb-100002
  5. 权利要求1-4任一项所述的磷光金属配合物的制备方法，其中，所述式(I)磷光金属配合物的制备方法包括如下步骤：1)将rac-(PPh2CH2PPhCH2-)2和Pt(PPh3)2(C≡CR)2在溶剂中反应，得到中间体；2)再将步骤1)中得到的中间体与[Ag(tht)](An-)和PR'3在溶剂中反应，得到所述式(I)磷光配合物；其中，所述tht(tetrahydrothiophene)为四氢噻吩，所述An-、R、R'、X如权利要求1-4任一项所定义；
    或者，
    所述式(II)磷光配合物的制备方法包括如下步骤：A)将meso-(PPh2CH2PPhCH2-)2和Pt(PPh3)2(C≡CR)2在溶剂中反应，得到中间体；B)将PR'3、nBu4NX、[Ag(tht)](Am-)与步骤A)中得到的中间体在溶剂中反应，得到所述式(II)磷光配合物；其中，所述tht(tetrahydrothiophene)为四氢噻吩，所述Am-、R、R'、X如权利要求1-4任一项所定义。
  6. 权利要求1-4任一项所述的磷光金属配合物用于有机发光二极管的用途。
  7. 一种有机发光二极管，包括发光层，其中，所述发光层中含有权利要求1-4任一项所述的式(I)或式(II)磷光配合物；
    优选的，在所述发光层中，权利要求1-4任一项所述的式(I)磷光配合物占所有材料的3-20％(重量百分比)；权利要求1-4任一项所述的式(II)磷光配合物占所有材料的5-25％(重量百分比)。
  8. 权利要求7所述的有机发光二极管，其中，所述有机发光二极管还包括：阳极层、空穴注入层、任选地空穴传输层、发光层、电子传输层、电子注入层、阴极层。
  9. 权利要求8所述的有机发光二极管，其中，所述阳极为铟锡氧化物，所述空穴注入层为PEDOT:PSS(PEDOT:PSS＝聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸))；所述空穴传输层为CuSCN、CuI、CuBr；所述发光层含有权利要求1-4任一项所述的磷光配合物，以及具有空穴传输特性的物质和/或具有电子传输特性的物质；所述电子传输层为BmPyPB(3,3”,5,5”-四(3-吡啶基)-1,1':3',1”-三联苯)、TPBi(1,3,5-三(1-苯基-1H-苯并[d]咪唑-2-基)苯)、BCP(2,9-二甲基-4,7-二苯基-1,10-菲珞啉)或OXD-7中的一种或多种；所述电子注入层为LiF，所述阴极为Al。
    优选的,含有所述式(I)磷光配合物的器件结构为：ITO/PEDOT:PSS/CuSCN/70.5％2,6-DCZPPY:23.5％OXD-7:6％wt权利要求1-4任一项所述的式(I)配合物/BmPyPB/LiF/Al，或者ITO/PEDOT:PSS/70.5％mCP:23.5％OXD-7:6％wt权利要求1-4任一项所述的式(I)配合物/BmPyPB/ LiF/Al；
    含有所述式(II)磷光配合物的器件结构为：ITO/PEDOT:PSS/CuSCN/90％2,6-DCZPPY:10％wt权利要求1-4任一项所述的式(II)配合物/BmPyPB/LiF/Al，或者ITO/PEDOT:PSS/90％mCP:10％wt权利要求1-4任一项所述的式(II)配合物/BmPyPB/LiF/Al；
    其中，ITO为氧化铟锡导电薄膜，PEDOT:PSS为聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)，2,6-DCZPPY为(2,6-二(3-(9-咔唑基)苯基)吡啶)、mCP为(1,3-双(9-咔唑基)苯)，OXD-7为1,3-双(5-(4-(叔丁基)苯基)-1,3,4-噁二唑-2-基)苯，BmPyPB为(3,3”,5,5”-四(3-吡啶基)-1,1':3',1”-三联苯)。
  10. 权利要求7-9任一项所述的有机发光二极管的用途，其用于平板显示和日常照明领域中。
PCT/CN2017/102504 2016-12-14 2017-09-20 一种磷光PtAg2配合物及其制备方法和用途 Ceased WO2018107841A1 (zh)

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