CN111116413B - Platinum (II) SCHIFF base complexes with increased emission quantum yields for red OLED applications - Google Patents

Platinum (II) SCHIFF base complexes with increased emission quantum yields for red OLED applications Download PDF

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CN111116413B
CN111116413B CN201811283945.3A CN201811283945A CN111116413B CN 111116413 B CN111116413 B CN 111116413B CN 201811283945 A CN201811283945 A CN 201811283945A CN 111116413 B CN111116413 B CN 111116413B
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支志明
邝俊霖
林子龙
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Sichuan Knowledge Express Institute for Innovative Technologies Co Ltd
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Abstract

A red-emitting platinum (II) Schiff base complex with high emission quantum efficiency was prepared. These materials can be used to make OLEDs.

Description

Platinum (II) SCHIFF base complexes with increased emission quantum yields for red OLED applications
Technical Field
The present invention describes platinum (II) based red emitters and their use in OLED applications.
Background
Platinum-based Organic Light Emitting Diode (OLED) emitters are potential alternatives to conventional iridium emitters, for which there are many reports of high phosphorescent quantum yields and emission colors across the entire visible spectrum. To achieve commercialization, the chemical stability and production costs of platinum OLED emitters must be addressed. Tetradentate Pt (II) -Schiff base complexes are attractive in these efforts due to their enhanced stability and ease of synthesis. The structure of the Pt (II) -Schiff base complex can be easily modified to have a high spectral purity in the red spectral regionThis is advantageous for red OLED applications. For example, chem et al chem.eur.j.,2010,16,233; opt.lett.,2013,38,2373; chem. Asian. J.,2014,9,984 discloses several Pt (II) -Schiff base complexes for making singular doped (white doped) nearly pure red OLED devices (CIE x,y :0.61-0.65,0.34-0.38) which shows a maximum Current Efficiency (CE) of up to 17.36 cd/a. Wong et al, J.Mater.chem.,2012,22,16448 discloses a red light device (CIE x,y :0.68,0.32) having a maximum CE of 1.3cd/A. Unfortunately, the photoluminescence quantum yield (which parameter is highly related to device efficiency) of all of the disclosed red-emitting Pt (II) -Schiff base complexes never exceeds 0.3. Thus, pt (II) -Schiff base complexes require different molecular designs to achieve enhanced photoluminescence quantum yields to achieve more efficient red OLEDs.
Disclosure of Invention
In one embodiment of the invention, a red-emitting platinum (II) Schiff base complex exhibiting a high photoluminescence quantum yield has the following chemical structure:
wherein Pt has a valence II oxidation state complexed with a tetradentate ligand, wherein: x is X 1 -X 4 Independently carbon, nitrogen, silicon or phosphorus; r is R 1 -R 12 Independently selected from hydrogen, halogen, hydroxy, unsubstituted alkyl, substituted alkyl, cycloalkyl, unsubstituted aryl, substituted aryl, acyl, alkoxy, acyloxy, amino, nitro, acylamino, aralkyl, cyano, carboxyl, mercapto, styryl, aminocarbonyl, carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or alkoxycarbonyl; and E is an emission intensity enhancing group comprising an aromatic group conjugated to the phenyl group of the ligand, wherein adjacent R 1 -R 12 And the E groups may independently form a 5-8 membered ring.
One embodiment of the invention relates to a red OLED device comprising a platinum (II) emitter having structure I. Advantageously, the OLED device exhibits high efficiency.
Drawings
FIG. 1 shows emitters 101-103 at CH 2 Cl 2 In 298K, and photoluminescence spectra.
FIG. 2 shows emitters 104-106 at CH 2 Cl 2 In 298K, and photoluminescence spectra.
FIG. 3 shows emitters 108-110 at CH 2 Cl 2 In 298K, and photoluminescence spectra.
FIG. 4 shows the composite EQE-luminance characteristics of emitters 102, 108, and 109.
Fig. 5 shows the composite electroluminescent spectra of emitters 102, 108 and 109.
Detailed Description
Definition of the definition
The disclosure, terms, abbreviations, or other shorthand definitions herein are defined as follows. Any undefined terms, abbreviations or shorthand should be understood to have the ordinary meaning as used by one of ordinary skill in the art at the time of filing this application.
"amino" refers to a primary, secondary or tertiary amine that may be optionally substituted. Specifically included are secondary or tertiary amine nitrogen atoms, which are members of the heterocyclic ring. Also specifically included are, for example, secondary or tertiary amino groups substituted with acyl groups. Some non-limiting examples of amino groups include-NR 'R ", wherein R' and R" are each independently H, alkyl, aryl, aralkyl, alkaryl, cycloalkyl, acyl, heteroalkyl, heteroaryl, or heterocyclyl.
"alkyl" refers to a fully saturated acyclic monovalent group containing carbon and hydrogen, which may be branched or straight chain. Examples of alkyl groups include, but are not limited to, alkyl groups having 1 to 20, 1 to 10, or 1 to 6 carbon atoms, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-heptyl, n-hexyl, n-octyl, and n-decyl.
"alkylamino" means a group-NHR or-NR 2 Wherein each R is independently alkyl. Representative examples of alkylamino groups include, but are not limited to, methylamino, (1-methylethyl) amino, methylaminoDimethylamino, methylethylamino and di (1-methylethylamino).
The term "hydroxyalkyl" refers to an alkyl group as defined herein substituted with one or more, preferably one, two or three hydroxyl groups. Representative examples of hydroxyalkyl groups include, but are not limited to, hydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 1- (hydroxymethyl) -2-methylpropyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 2, 3-dihydroxypropyl, 2-hydroxy-1-hydroxymethylethyl, 2, 3-dihydroxybutyl, 3, 4-dihydroxybutyl and 2- (hydroxymethyl) -3-hydroxy-propyl, preferably 2-hydroxyethyl, 2, 3-dihydroxypropyl, and 1- (hydroxymethyl) -2-hydroxyethyl.
The term "alkoxy" as used herein refers to the group-OR, where R is alkyl. Exemplary alkoxy groups include, but are not limited to, methoxy, ethoxy, and propoxy.
"aromatic" or "aromatic group" refers to an aryl or heteroaryl group.
"aryl" refers to an optionally substituted carbocyclic aromatic group (e.g., having 6-20 carbon atoms). In some embodiments, the aryl group comprises phenyl, biphenyl, naphthyl, substituted phenyl, substituted biphenyl, or substituted naphthyl. In other embodiments, the aryl is phenyl or substituted phenyl.
"heteroaryl" refers to an aromatic group having at least one non-carbon atom in at least one five-or six-membered aromatic ring of the group. Heteroaryl groups may be substituted or unsubstituted. Some non-limiting examples of heteroaryl groups include furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyridyl, pyrimidinyl, phosphaphenyl (phosphininyl), diazinyl, oxazinyl, thiazinyl, dioxanyl, indolyl, isoindolyl, indolizinyl, quinolinyl, isoquinolinyl, purinyl, carbazolyl, and dibenzofuranyl, wherein the linkage may be through the substitution of hydrogen of the heteroaryl group.
"aralkyl" refers to an alkyl group substituted with an aryl group. Some non-limiting examples of aralkyl groups include benzyl and phenethyl.
"acyl" refers to a monovalent group of the formula-C (=o) H, -C (=o) -alkyl, -C (=o) -aryl, -C (=o) -aralkyl, -C (=o) -alkylaryl.
"halogen" refers to fluorine, chlorine, bromine and iodine.
"styryl" means a monovalent group C derived from styrene 6 H 5 -CH＝CH-。
"substituted" as used herein to describe a compound or chemical group means that at least one hydrogen atom of the compound or chemical group is replaced with a second chemical group. Non-limiting examples of substituents are those present in the exemplary compounds and embodiments disclosed herein, as well as halogens; an alkyl group; a heteroalkyl group; alkenyl groups; alkynyl; an aryl group; heteroaryl; a hydroxyl group; an alkoxy group; an amino group; a nitro group; a mercapto group; a thioether group; an imino group; cyano group; amide groups (amido); phosphonic acid groups (phosphonato); phosphine; a carboxyl group; thiocarbonyl group; a sulfonyl group; a sulfonamide group; a ketone; an aldehyde; an ester; oxo; haloalkyl (e.g., trifluoromethyl); carbocyclic cycloalkyl, which may be monocyclic or fused or unfused polycyclic (e.g., cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl) or heterocycloalkyl, which may be monocyclic or fused or unfused polycyclic (e.g., pyrrolidinyl, piperidinyl, piperazinyl, morpholinyl, or thiazinyl); carbocyclic or heterocyclic, monocyclic or fused or unfused polycyclic aryl (e.g., phenyl, naphthyl, pyrrolyl, indolyl, furanyl, thienyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, quinolinyl, isoquinolinyl, acridinyl, pyrazinyl, pyridazinyl, pyrimidinyl, benzimidazolyl, benzothienyl, or benzofuranyl); amino (primary, secondary or tertiary); ortho lower alkyl; ortho aryl, aryl; aryl-lower alkyl; -CO 2 CH 3 ；-CONH 2 ；-OCH 2 CONH 2 ；-NH 2 ；-SO 2 NH 2 ；-OCHF 2 ；-CF 3 ；-OCF 3 The method comprises the steps of carrying out a first treatment on the surface of the -NH (alkyl); -N (alkyl) 2 The method comprises the steps of carrying out a first treatment on the surface of the -NH (aryl); -N (alkyl) (aryl); -N (aryl) 2 The method comprises the steps of carrying out a first treatment on the surface of the -CHO; -CO (alkyl); -CO (aryl))；-CO 2 (alkyl); and-CO 2 (aryl); and these groups may also be optionally substituted with condensed ring structures or bridges, e.g., -OCH 2 O-. These substituents may optionally be further substituted with substituents selected from these groups. Unless otherwise indicated, all chemical groups disclosed herein may be substituted. For example, a "substituted" alkyl, alkenyl, alkynyl, aryl, hydrocarbyl, or heterocyclic group as described herein is a group substituted with a hydrocarbyl group, a substituted hydrocarbyl group, a heteroatom, or a heterocyclic group. In addition, substituents may include groups in which a carbon atom is replaced by a heteroatom such as a nitrogen, oxygen, silicon, phosphorus, boron, sulfur, or halogen atom. Such substituents may include halogen, heterocycle, alkoxy, alkenyloxy, alkynyloxy, aryloxy, hydroxy, protected hydroxy, keto, acyl, acyloxy, nitro, amino, amido, cyano, mercapto, ketals, acetals, esters, and ethers.
Platinum (II) emitters
In an embodiment of the invention, the platinum (II) emitter has the chemical structure of structure I:
wherein Pt has a valence II oxidation state complexed with a tetradentate ligand, wherein: x is X 1 -X 4 Independently carbon, nitrogen, silicon or phosphorus; r is R 1 -R 12 Independently selected from hydrogen, halogen, hydroxy, unsubstituted alkyl, substituted alkyl, cycloalkyl, unsubstituted aryl, substituted aryl, acyl, alkoxy, acyloxy, amino, nitro, acylamino, aralkyl, cyano, carboxyl, mercapto, styryl, aminocarbonyl, carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or alkoxycarbonyl; and E is an emission intensity enhancing group comprising an aromatic group conjugated to the phenyl group of the ligand, wherein adjacent R 1 -R 12 And the E groups may independently form a 5-8 membered ring.
In one embodiment of the invention, E of the Pt (II) complex isWherein R is 13 -R 17 Independently is an unsubstituted alkyl, substituted alkyl, cycloalkyl, unsubstituted aryl, substituted aryl, alkoxy, or amino group.
In another embodiment of the present invention, E of the Pt (II) complex isWherein R is 18 And R is 31 Independently hydrogen, methyl, isopropyl, or phenyl; r is R 19 -R 30 Independently is hydrogen, halogen, hydroxy, unsubstituted alkyl, substituted alkyl, cycloalkyl, unsubstituted aryl, substituted aryl, acyl, alkoxy, acyloxy, amino, nitro, acylamino, aralkyl, cyano, carboxyl, mercapto, styryl, aminocarbonyl, carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or alkoxycarbonyl. R is R 19 -R 30 Independently from each other pair of adjacent R groups may form a 5-8 membered ring.
In one embodiment of the invention, R of the Pt (II) complex 1 、R 2 、R 11 And R is 12 Is not an amino group, or is not part of a substituted azacyclic aromatic group (wherein the nitrogen is bound to the aromatic ring).
The platinum (II) emitter according to an embodiment of the present invention is as follows:
one embodiment of the present invention relates to Schiff base ligands of structure II:
wherein: x is X 1 -X 4 Independently carbon, nitrogen, silicon or phosphorus; r is R 1 -R 12 Independently selected from hydrogen, halogen, hydroxy, unsubstituted alkyl, substituted alkyl, cycloalkyl, unsubstituted aryl, substituted aryl, acyl, alkoxy, acyloxy, amino, nitro, acylamino, aralkyl, cyano, carboxyl, mercapto, styryl, aminocarbonyl, carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or alkoxycarbonyl; and E is an emission intensity enhancing group comprising an aromatic group conjugated to the phenyl group of the ligand, wherein adjacent R 1 -R 12 And the E groups may independently form a 5-8 membered ring.
In one embodiment of the invention E is a Schiff base tetradentate ligandWherein R is 13 -R 17 Independently is an unsubstituted alkyl, substituted alkyl, cycloalkyl, unsubstituted aryl, substituted aryl, alkoxy, or amino group.
In another embodiment of the invention E is a Schiff base tetradentate ligandWherein R is 18 And R is 31 Independently hydrogen, methyl, isopropyl, or phenyl; r is R 19 -R 30 Independently is hydrogen, halogen, hydroxy, unsubstituted alkyl, substituted alkyl, cycloalkyl, unsubstituted aryl, substituted aryl, acyl, alkoxy, acyloxy, amino, nitro, acylamino, aralkyl, cyano, carboxyl, mercapto, styryl, aminocarbonyl, carbamoyl, aryloxycarbonyl, phenoxycarbonyl, or alkoxycarbonyl. R is R 19 -R 30 Can be independently selected from each pair of adjacent R groupsForming a 5-8 membered ring.
In one embodiment of the invention, R is a Schiff base tetradentate ligand 1 、R 2 、R 11 And R is 12 Is not amino or is not part of a substituted azacyclic aromatic ring (wherein the nitrogen is bound to the aromatic ring).
Preparation of emitters
In one embodiment of the present invention, a platinum (II) emitter having the chemical structure of structure I can be prepared by reacting the corresponding ligand of structure II with a platinum salt in the presence of a suitable solvent and under suitable conditions.
Materials and methods
The following examples illustrate embodiments for practicing the invention. These examples should not be construed as limiting. All percentages are by weight and all solvent mixture proportions are by volume unless otherwise indicated.
EXAMPLE 201 general procedure for the preparation of platinum (II) emitters
A mixture of Schiff base ligand (1 eq) and sodium acetate (2 eq) was dissolved in a minimum amount of hot DMF. Potassium tetrachloroplatinate (1 eq.) in hot DMSO was added and the reaction mixture was kept at 80℃overnight.
If a precipitate forms, it is collected by filtration, recrystallized from hot DMF and taken up in CH 2 Cl 2 And (5) washing. If no precipitate forms, the solvent is removed under reduced pressure. Water was added to the reaction mixture and used with CH 2 Cl 2 And (5) extracting. The crude product was purified by alumina column chromatography (CH 2 Cl 2 Hexane). Further purification is carried out by recrystallisation from hexane if required.
Example 202 preparation of emitter 101
The synthetic procedure of example 201 was employed. The crude product was purified by alumina column chromatography (CH 2 Cl 2 Hexane=1:1).Further purification was performed by recrystallisation from hexane. 0.06g (46% yield) of red product was obtained.
1 H NMR(500MHz,CDCl 3 )δ8.78(s,2H),7.92(dd,J＝5.9,3.4Hz,2H),7.71(d,J＝7.1Hz,4H),7.66(d,J＝0.8Hz,2H),7.56(d,J＝8.3Hz,2H),7.47(t,J＝7.3Hz,4H),7.43(d,J＝7.1Hz,2H),7.30–7.27(m,2H),7.02(dd,J＝8.3,1.3Hz,2H). 13 C NMR(101MHz,CDCl 3 ) Delta 148.92,148.56,145.90,140.90,135.84,129.72,129.12,128.31,127.86,121.65,121.42,117.12,116.08. FIG. 1 shows emitter 101 at CH 2 Cl 2 UV-vis and photoluminescence spectra at 298K.
Example 203 preparation of emitter 102
The synthetic procedure of example 201 was employed. A red precipitate formed and was collected by filtration, recrystallized from hot DMF and taken up with CH 2 Cl 2 And (5) washing. 0.16g (71% yield) of red product was obtained.
1 H NMR(400MHz,CDCl 3 )δ8.91(s,2H),8.02(dd,J＝6.1,3.5Hz,2H),7.61(d,J＝8.2Hz,2H),7.37(dd,J＝6.3,3.2Hz,2H),7.19(s,2H),6.93(s,4H),6.57(d,J＝8.1Hz,2H),2.33(s,6H),2.05(s,12H). 13 C NMR(101MHz,CDCl 3 ) Delta 166.69,150.32,149.27,146.04,139.26,137.59,135.88,135.34,128.81,128.42,124.31,121.17,119.82,116.05,21.84,21.21. Fig. 1 shows emitter 102 at CH 2 Cl 2 UV-vis and photoluminescence spectra at 298K.
Example 204 preparation of emitter 103
The synthetic procedure of example 201 was employed. The crude product was purified by alumina column chromatography (CH 2 Cl 2 Hexane=1:1). Further purification was performed by recrystallisation from MeOH.0.05g (29% yield) of red product is obtained.
1 H NMR(500MHz,CDCl 3 )δ8.93(s,1H),8.85(s,1H),8.06(d,J＝8.6Hz,1H),7.77(d,J＝0.9Hz,0H),7.62(d,J＝8.2Hz,1H),7.53(d,J＝8.2Hz,1H),7.19(d,J＝8.1Hz,3H),7.02(s,2H),6.93(s,2H),6.92(s,2H),6.58(dd,J＝8.2,1.3Hz,1H),6.54(dd,J＝8.2,1.3Hz,1H),2.38(s,3H),2.33(s,3H),2.32(s,3H),2.08(s,6H),2.06(s,6H),2.03(s,6H). 13 C NMR(126MHz,CDCl 3 ) Delta 165.92,165.81,149.55,149.47,148.56,148.30,145.43,143.93,141.13,138.45,138.44,137.70,136.97,136.76,135.89,135.08,135.04,134.54,134.49,128.62,128.36,128.00,123.47,120.43,120.37,119.05,119.01,116.05,115.17,21.04,21.03,20.77,20.41,20.35. FIG. 1 shows emitter 103 at CH 2 Cl 2 UV-vis and photoluminescence spectra at 298K.
Example 205 preparation of emitter 104
The synthetic procedure of example 201 was employed. The crude product was purified by alumina column chromatography (CH 2 Cl 2 Hexane=1:4). 0.37g of red product was obtained (58% yield).
1 H NMR(400MHz,CDCl 3 ) Delta 8.88 (s, 2H), 8.00 (dd, j=6.0, 3.2hz, 2H), 7.82 (d, j=7.2 hz, 2H), 7.76 (s, 2H), 7.54 (s, 2H), 7.49-7.41 (m, 4H), 7.41-7.35 (m, 2H), 7.32 (dd, j=5.8, 3.1hz, 2H), 1.54 (s, 12H). Fig. 2 shows emitter 104 on CH 2 Cl 2 UV-vis and photoluminescence spectra at 298K.
Example 206 preparation of emitter 105
The synthetic procedure of example 201 was employed. The crude product was purified by alumina column chromatography (CH 2 Cl 2 Hexane=1:4). 0.64g (60% yield) of red product was obtained)。
1 H NMR(300MHz,CDCl 3 ) Delta 13.39 (s, 2H), 8.73 (s, 2H), 7.80-7.66 (m, 4H), 7.45-7.28 (m, 14H), 1.96 (t, j=8.2 hz, 8H), 1.18-0.97 (m, 8H), 0.76-0.55 (m, 20H). Fig. 2 shows emitter 105 at CH 2 Cl 2 UV-vis and photoluminescence spectra at 298K.
EXAMPLE 207 preparation of emitter 106
The synthetic procedure of example 201 was employed. The crude product was purified by alumina column chromatography (CH 2 Cl 2 Hexane=1:4). 1.0g (69% yield) of red product was obtained.
1 H NMR(400MHz,CD 2 Cl 2 ) Delta 13.38 (s, 2H), 8.75 (s, 2H), 7.75 (s, 2H), 7.36 (m, 14H), 1.98 (t, j=7.9 hz, 8H), 1.06 (m, 24H), 0.76 (t, j=6.7 hz, 12H), 0.65 (d, j=20.9 hz, 8H). Fig. 2 shows emitter 106 at CH 2 Cl 2 UV-vis and photoluminescence spectra at 298K.
Example 208 preparation of emitter 107
The synthetic procedure of example 201 was employed. The red precipitate was collected by filtration, followed by water, meOH, and CH 2 Cl 2 And (5) washing. 0.12g (30% yield) of red product was obtained.
1 H NMR(500MHz,CDCl 3 )δ8.92(s,1H),8.84(s,1H),8.07(d,J＝8.5Hz,1H),7.80(t,J＝6.4Hz,2H),7.77(d,J＝7.4Hz,3H),7.45(s,1H),7.44–7.30(m,7H),7.13(d,J＝8.3Hz,1H),7.00(s,2H),2.37(s,3H),2.07(s,6H),1.98(t,J＝8.2Hz,4H),1.93(t,J＝7.9Hz,4H),1.19–1.01(m,8H),0.83–0.62(m,20H). 13 C NMR(126MHz,CDCl 3 )δ166.42,166.29,152.82,152.79,149.78,149.71,148.33,148.17,145.44,143.94,140.53,140.07,140.03,138.93,137.44,137.19,135.84,128.98,128.96,128.24,127.86,127.16,127.13,127.10,123.15,121.40,120.83,120.74,115.83,114.98,112.81,53.82,53.76,40.86,40.84,27.38,26.19,26.17,23.13,23.10,21.03,20.74,13.84,13.82.。
EXAMPLE 209 preparation of emitter 108
The synthetic procedure of example 201 was employed. The red precipitate was collected by filtration and redissolved in a large amount of CH 2 Cl 2 And washed with water. The solution was concentrated and the red precipitate was collected by filtration. 1.4g (57% yield) of red product was obtained.
1 H NMR(400MHz,DMSO)δ9.41(s,2H),8.38(s,2H),7.85(d,J＝8.2Hz,2H),7.73(d,J＝8.1Hz,4H),7.59–7.26(m,12H),7.26–7.04(m,14H),7.00(d,J＝8.0Hz,4H). 13 C NMR(126MHz,CDCl 3 ) Delta 165.62,148.18,147.66,147.38,146.80,144.93,134.99,133.10,129.36,127.68,127.17,124.91,123.35,122.97,120.52,119.28,115.63,115.15. Fig. 3 shows emitter 108 at CH 2 Cl 2 UV-vis and photoluminescence spectra at 298K.
Example 210 preparation of emitter 109
The synthetic procedure of example 201 was employed. The crude product was purified by alumina column chromatography and CH 2 Cl 2 And (5) purifying a mobile phase. Further purification was achieved by recrystallisation from hexane. 0.05g (70% yield) of red product is obtained.
1 H NMR(500MHz,CDCl 3 )δ8.86(s,2H),7.98(dd,J＝6.1,3.2Hz,2H),7.58(d,J＝8.2Hz,2H),7.33(dd,J＝6.2,3.2Hz,2H),7.28(t,J＝7.9Hz,8H),7.22(s,2H),7.16(d,J＝7.7Hz,8H),7.02(t,J＝7.3Hz,4H),6.81(s,4H),6.59(dd,J＝8.2,1.1Hz,2H),1.99(s,12H). 13 C NMR(126MHz,CDCl 3 )δ163.37,161.39,147.87,146.99,146.54,142.82,136.54,135.63,132.26,129.14,127.67,124.28,122.71,122.52,120.74,119.67,118.59,117.87,20.79. Fig. 3 shows emitter 109 in CH 2 Cl 2 UV-vis and photoluminescence spectra at 298K.
Example 211 preparation of emitter 110
The synthetic procedure of example 201 was employed. The red precipitate was collected by filtration and washed with water, meOH, and CH in sequence 2 Cl 2 And (5) washing. 0.06g (45% yield) of red product was obtained.
1 H NMR(500MHz,CDCl 3 )δ8.92(s,2H),8.16(d,J＝7.3Hz,4H),8.02(s,2H),7.96(d,J＝7.3Hz,4H),7.81(s,2H),7.77–7.62(m,6H),7.53(d,J＝7.6Hz,4H),7.44(t,J＝7.0Hz,4H),7.38(s,2H),7.31(t,J＝7.1Hz,4H),7.16(d,J＝7.6Hz,2H). 1 H NMR(500MHz,DMSO)δ9.58(s,2H),8.48(s,2H),8.25(d,J＝7.7Hz,4H),8.13(d,J＝7.5Hz,4H),8.02(d,J＝8.4Hz,2H),7.76(d,J＝7.8Hz,4H),7.55(s,2H),7.53–7.39(m,10H),7.35–7.21(m,J＝7.4Hz,6H). 13 C NMR (at 370K,126MHz, DMSO). Delta. 165.59,151.15,146.30,145.34,140.88,139.04,137.86,136.76,128.90,128.37,127.59,126.66,123.58,122.00,120.80,120.63,119.14,117.13,115.74,110.23. Fig. 3 shows emitter 110 at CH 2 Cl 2 UV-vis and photoluminescence spectra at 298K.
Example 212 photophysical data
Fig. 4 shows the EQE-luminance characteristics of emitters 102, 108, and 109. Fig. 5 shows the electroluminescent spectra of emitters 102, 108 and 109.
TABLE 1 emitters 101-110 a Photophysical data of (a)
a In a dichloromethane solution at 2X 10 -5 M is measured. b Measured by an integrating sphere. sh denotes the shoulder of the emission band.
The above data demonstrate that the red-emitting Pt (II) Schiff base complex of structure I with emission intensity enhancing group E shows a high Φ of greater than 0.38 em 。
Example 213-OLED manufacturing procedure
Materials: PEDOT PSS [ poly (3, 4-ethylenedioxythiophene): poly (styrenesulfonic acid) ] (clevelos P AI 4083) from Heraeus, PVK (polyvinylcarbazole) from Sigma-Aldrich, OXD-7[ (1, 3-bis [ (4-tert-butylphenyl) -1,3, 4-oxadiazolyl ] phenylene) ] and TPBi [2,2' - (1, 3, 5-benzenetriyl) -tris (1-phenyl-1-H-benzimidazole) ] from Luminescence Technology Corp. All materials were used as received.
Cleaning a substrate: glass slides with pre-patterned ITO electrodes used as substrates for OLEDs were washed in an ultrasonic bath of Decon 90 detergent and deionized water, rinsed with deionized water, then cleaned in a continuous ultrasonic bath of deionized water, acetone and isopropyl alcohol, and then dried in an oven for 1 hour.
Device fabrication and characterization: PEDOT PSS was spin coated on a clean ITO coated glass substrate and baked at 120℃for 20 minutes to remove residual aqueous solvent in a clean room. Blend of emissive layers at N 2 The filled glove box was spin coated with benzene chloride on the PEDOT: PSS layer. All EMLs were about 60nm thick. Then, annealing was performed at 110℃for 10 minutes in a glove box, and then transferred to a Kurt J.Lesker SPECTROS vacuum deposition system without exposure to air. Finally, at 10 by thermal evaporation -8 TPBi (40 nm), liF (1.2 nm), and Al (100 nm) were deposited in sequence at a pressure of mbar. EQE, PE, CE, and CIE coordinates were measured using a Keithley 2400 source table and absolute external quantum efficiency measurement system (C9920-12,Hamamatsu Photonics). All devices were characterized at room temperature without encapsulation. EQE and power efficiency are calculated by assuming a Lambertian distribution.
Example 214 Critical Performance data for solution processed OLEDs
Table 2. Data for OLEDs treated with solutions made by emitters 102, 108 and 109.
TABLE 3 Phi in solution model Complex 1 and model Complex 2 without E groups with emitters 102, 108 and 110 em The CIE aspects of the maximum CE, PE and EQE and the corresponding devices were compared. It can be seen that emitters 102, 108 and 110 exhibit superior Φ em Maximum CE, PE and EQE, which result from the presence of an E group at a particular position.
Table 3. Comparison of PL and EL data for model complexes and emitters 102, 108 and 109.
a On CH 2 Cl 2 Measured at room temperature. b Chem.Eur.J.,2010,16,233。 c Chem.Asian.J.,2014,9,2984。
For any graph or range of values for a given feature, a graph or parameter from one range may be combined with another graph or parameter from a different range for the same feature to produce the range of values.
Except in the operating examples, or where otherwise indicated, all numbers, values, and/or expressions referring to amounts of ingredients, reaction conditions, and the like, used in the specification and claims are to be understood as modified in all instances by the term "about".
It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application.
It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be included within the spirit and purview of this application and scope of the appended claims. Furthermore, any element or limitation of any invention disclosed herein or embodiments thereof may be combined with any and/or all other elements or limitations disclosed herein (alone or in any combination) or any other invention or embodiment thereof and all such combinations are intended to be within the scope of the present invention without limiting the invention.
All patents, patent applications, provisional applications, and publications mentioned or cited herein are hereby incorporated by reference in their entirety, including all figures and tables, provided they are not inconsistent with the explicit teachings of this specification.
The following is an example illustrating a program embodying the present invention. These examples should not be taken to be is to be construed as limiting. All percentages are by weight and all solvent mixture proportions are by volume unless otherwise indicated.

Claims (11)

1. Chemical having structure I OLED emitters of structure:
wherein Pt is in the oxidation state II complexed with a tetradentate ligand, wherein: x is X 1 -X 4 Independently carbon or nitrogen; r is R 1 -R 3 And R is 10 -R 12 Independently selected from hydrogen, halogen, hydroxy, unsubstituted C 1-10 Alkyl, halogen substituted C 1-10 Alkyl group、C 1-10 Alkyl substituted C 1-10 Alkyl and amino groups;
R 4 and R is 9 Independently selected from hydrogen and unsubstituted C 1-10 An alkyl group;
R 5 -R 8 independently selected from hydrogen, halogen, hydroxy, unsubstituted C 1-10 Alkyl, halogen substituted C 1-10 Alkyl, C 1-10 Alkyl substituted C 1-10 Alkyl, amino, unsubstituted C 6-20 Aryl, halogen substituted C 6-20 Aryl and C 1-10 Alkyl substituted C 6-20 An aryl group;
wherein the E group is:
wherein R is 13 -R 17 Independently unsubstituted C 1-10 Alkyl, halogen substituted C 1-10 Alkyl, C 1-10 Alkyl substituted C 1-10 Alkyl, unsubstituted C 6-20 Aryl, halogen substituted C 6-20 Aryl, C 1-10 Alkyl substituted C 6-20 Aryl or amino;
R 18 and R is 31 Independently hydrogen, methyl, isopropyl, or phenyl; r is R 19 -R 30 Independently hydrogen, halogen, hydroxy, unsubstituted C 1-10 Alkyl, halogen substituted C 1-10 Alkyl, C 1-10 Alkyl substituted C 1-10 Alkyl, unsubstituted C 6-20 Aryl, halogen substituted C 6-20 Aryl, C 1-10 Alkyl substituted C 6-20 Aryl or amino; and optionally, wherein R 24 And R is 25 Combining into a 5-8 membered ring;
wherein R is 1 、R 2 、R 11 And R is 12 Is not part of an amino group or a substituted azacyclic aromatic group, and optionally wherein R 1 、R 2 、R 11 And R is 12 Independently and independently from the E group into a 5-8 membered ring.
2. The OLED emitter of claim 1, wherein R 1 -R 3 And R is 10 -R 12 Independently hydrogen, unsubstituted C 1-10 Alkyl or C 1-10 Alkyl substituted C 1-10 An alkyl group;
R 4 and R is 9 Independently selected from hydrogen and unsubstituted C 1-6 An alkyl group;
R 5 -R 8 independently selected from hydrogen, unsubstituted C 1-6 Alkyl, phenyl and C 1-6 An alkyl-substituted phenyl group;
and optionally wherein adjacent R' s 1 -R 2 And R is 11 -R 12 And E groups are independently combined to form a 5-membered ring.
3. The OLED emitter of claim 1, wherein R 13 -R 17 Independently unsubstituted C 1-10 Alkyl, C 1-10 Alkyl substituted C 1-10 Alkyl, unsubstituted phenyl or C 1-10 An alkyl-substituted phenyl group.
4. The OLED emitter of claim 1, wherein R 18 And R is 31 Independently hydrogen, methyl, isopropyl, or phenyl; r is R 19 -R 30 Independently hydrogen, unsubstituted C 1-10 Alkyl, halogen substituted C 1-10 Alkyl, C 1-10 Alkyl substituted C 1-10 Alkyl, unsubstituted phenyl or C 1-10 An alkyl-substituted phenyl group; and optionally, wherein R 24 And R is 25 Is combined into a 5-8 membered ring.
5. An OLED emitter, wherein the emitter comprises at least one selected from the group consisting of emitter 101-emitter 122:
6. an emitter light emitting device comprising at least one emissive layer, wherein at least one of the emissive layers comprises one or more OLED emitters according to claims 1 to 5.
7. The emitter light emitting device according to claim 6, wherein the device is an organic light emitting diode.
8. The emitter light emitting device according to claim 6, wherein the device comprises a plurality of emissive layers.
9. A method of making an emitter light emitting device, comprising:
providing a transparent substrate;
providing a transparent electrode;
depositing an emissive layer comprising an emitter according to one or more of claims 1 to 5; and
a counter electrode is deposited to the transparent electrode.
10. The method of claim 9, wherein depositing the emissive layer is performed in solution.
11. The method of claim 9, wherein depositing the emissive layer is vapor deposition.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101878279A (en) * 2007-11-12 2010-11-03 默克专利有限公司 Organic electroluminescent devices comprising azomethine-metal complexes
CN105273712A (en) * 2014-07-11 2016-01-27 广东阿格蕾雅光电材料有限公司 Luminescent material used for light emitting diodes
CN108569995A (en) * 2017-03-07 2018-09-25 香港大学 Platinum complex and its device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101878279A (en) * 2007-11-12 2010-11-03 默克专利有限公司 Organic electroluminescent devices comprising azomethine-metal complexes
CN105273712A (en) * 2014-07-11 2016-01-27 广东阿格蕾雅光电材料有限公司 Luminescent material used for light emitting diodes
CN108569995A (en) * 2017-03-07 2018-09-25 香港大学 Platinum complex and its device

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Pietrangelo, A. et al..Synthesis and electrochemistry of new thienyl-Schiff base complexes.《Canadian Journal of Chemistry》.2008,第87卷(第87期),第314-320页. *
Youming Zhang et al..Achieving NIR emission for tetradentate platinum (II) salophen complexes by attaching dual donor-accepter frameworks in the heads of salophen.《Dyes and Pigments》.2016,第138卷第100-106页. *

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