Organic optoelectronic device and display or lighting device comprising same
阅读说明：本技术 有机光电器件及包含其的显示或照明装置 (Organic optoelectronic device and display or lighting device comprising same ) 是由 王鹏 于 2021-10-22 设计创作，主要内容包括：本发明公开了一种有机光电器件及包含其的显示或照明装置,其中该有机光电器件包含金属有机化合物,其具有下列式1所示的结构：本发明的有机光电器件的电流效率有了显著提升,同时其寿命也有所提升。(The present invention discloses an organic photoelectric device and a display or lighting device comprising the same, wherein the organic photoelectric device comprises a metal organic compound having a structure represented by the following formula 1:)
1. An organic optoelectronic device comprising a cathode layer, an anode layer and an organic layer, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer or an electron transport layer, wherein the organic layer comprises a metal organic compound having a structure represented by the following general formula 1:
wherein the content of the first and second substances,
m is selected from beryllium, magnesium, aluminum, calcium, titanium, manganese, cobalt, copper, zinc, gallium, germanium, zirconium, ruthenium, rhodium, palladium, silver, rhenium, platinum or gold;
X1selected from O,S, N (R), P (R), B (R), C (R), Si (R), (R '), Ge (R), (R') or a bond, and when X is1Selected from the group consisting of chemical bonds, Y1Directly bonded to M;
X2、X3、X5or Y1-Y4Are identical or different from each other and are each independently selected from a C or N atom;
X4selected from O, S, N, N (R), C (R), (R '), si (R), (R '), ge (R), (R '), C (═ O), C (R), si (R), or ge (R);
X1or Y1And the chemical bond between M is a covalent bond;
X2chemical bond between M, X3Chemical bond between M, X5One of the chemical bonds with M is a covalent bond, and the remaining two chemical bonds are coordination bonds;
Z1-Z5each independently is deuterium or a deuterium-containing group;
n1-n5each independently is an integer from 0 to 20;
CY1-CY6each independently selected from C5-C30And C is a carbocyclic group1-C30And CY1、CY3、CY4Or CY5Each independently is not a benzimidazole group;
CY3and CY4Directly connected to each other, sharing at least one atom, CY4And CY5Are directly connected, and at least share one atom;
R1-R5are identical or different from each other and are each independently selected from the group consisting of hydrogen, deuterium, a group containing deuterium, halogen, SF5Hydroxy, mercapto, cyano, nitro, hydrazone, hydrazine, amidino, carboxy or carboxylate, sulfonic or sulfonate, phosphoric or phosphate, substituted or unsubstituted C1-C60Alkyl, substituted or unsubstituted C3-C10Cycloalkyl, substituted or unsubstituted C3-C10Heterocycloalkyl, substituted or unsubstituted C2-C60Alkenyl, substituted or unsubstituted C3–C10Cycloalkenyl radicals, derivatives thereofSubstituted or unsubstituted C3-C10Heterocycloalkenyl, substituted or unsubstituted C2-C6Alkynyl, substituted or unsubstituted C2-C6Cycloalkynyl, substituted or unsubstituted C2-C6Heterocycloalkynyl, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C1-C60Sulfoxy, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C7-C60Alkylaryl, substituted or unsubstituted C6-C60Aryloxy, substituted or unsubstituted C6-C60Arylthio, substituted or unsubstituted C7-C60Aralkyl, substituted or unsubstituted C1-C60Heteroaryl, substituted or unsubstituted C1-C60Heteroaryloxy, substituted or unsubstituted C1-C60Heteroarylthio, substituted or unsubstituted C2-C60Heteroaralkyl, substituted or unsubstituted C2-C60One or more of an alkylheteroaryl group, a substituted or unsubstituted monovalent non-aromatic fused polycyclic group, a substituted or unsubstituted monovalent non-aromatic fused heteropolycyclic group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted silane group, a substituted or unsubstituted arylsilicon group, a substituted or unsubstituted boryl group, a substituted or unsubstituted phosphinoxy group;
L1selected from the group consisting of a single bond, a double bond, x-n- (R) -, ' b- (R) -, ' p- (R) -, ' C- (R '), ' si- (R '), ' ge- (R '), ' O ', ' S- (S) -, ' Se- (Se '), ' C (═ O) ', ' S (═ O '), ' S (═ O) ') and ' S (═ O) ')2-C (R) -, (R '), (S) -, or ≡ C-', wherein each of ═ and ≡ denotes a binding site to an adjacent atom;
wherein R and R' are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C4～C30One or more of heteroaryl groups.
2. The organic optoelectronic device of claim 1, wherein CY in the metal-organic compound structure4Selected from any one of the following groups:
wherein R is6-R11Are identical or different from each other and are each independently selected from the group consisting of hydrogen, deuterium, a group containing deuterium, halogen, SF5Hydroxy, mercapto, cyano, nitro, hydrazone, hydrazine, amidino, carboxy or carboxylate, sulfonic or sulfonate, phosphoric or phosphate, substituted or unsubstituted C1-C60Alkyl, substituted or unsubstituted C3-C10Cycloalkyl, substituted or unsubstituted C3-C10Heterocycloalkyl, substituted or unsubstituted C2-C60Alkenyl, substituted or unsubstituted C3–C10Cycloalkenyl, substituted or unsubstituted C3-C10Heterocycloalkenyl, substituted or unsubstituted C2-C6Alkynyl, substituted or unsubstituted C2-C6Cycloalkynyl, substituted or unsubstituted C2-C6Heterocycloalkynyl, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C1-C60Sulfoxy, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C7-C60Alkylaryl, substituted or unsubstituted C6-C60Aryloxy, substituted or unsubstituted C6-C60Arylthio, substituted or unsubstituted C7-C60Aralkyl, substituted or unsubstituted C1-C60Heteroaryl, substituted or unsubstituted C1-C60Heteroaryloxy, substituted or unsubstituted C1-C60Heteroarylthio, substituted or unsubstituted C2-C60Heteroaralkyl, substituted or unsubstituted C2-C60One or more of an alkylheteroaryl group, a substituted or unsubstituted monovalent non-aromatic fused polycyclic group, a substituted or unsubstituted monovalent non-aromatic fused heteropolycyclic group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted silane group, a substituted or unsubstituted arylsilicon group, a substituted or unsubstituted boryl group, a substituted or unsubstituted phosphinoxy group;
r and R' are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C4～C30One or more of heteroaryl;
wherein denotes the binding site to the adjacent atom.
3. The organic optoelectronic device according to claim 1 or 2, wherein the metal-organic compound is selected from any one of the following structures:
4. the organic optoelectronic device according to claim 1 or 2, wherein the organic layer is a light emitting layer.
5. The organic optoelectronic device according to claim 1 or 2, wherein the organic optoelectronic device is an organic photovoltaic device, an organic light emitting device, an organic solar cell, electronic paper, an organic photoreceptor, an organic thin film transistor, or an organic memory device.
6. A display or lighting device comprising the organic optoelectronic device of claim 1 or 2.
Technical Field
The invention relates to an organic photoelectric device and a display or lighting device comprising the same, belonging to the field of organic electroluminescence.
Background
Organic light-emitting devices (OLEDs) have been attracting attention and research since their birth as a new generation of flat panel display technology. Typical OLEDs have the following characteristics: the material adopts organic matters, and the range of optional compounds is wide, so that full-color display from red light to blue light can be realized; the driving voltage is low, and only 3-12V direct current voltage is needed; the luminous brightness and luminous efficiency are high, and the response speed is high; ultra-thin, ultra-light, because the materials used are organic, OLEDs can be bent and not limited by size compared to inorganic devices; the working temperature range is wide; relatively simple and convenient manufacturing and processing, and the like. Therefore, in the field of flat panel display, the OLED device plays an important role because of its characteristics of high efficiency, energy saving and environmental protection. However, the industrialization of OLEDs is far less than expected and some key theoretical issues are not solved. Mainly focuses on the optimization of OLED materials, colorization technology, high-resolution display technology, film manufacturing technology, packaging technology, active driving technology and the like. The problems of low efficiency and short lifetime of the device are the biggest problems among them. To solve these problems, the material properties, device structure, operation principle, and interface characteristics are considered. In recent years, research on metal complex phosphorescent materials (Ph-OLEDs) has been rapidly developed, and luminescent properties of metal complex compounds such as rhenium (I), ruthenium (ii), osmium (ii), iridium (I, iii), platinum (ii), and the like have been sufficiently theoretically and experimentally researched, and they have good luminescent properties and wide application prospects. The metal complex has electron absorption in the ultraviolet region and electron emission in the visible region, and can be used as an excellent luminescent material. At present, phosphorescent light-emitting materials have a short lifetime and poor device stability, and how to design materials with better performance is always a problem to be solved by those skilled in the art.
Disclosure of Invention
In order to overcome the defects in the prior art, an object of the present invention is to provide an organic photoelectric device having high luminous efficiency and improved lifetime, and a display or lighting apparatus including the same.
In order to realize the purpose of the invention, the technical scheme of the invention is as follows:
the invention provides an organic photoelectric device, which comprises a cathode layer, an anode layer and an organic layer, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer or an electron transport layer, the organic layer comprises a metal organic compound and has a structure shown in the following formula 1:
wherein the content of the first and second substances,
m is a metal selected from beryllium (Be), magnesium (Mg), aluminum (Al), calcium (Ca), titanium (Ti), manganese (Mn), cobalt (Co), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), zirconium (Zr), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), rhenium (Re), platinum (Pt) or gold (Au);
X1selected from O, S, N (R), P (R), B (R), C (R), Si (R) (R '), Ge (R) (R') or a bond, and when X is1When the chemical bond is selected from the group consisting of chemical bonds,
Y1directly bonded to M;
X2、X3、X5or Y1-Y4Are identical or different from each other and are each independently selected from a C or N atom;
X4selected from O, S, N, N (R), C (R), (R '), si (R), (R '), ge (R), (R '), C (═ O), C (R), si (R), or ge (R);
X1or Y1And the chemical bond between M is a covalent bond;
X2chemical bond between M, X3Chemical bond between M, X5One of the chemical bonds with M is a covalent bond, and the remaining two chemical bonds are coordination bonds;
Z1-Z5each independently is deuterium or a deuterium-containing group;
n1-n5each independently is an integer from 0 to 20;
CY1-CY6each independently selected from C5-C30And C is a carbocyclic group1-C30And CY1、CY3、CY4Or CY5Each independently is not a benzimidazole group;
CY3and CY4Directly connected to each other, sharing at least one atom, CY4And CY5Are directly connected, and at least share one atom;
R1-R5are identical or different from each other and are each independently selected from the group consisting of hydrogen, deuterium, a group containing deuterium, halogen, SF5Hydroxy, mercapto, cyano, nitro, hydrazone, hydrazine, amidino, carboxy or carboxylate, sulfonic or sulfonate, phosphoric or phosphate, substituted or unsubstituted C1-C60Alkyl, substituted or unsubstituted C3-C10Cycloalkyl, substituted or unsubstituted C3-C10Heterocycloalkyl, substituted or unsubstituted C2-C60Alkenyl, substituted or unsubstituted C3–C10Cycloalkenyl, substituted or unsubstituted C3-C10Heterocycloalkenyl, substituted or unsubstituted C2-C6Alkynyl, substituted or unsubstituted C2-C6Cycloalkynyl, substituted or unsubstituted C2-C6Heterocycloalkynyl, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C1-C60Sulfoxy, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C7-C60Alkylaryl, substituted or unsubstituted C6-C60Aryloxy, substituted or unsubstituted C6-C60Arylthio, substituted or unsubstituted C7-C60Aralkyl, substituted or unsubstituted C1-C60Heteroaryl, substituted or unsubstituted C1-C60Heteroaryloxy, substituted or unsubstituted C1-C60Heteroarylthio, substituted or unsubstituted C2-C60Heteroaralkyl, substituted or unsubstituted C2-C60One or more of an alkylheteroaryl group, a substituted or unsubstituted monovalent non-aromatic fused polycyclic group, a substituted or unsubstituted monovalent non-aromatic fused heteropolycyclic group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted silane group, a substituted or unsubstituted arylsilicon group, a substituted or unsubstituted boryl group, a substituted or unsubstituted phosphinoxy group;
L1selected from the group consisting of single bond, double bond, [ n ], [ b ], [ R ], [ p ], [ R ], [ c ] (R '), [ si ] (R '), [ p ], [ R ], [ p ], [ R '), [ c ], [ p ], [ R ], [ c, and the like,
*—Ge(R)(R’)—*’、*—O—*’、*—S—*’、*—Se—*’、*—C(＝O)—*’、*—S(＝O)—*’、*—S(＝O)2—*’、
-C (R) ═ C (R) ·, — C (R) ·, — C (R') —, — C (═ S) — or ≡ C —, wherein ·and ≡ each represent a binding site to an adjacent atom;
wherein R and R' are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C4～C30One or more of heteroaryl groups.
Preferably, wherein C in the structure of the metal-organic compoundY4Selected from any one of the following groups:
wherein R is6-R11Are identical or different from each other and are each independently selected from the group consisting of hydrogen, deuterium, a group containing deuterium, halogen, SF5Hydroxy, mercapto, cyano, nitro, hydrazone, hydrazine, amidino, carboxy or carboxylate, sulfonic or sulfonate, phosphoric or phosphate, substituted or unsubstituted C1-C60Alkyl, substituted or unsubstituted C3-C10Cycloalkyl, substituted or unsubstituted C3-C10Heterocycloalkyl, substituted or unsubstituted C2-C60Alkenyl, substituted or unsubstituted C3–C10Cycloalkenyl, substituted or unsubstituted C3-C10Heterocycloalkenyl, substituted or unsubstituted C2-C6Alkynyl, substituted or unsubstituted C2-C6Cycloalkynyl, substituted or unsubstituted C2-C6Heterocycloalkynyl, substituted or unsubstituted C1-C60Alkoxy, substituted or unsubstituted C1-C60Sulfoxy, substituted or unsubstituted C6-C60Aryl, substituted or unsubstituted C7-C60Alkylaryl, substituted or unsubstituted C6-C60Aryloxy, substituted or unsubstituted C6-C60Arylthio, substituted or unsubstituted C7-C60Aralkyl, substituted or unsubstituted C1-C60Heteroaryl, substituted or unsubstituted C1-C60Heteroaryloxy, substituted or unsubstituted C1-C60Heteroarylthio, substituted or unsubstituted C2-C60Heteroaralkyl, substituted or unsubstituted C2-C60An alkylheteroaryl group, a substituted or unsubstituted monovalent non-aromatic fused polycyclic group, a substituted or unsubstituted monovalent non-aromatic fused heteropolycyclic group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted siliconOne or more of alkyl, substituted or unsubstituted aromatic silicon base, substituted or unsubstituted boryl, substituted or unsubstituted phosphino;
r and R' are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C15Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C4～C30One or more of heteroaryl;
wherein denotes the binding site to the adjacent atom.
More preferably, the metal organic compound is selected from any one of the following structures:
preferably, the organic layer is a light emitting layer.
Preferably, the organic optoelectronic device is an organic photovoltaic device, an organic light emitting device, an organic solar cell, electronic paper, an organic photoreceptor, an organic thin film transistor, or an organic memory device.
The invention also provides a display or lighting device comprising an organic optoelectronic device of the invention.
Detailed Description
The present invention provides an organic opto-electronic device comprising: a first electrode;
a second electrode facing the first electrode;
an organic layer sandwiched between the first electrode and the second electrode; wherein the organic layer comprises the organometallic compound of the present invention.
The organic layer is preferably a light-emitting layer, wherein the metal organic compound is a doping material.
The organic photoelectric device comprising the metal organic compound of the present invention includes a substrate, a first electrode, an organic layer, a second electrode, and a capping layer. Preferably, the organic optoelectronic device comprises a substrate, a first electrode located on the substrate, an organic layer located on the first electrode, a second electrode located on the organic layer, and a covering layer located on the outer side of the second electrode, wherein the outer side of the second electrode refers to the side facing away from the first electrode.
The organic layer of the present invention is at least one of a light-emitting layer (active layer), a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer. And the organic layer may be formed of a single layer structure or a stacked (multi-layer structure including a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer) structure. Wherein the hole transport layer may further include a first hole transport layer and a second hole transport layer. In the organic photoelectric device of the present invention (e.g., organic electroluminescent diode), any material known in the art for the layer may be used for the layer except that the light-emitting layer contains the metal-organic compound of the present invention.
In the light-emitting element of the present invention, the substrate material can be any substrate typically used in organic light-emitting elements, such as soda glass, alkali-free glass or transparent flexible substrate, a substrate made of an opaque material such as silicon or stainless steel, or a flexible polyimide film, and different substrate materials have different properties and different application directions. The hole transport layer of the present invention can be formed by a method of stacking or mixing one or two or more kinds of hole transport materials, or a method of using a mixture of a hole transport material and a polymer binder. Since the hole transport material needs to transport holes from the positive electrode efficiently between electrodes to which an electric field is applied, it is desirable that the hole transport material has high hole injection efficiency and can transport injected holes efficiently. Therefore, the hole transport material should have an appropriate ionization potential and an appropriate energy level and have a large hole mobility, and further, the material is excellent in stability and impurities that become traps are not easily generated during manufacturing and use. The substance satisfying such conditions is not particularly limited, and examples thereof include carbazole derivatives, triarylamine derivatives, biphenyldiamine derivatives, fluorene derivatives, phthalocyanine compounds, hexacarbonitrile hexaazatriphenylene compounds, quinacridone compounds, perylene derivatives, anthraquinone compounds, F4-TCNQ, polyaniline, polythiophene, and polyvinylcarbazole, but are not limited thereto.
The organic layer materials of the present invention, when they are used, may be formed into a single layer structure by film-forming alone, or may be mixed with other materials to form a single layer structure, or may be formed into a laminated structure of single layers formed alone, a laminated structure of single layers mixed into a film, a laminated structure of single layers formed alone and a laminated structure of single layers mixed into a film, but are not limited thereto. The organic photoelectric device (e.g., organic electroluminescent diode) of the present invention can be manufactured by sequentially stacking the above-described structures. As the production method, known methods such as a dry film formation method and a wet film formation method can be used, and examples of the dry film formation method include a vacuum deposition method, a sputtering method, a plasma method, and an ion plating method; the wet film formation method may be, for example, various coating methods such as a spin coating method, a dipping method, a casting method, an ink jet method, but is not limited thereto. The organic photoelectric device (such as an organic electroluminescent diode) of the present invention can be widely applied to the fields of panel display, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, signs, signal lamps, and the like.
The Organic light emitting device of the present invention is an Organic photovoltaic device, an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), electronic paper (e-paper), an Organic Photoreceptor (OPC), an Organic Thin Film Transistor (OTFT), and an Organic Memory device (Organic Memory Element).
Examples
The organometallic compounds of the invention are illustrated by, but not limited to, the following examples.
The initial raw materials and solvents adopted in the embodiments and the comparative examples of the invention are purchased from national medicine, and part of commonly used products such as OLED intermediates are purchased from domestic OLED intermediate manufacturers and various palladium catalysts, ligands and the like are purchased from sigma-Aldrich companies.
1H-NMR data were determined using a JEOL (400MHz) nuclear magnetic resonance apparatus;
HPLC data were determined using a Shimadzu LC-20AD HPLC.
Example 1
Synthesis of Compound 11
(1) 43.0 g (100mmol) of the compound 11-A, 11-B45.0g (110mmol) of the compound 11-B, 648 mg of [1, 3-bis (2, 6-di-isopropylphenyl) -4, 5-dihydroimidazol-2-ylidene ] chloro ] [ 3-phenylallyl ] palladium (II) catalyst, 200ml (300mmol) of 1.5M aqueous sodium carbonate solution and 1000ml of ethylene glycol dimethyl ether (DME) were charged into a reaction vessel under an argon atmosphere, and the mixture was stirred at 80 ℃ overnight. Cooled to room temperature, 800ml of water was added, a solid was precipitated, filtered, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 48.1g of compound 11-C, yield 76%, purity by HPLC 99.3%.
1HNMR(DMSO)：δ9.61(s，1H),8.66(d，1H),8.19(d，1H),8.13(m,2H),8.03(s,1H),7.76(s,1H),7.62(m,1H),7.48(m,3H),7.41(m,1H),7.38(d,2H),7.01(d,1H),6.92(d,1H),6.86(m,1H),1.72(s,6H),1.40(s,9H).
(2) Under argon atmosphere, the compound 11-C63.3 g (100mmol), K are added into a reaction vessel in turn2PtCl445.7 g (110mmol), 2100ml of acetic acid and 300ml of chloroform, and the reaction was refluxed for 4 days. After the reaction is finished, neutralizing with potassium carbonate, extracting with dichloromethane, removing the solvent by organic phase under reduced pressure, separating the obtained solid by using a silica gel chromatographic column with a mobile phase of a normal hexane/dichloromethane system, and then recrystallizing with methanol to obtain 1137.17 g of a target compound, wherein the HPLC purity is 99.9%, and the yield is 45%
1HNMR(DMSO)：δ8.66(d，1H),8.32(d，1H),8.19(d,1H),8.03(s,1H),7.76(s,1H),7.62(m,1H),7.48(m,3H),7.41(m,1H),7.38(d,2H),7.10(m,1H),7.01(d,1H),6.92(d,1H),1.72(s,6H),1.40(s,9H).
Example 2
Synthesis of Compound 24
Same as example 1 except that the starting materials were changed to 24-A and 24-B
1HNMR(DMSO)：δ8.66(d，1H),8.51(d，1H),8.19(d,1H),8.15(m,1H),8.03(s,1H),7.80(d,1H),7.77(d,1H),7.66(m,1H),7.56(s,1H),7.50(m,1H),7.41(m,2H),7.19(m,4H),1.72(s,6H),1.40(s,9H),1,32(s,9H).
Example 3
Synthesis of Compound 71
The procedure of example 1 was repeated, except that the starting materials were changed to 71-A and 71-B.
1HNMR(DMSO)：δ8.66(d，1H),8.51(d，1H),8.19(d,1H),8.15(m,1H),7.86(s,1H),7.62(m,1H),7.56(s,1H),7.48(m,2H),7.43(m,1H),7.41(m,2H),7.38(d,2H),7.06(d,2H),2.33(s,6H),1.40(s,18H),1,32(s,9H).
Example 4
Synthesis of Compound 102
The procedure of example 1 was repeated, except that the starting materials were changed to 102-A and 102-B.
1HNMR(DMSO)：δ8.66(d，1H),8.51(d，1H),8.19(d,1H),8.15(m,1H),7.86(s,1H),7.80(d,1H),7.77(d,1H),7.66(m,1H),7.56(s,1H),7.51(d,2H),7.50(m,1H),7.46(m,2H),7.43(m,1H),7.41(m,3H),7.19(m,2H),7.06(d,2H)，2.33(s,6H),1.40(s,9H),1,32(s,9H).
Example 5
Synthesis of Compound 126
The procedure of example 1 was repeated, except that the starting materials were changed to 126-A and 126-B.
1HNMR(DMSO)：δ8.73(d，1H),8.66(d，1H),8.19(d,1H),7.95(s,1H),7.91(d,1H),7.62(m,1H),7.56(s,1H),7.48(m,2H),7.41(m,2H),7.38(d,2H),1.40(s,9H),1.35(s,21H),1,32(s,9H),0.89(s,6H).
Example 6
Synthesis of Compound 141
The procedure of example 1 was repeated, except that the starting materials were changed to 141-A and 141-B.
1HNMR(DMSO)：δ8.73(d，1H),8.66(d，1H),8.19(d,1H),8.03(s,1H),7.91(d,1H),7.62(m,1H),7.51(s,1H),7.48(m,2H),7.41(m,1H),7.38(d,2H),7.33(d，4H),7.15(d,4H),7.00(s,1H),2.34(s,6H),1.35(s,12H),0.89(s,6H).
Example 7
Synthesis of Compound 173
The procedure of example 1 was repeated, except that the starting materials were changed to 173-A and 173-B.
1HNMR(DMSO)：δ8.82(s，1H),8.66(d，1H),8.60(d,1H),8.19(d,1H),7.62(m,3H),7.60(d,1H),7.58(m,1H),7.50(d,2H),7.48(m,2H),7.41(m,1H),7.38(d,2H),7.32(m,1H),7.22(m，1H),7.06(m,1H),7.00(m,1H),1.35(s,9H).
Example 8
Synthesis of Compound 212
The procedure of example 1 was repeated, except that the starting materials were changed to 212-A and 212-B.
1HNMR(DMSO)：δ8.82(s，1H),8.66(d，1H),8.60(d,1H),8.19(d,1H),7.62(m,3H),7.60(d,1H),7.58(m,1H),7.50(d,2H),7.48(m,2H),7.41(m,1H),7.38(d,2H),7.32(m,1H),7.22(m，1H),7.06(m,1H),7.00(m,1H),1.35(s,9H).
Example 9
Synthesis of Compound 241
The procedure of example 1 was repeated, except that the starting materials were changed to 241-A and 241-B.
1HNMR(DMSO)：δ8.73(d，1H),8.66(d，1H),8.19(d,1H),8.02(s,1H),7.91(d,1H),7.56(s,1H),7.41(m,2H),7.31(d,2H),7.09(d,2H),1.69(s,6H),1.40(s,9H),1.35(s,18H),1.33(s,9H),1.32(s,9H).
Example 10
Synthesis of Compound 275
The procedure of example 1 was repeated, except that the starting materials were changed to 275-A and 275-B.
1HNMR(DMSO)：δ8.73(d，1H),8.66(d，1H),8.19(d,1H),8.02(s,1H),7.91(d,1H),7.80(d,2H),7.77(d,2H),7.75(d,2H),7.56(s,1H),7.49(m,2H),7.46(m,2H),7.41(m,4H),7.38(d,2H),1.69(s,6H),1.40(s,9H),1.32(s,9H).
Example 11
Synthesis of Compound 315
The procedure of example 1 was repeated, except that the starting materials were changed to 315-A and 315-B.
1HNMR(DMSO)：δ8.66(d，1H),8.54(d，1H),8.19(d,1H),7.90(d,2H),7.86(d,1H),7.62(m,1H),7.56(d,1H),7.55(d,2H),7.51(s,1H),7.48(m,2H),7.41(m,1H),7.38(m,4H),7.29(d,1H),7.28(m,2H),7.00(s,1H),6.86(m,1H).
Example 12
Synthesis of Compound 319
The procedure of example 1 was repeated, except that the starting materials were changed to 319-A and 319-B.
1HNMR(DMSO)：δ8.54(d，1H),7.90(d,2H),7.86(d,1H),7.62(m,1H),7.56(d,1H),7.55(d,2H),7.50(s,1H),7.51(s,1H),7.48(m,3H),7.41(m,1H),7.38(m,4H),7.29(d,1H),7.28(m,2H),7.00(s,1H),6.86(m,1H),2.36(s,3H),2.15(s,3H).
Example 13
Synthesis of Compound 340
The procedure of example 1 was repeated, except that the starting materials were changed to 340-A and 340-B.
1HNMR(DMSO)：δ8.66(d，1H),8.59(d，1H),8.19(d,1H),8.10(s,1H),7.73(s,2H),7.60(d,1H),7.55(s,1H),7.41(m,1H),7.36(m,1H),7.33(d,1H),7.32(m,1H),7.06(m,1H),7.00(d,1H),1.32(s,18H)..
Example 14
Synthesis of Compound 354
The procedure of example 1 was repeated, except that the starting materials were changed to 354-A and 354-B.
1HNMR(DMSO)：δ8.78(d，1H),8.66(d，1H),8.19(d,1H),7.99(d,1H),7.80(d,1H),7.79(s,1H),7.77(d,1H),7.66(m,1H),7.56(s,1H),7.50(m,1H),7.41(m,3H),7.19(m,4H),1.40(s,9H),1.35(s,9H),1.32(s,9H).
Example 15
Synthesis of Compound 405
The procedure of example 1 was repeated, except that the starting materials were changed to 405-A and 405-B.
1HNMR(DMSO)：δ8.78(d，1H),8.66(d，1H),8.19(d,1H),7.99(d,1H),7.63(s,1H),7.60(d,1H),7.41(m,1H),7.32(m,1H),7.31(d,2H),7.09(d,2H),7.06(m,1H),7.00(d,1H),1.35(s,9H),1.33(s,9H).
Example 16
Synthesis of Compound 437
The procedure was as in example 1 except that the starting materials were changed to 437-A and 437-B.
1HNMR(DMSO)：δ8.78(d，1H),8.66(d，1H),8.19(d,1H),7.99(d,1H),7.93(s,1H),7.72(d,1H),7.63(s,1H),7.56(s,1H),7.51(d,2H),7.46(m,2H),7.41(m,5H),7.19(m,4H),1.43(s,9H),1.40(s,9H),1.32(s,9H).
Example 17
Synthesis of Compound 450
The procedure of example 1 was repeated, except that the starting materials were changed to 450-A and 450-B.
1HNMR(DMSO)：δ8.73(d，1H),8.66(d，1H),8.32(s,1H),8.19(d,1H),7.86(d,1H),7.73(s,2H),7.60(d,1H),7.55(s,1H),7.41(m,1H),7.32(m,1H),7.16(m,1H),7.06(m,5H),7.00(d,1H),1.32(s,18H).
Example 18
Synthesis of Compound 485
The procedure of example 1 was repeated, except that the starting materials were changed to 485-A and 485-B.
1HNMR(DMSO)：δ8.92(d，1H),8.66(d，1H),8.32(s,1H),8.21(d,1H),8.19(d,1H),7.51(m,4H),7.46(m,4H),7.41(m,3H),7.00(s,1H),2.36(s,3H),2.15(s,3H).
Example 19
Synthesis of Compound 508
The procedure of example 1 was repeated, except that the starting materials were changed to 508-A and 508-B.
1HNMR(DMSO)：δ8.66(d，1H),8.38(s,1H),8.33(d,1H),8.19(d,1H),8.15(d,2H),8.13(d,1H),8.12(d,1H)，7.79(d,1H),7.73(d,1H),7.65(m,1H),7.59(m,1H),7.52(m,1H),7.41(m,1H),7.33(s,1H),7.12(m,1H),6.81(d,1H),1.35(s,9H).
Example 20
Synthesis of Compound 539
The procedure was as in example 1 except that the starting materials were changed to 539-A and 539-B.
1HNMR(DMSO)：δ8.33(d,1H),8.22(m,1H),8.18(m,1H),8.13(d,1H),7.62(m,1H)，7.51(s,1H),7.50(s,1H),7.48(m,3H),7.38(d,2H),7.12(m,1H),7.00(s,1H),2.36(s,3H),2.15(s,3H).
Example 21
Synthesis of Compound 574
The procedure of example 1 was repeated, except that the starting materials were changed to 574-A and 574-B.
1HNMR(DMSO)：δ8.33(d,1H),8.22(m,1H),8.18(m,1H),8.13(d,1H),7.62(m,1H)，7.51(s,1H),7.50(s,1H),7.48(m,3H),7.38(d,2H),7.12(m,1H),7.00(s,1H),2.36(s,3H),2.15(s,3H).
Example 22
Synthesis of Compound 605
The procedure of example 1 was repeated, except that the starting materials were changed to 605-A and 605-B.
1HNMR(DMSO)：δ8.73(d，1H),8.66(d，1H),8.19(d,1H),7.95(s,1H),7.91(d,1H),7.80(d,2H),7.77(d,2H),7.75(d,2H),7.56(s,1H),7.49(m,2H),7.41(m,4H),7.38(d,2H),1.40(s,9H),1.35(s,6H),1.32(s,9H).
Example 23
Synthesis of Compound 623
The procedure of example 1 was repeated, except that the starting materials were changed to 623-A and 623-B.
1HNMR(DMSO)：δ8.66(d，1H),8.33(d,1H),8.19(d,1H),8.06(s,1H),7.60(s,1H),7.41(m,1H),7.35(d,1H),7.32(m,1H),7.06(m,1H),7.00(d,1H),6.95(m,1H),1.35(s,9H),
Example 24
Synthesis of Compound 656
The procedure of example 1 was repeated, except that the starting materials were changed to 656-A and 656-B.
1HNMR(DMSO)：δ8.66(d，1H),8.52(d,1H),8.19(d,1H),8.06(s,1H),8.00(d,1H),7.62(m,1H),7.56(m,1H),7.48(m,2H),7.46(d,2H),7.41(m,3H),7.38(m,4H),6.95(m,1H),1.40(s,9H),1.32(s,9H).
Example 25
Synthesis of Compound 680
The procedure of example 1 was repeated, except that the starting materials were changed to 656-A and 656-B.
1HNMR(DMSO)：δ8.66(d，1H),8.51(d,1H),8.19(d,1H),8.15(d,1H),8.06(s,1H),7.60(d,1H),7.41(m,1H),7.32(m,1H),7.31(d,2H),7.09(d,1H),7.06(m,1H),7.00(m,1H),1.57(s,6H),1.35(s,9H),1.33(s,9H).
Example 26
Synthesis of Compound 704
The procedure of example 1 was repeated, except that the starting materials were changed to 704-A and 704-B.
1HNMR(DMSO)：δ8.66(d，1H),8.51(d,1H),8.19(d,1H),8.15(d,1H),7.93(s,1H),7.90(d,1H),7.72(d,1H),7.66(d,1H),7.56(s,1H),7.41(m,4H),7.19(m,4H),1.57(s,4H),1.43(s,9H),1.40(s,9H),1.32(s,9H).
Example 27
Synthesis of Compound 721
The procedure was as in example 1 except that the starting materials were changed to 721-A and 721-B.
1HNMR(DMSO)：δ8.66(d，1H),8.52(d,1H),8.19(d,1H),8.03(s,1H),7.66(d,1H),7.62(m,1H),7.50(d,1H),7.48(m,2H),7.41(m,1H),7.38(d,2H),7.32(m,1H),7.06(m,1H),7.00(m,1H),6.99(m,1H),1.57(s,6H),1.40(s,9H).
Example 28
Synthesis of Compound 766
The procedure of example 1 was repeated, except that the starting materials were changed to 766-A and 766-B.
1HNMR(DMSO)：δ8.71(d，1H),8.66(d,1H),8.19(d,1H),8.04(d,1H),8.03(s,1H),7.56(d,1H),7.48(m,2H),7.46(m,2H),7.41(m,3H),7.38(d,4H),1.57(s,6H),1.40(s,9H),1.32(s,9H).
Example 29
Synthesis of Compound 943
The procedure of example 1 was repeated, except that the starting materials were changed to 943-A and 943-B.
1HNMR(DMSO)：δ8.66(d，1H),8.33(d,1H),8.24(s,1H),8.19(d,1H),7.66(d,1H),7.62(m,1H),7.48(m,2H),7.41(m,1H),7.38(d,2H),7.32(m,1H),7.20(d,1H),7.06(m,1H),7.00(d,1H),1.35(s,9H).
Example 30
Synthesis of Compound 1024
The procedure of example 1 was repeated, except that the starting materials were changed to 1024-A and 1024-B.
1HNMR(DMSO)：δ8.76(d，1H),7.84(d,1H),7.75(d,1H),7.62(m,1H),7.53(d,1H),7.51(s,1H),7.50(d,1H),7.48(m,3H),7.38(d,2H),7.07(m,1H),7.00(s,1H),2.36(s,3H).
Example 31
Synthesis of Compound 1075
The procedure was as in example 1 except that the starting materials were replaced with 1075-A and 1075-B.
1HNMR(DMSO)：δ8.66(d，1H),8.51(d,1H),8.19(d,1H),8.15(d,1H),8.03(s,1H),7.55(d,2H),7.66(m,1H),7.60(d,1H),7.50(m,1H),7.41(m,2H),7.36(m,1H),7.35(m,2H),7.32(m,1H),7.19(m,4H),7.06(m,1H),7.00(m,1H),1.35(s,9H).
Device embodiments
Evaluation of luminescent Material devices
The compounds of the respective organic layers used in the device examples and comparative examples are as follows:
the preparation method of the device comprises the following steps:
the basic structural model of the device is as follows:
ITO/HAT-CN (10nm)/TAPC (40nm)/TCTA (10nm)/EML host compound (EML): pt (ii) (40nm) ═ 94: 6/ETL (30nm) </>
LiF(1nm)/Al(80nm)
A transparent anodic Indium Tin Oxide (ITO)20(10 Ω/sq) glass substrate was subjected to ultrasonic cleaning using acetone, ethanol, and distilled water in this order, and then treated with ozone plasma for 15 minutes.
Then, an ITO substrate was mounted on a substrate holder of a vacuum vapor deposition apparatus. In the evaporation equipment, the system pressure is controlled at 10-6 torr. And evaporating the hole transport layer material HAT-CN with the thickness of 60nm onto the ITO substrate.
Then, the light emitting layer material EML was evaporated to a thickness of 40nm, in which the platinum (II) complex dopant was doped.
The electron transport layer material ETL was then evaporated to a thickness of 30 nm.
Then, LiF with a thickness of 1nm was evaporated to form an electron injection layer.
And finally evaporating Al with the thickness of 80nm as a cathode, and packaging the device by using a glass packaging cover.
Example 32
Wherein the platinum (II) complex dopant is compound 11
The device test results are shown in table 1.
Example 33
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 24. The device test results are shown in table 1.
Example 34
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 71. The device test results are shown in table 1.
Example 35
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 102. The device test results are shown in table 1.
Example 36
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 126. The device test results are shown in table 1.
Example 37
The device in this example was fabricated as in example 17 except that the platinum (II) complex dopant was compound 141. The device test results are shown in table 1.
Example 38
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 173. The device test results are shown in table 1.
Example 39
The device in this example was fabricated as in example 17 except that the platinum (II) complex dopant was compound 212. The device test results are shown in table 1.
Example 40
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 241. The device test results are shown in table 1.
EXAMPLE 41
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 275. The device test results are shown in table 1.
Example 42
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 315. The device test results are shown in table 1.
Example 43
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 319. The device test results are shown in table 1.
Example 44
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 340. The device test results are shown in table 1.
Example 45
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 354. The device test results are shown in table 1.
Example 46
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 405. The device test results are shown in table 1.
Example 47
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 437. The device test results are shown in table 1.
Example 48
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 450. The device test results are shown in table 1.
Example 49
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 485. The device test results are shown in table 1.
Example 50
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 508. The device test results are shown in table 1.
Example 51
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 539. The device test results are shown in table 1.
Example 52
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 574. The device test results are shown in table 1.
Example 53
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 605. The device test results are shown in table 1.
Example 54
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 623. The device test results are shown in table 1.
Example 55
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 656. The device test results are shown in table 1.
Example 56
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 680. The device test results are shown in table 1.
Example 57
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 704. The device test results are shown in table 1.
Example 58
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 721. The device test results are shown in table 1.
Example 59
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 766. The device test results are shown in table 1.
Example 60
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 943. The device test results are shown in table 1.
Example 61
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 1024. The device test results are shown in table 1.
Example 62
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was compound 1075. The device test results are shown in table 1.
Comparative example 1
The device in this example was fabricated as in example 32 except that the platinum (II) complex dopant was the compound Pt-ref. The device test results are shown in table 1.
Table 1 shows the results of the performance tests of the devices of examples 32-62 and comparative example 1
TABLE 1
Doping material
Starting voltage (V)
CE(cd/A)
Pt-ref
3.95
158
Compound 11
3.80
177
Compound 24
3.85
179
Compound 71
3.78
165
Compound 102
3.9
166
Compound 126
3.87
171
Compound 141
3.79
160
Compound 173
3.89
171
Compound 212
3.73
166
Compound 241
3.75
165
Compound 275
3.77
160
Compound 315
3.76
170
Compound 319
3.77
163
Compound 340
3.79
162
Compound 354
3.81
170
Compound 405
3.74
168
Compound 437
3.77
169
Compound 450
3.81
171
Compound 485
3.79
172
Compound 508
3.78
168
Compound 539
3.83
167
Compound 574
3.81
178
Compound 605
3.79
182
Compound 623
3.80
172
Compound 656
3.82
173
Compound 680
3.76
183
Compound 704
3.77
180
Compound 721
3.81
183
Compound 766
3.80
182
Compound 943
3.78
173
Compound 1024
3.76
170
Compound 1075
3.79
168
The device structures in the above examples and comparative examples were identical except for the difference in dopant, and the starting voltage V of the devices comprising the metal-organic compound of the present invention was somewhat lowered with reference to the device performance of Pt-ref. The current efficiency is remarkably improved while the voltage is reduced. In conclusion, the novel metal organic compound prepared by the invention has a great application value in organic photoelectric devices. The foregoing has described the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
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