CN111848689A - Benzofuran-containing organic iridium complex, preparation method thereof and photoelectric device - Google Patents
Benzofuran-containing organic iridium complex, preparation method thereof and photoelectric device Download PDFInfo
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0033—Iridium compounds
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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Abstract
The invention discloses an organic iridium complex containing benzofuran, a preparation method thereof and a photoelectric device, belonging to the technical field of luminescent materials, wherein the organic iridium complex has a structural general formula as follows:
in the formula, R1、R2Each independently represents a mono, di, or unsubstituted group; r3、R4Each independently represents a mono, di, tri, tetra or unsubstituted substituent; r5、R6、R7Each independently represents a single or no substituent; and R is1、R2、R3、R4、R5、R6、R7Each independently is at least one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C18 aryl, and substituted or unsubstituted C4-C12 aromatic heterocyclic group. The organic iridium complex can obviously reduce the driving voltage of the photoelectric device, obviously improve the current efficiency and the power efficiency of the photoelectric device and prolong the service life of the photoelectric device.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to an organic iridium complex containing benzofuran, a preparation method thereof and a photoelectric device.
Background
The university of c.w.tang dung qing cloud in 1987 produced OLEDs with a "sandwich" structure, which attracted much attention from scholars, and since then c.w.tang was valued as the father of OLEDs. In 2001, professor Adachi et al prepared phosphorescent devices to achieve 100% internal quantum efficiency. In the same year, they utilized DCM: ir (ppy) 3: the CBP doping system is used for preparing a multilayer structure device, a high-efficiency device with the EQE of 9% is obtained, and the efficiency of a phosphorescent device is gradually improved.
Besides the performance of the devices is improved by adopting high-efficiency materials, researchers improve the luminescence performance and stability of OLEDs through the structural improvement of the devices, and well solve the problems of low efficiency and poor service life of the traditional OLEDs.
In 2015, Ma et al utilized HAT-CN/HAT-CN: the TAPC/TAPC is used as an internal connecting layer of the red, green and blue light laminated OLED, so that the power efficiency of the red, green and blue light laminated OLED can reach 57.5, 126.8 and 52.7Lm/W respectively.
In 2017, the Forrest et al designed 5 light emitting cells stacked on a white phosphorescent OLED, stabilized the charge generation layer with a red light emitting blocking layer to achieve a long lifetime effect, the device reached 80000h at a lifetime (T70 is the standard lifetime of the illumination display) of T70, and the Color Rendering Index (CRI) reached 89. Efficient and stable OLEDs are one of the ultimate goals of organic electroluminescent device industrialization. However, the performance of organic electrophosphorescent devices is not sufficiently consistent in some aspects, and is in the advanced stage of development, and the revolution of OLEDs has not been successful, and efforts are still needed to compete with other display technologies.
Currently, iridium (III) complexes among phosphorescent materials have characteristics such as short exciton lifetime, wide emission color range, high quantum efficiency, and the like, compared to other metal phosphorescent materials, and thus are favored by researchers, and thus are widely studied make internal disorder or usurp as phosphorescent materials. The practical application of the OLED requires that the device has the characteristics of high efficiency and long service life, but the service life of the phosphorescent material high-efficiency OLED is still very short, which seriously hinders the OLED production of red, green and blue phosphorescent materials.
Disclosure of Invention
An object of the embodiments of the present invention is to provide an organic iridium complex containing benzofuran, so as to solve the problems mentioned in the above background art.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions: an organic iridium complex containing benzofuran has a structural general formula as shown in formula I:
in the formula, R1、R2Each independently represents a mono, di, or unsubstituted group; r3、R4Each independently represents a mono, di, tri, tetra or unsubstituted substituent; r5、R6、R7Each independently represents a single or no substituent;
and R is1、R2、R3、R4、R5、R6、R7Each independently is at least one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C18 aryl, and substituted or unsubstituted C4-C12 aromatic heterocyclic group.
Preferably, the halogen is any one of fluorine, chlorine, bromine and iodine.
Preferably, alkyl is straight chain alkyl or branched alkyl;
the cycloalkyl is any one of monocycloalkyl, polycycloalkyl and spiroalkyl;
aryl is a monocyclic group or a polycyclic system; wherein the polycyclic ring system comprises a plurality of rings shared by two adjacent rings with two carbons, wherein at least one ring is aromatic, and the other rings are one or more of cycloalkyl, cycloalkenyl, aryl and heteroaryl;
the aromatic heterocyclic group is any one of furan, thiophene and pyridine.
Preferably, the alkyl group is any one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl;
the cycloalkyl is any one of cyclopropyl, cyclopentyl, cyclohexyl and adamantylamine;
the aryl is any one of benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene and pyrene.
Preferably, the carbon atoms on the cycloalkyl group are substituted with at least one heteroatom; the heteroatom is at least one of N, O, S, Si, Se and Ge.
Preferably, R is as defined above5、R6、R7Each independently represents hydrogen, deuterium, fluorine, cyano, substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C4-C12 aromatic heterocyclic group;
wherein, the above-mentioned "substitution" means that a hydrogen atom bonded to a carbon atom of a compound becomes another substituent, and the position of substitution is not limited as long as the position is a position at which the hydrogen atom is substituted, that is, a position at which the substituent may be substituted, and when two or more substituents are substituted, the two or more substituents may be the same as or different from each other.
In addition, the "substitution" in the above "substituted or unsubstituted" means substitution with one, two or more of the following substituents: deuterium, halogen, a nitrile group, a hydroxyl group, a carbonyl group, an ester group, a silyl group, a boron group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituent connected through two or more of the above substituents.
Preferably, R1、R2、R3、R4、R5、R6、R7Each independently is at least one of the groups represented by the following structural formula:
in the formula (I), the compound is shown in the specification,
is the position of attachment of the group.
Preferably, the chemical structural formula of the organic iridium complex is any one of formula K001 to formula K117, but is not limited thereto:
another object of an embodiment of the present invention is to provide a preparation method of the above organic iridium complex, which includes the following steps:
taking a compound A with a structural general formula of A, and a compound C with a structural general formula of C:
reacting the compound A with iridium trichloride to obtain a bridged ligand B with a structural general formula of formula B:
and reacting the bridging ligand B, the compound C, ethylene glycol ethyl ether and potassium carbonate to obtain the organic iridium complex.
The synthetic route of the preparation method is as follows:
preferably, the preparation method of the organic iridium complex specifically comprises the following steps:
(1) under the protection of nitrogen, mixing the compound A and iridium trichloride trihydrate, adding ethylene glycol ethyl ether aqueous solution for heating reaction, then cooling to room temperature, separating out precipitates, carrying out reduced pressure suction filtration, leaching with water, absolute ethyl alcohol and petroleum ether in sequence, and drying to obtain a bridging ligand B;
(2) under the protection of nitrogen, mixing the bridged ligand B obtained in the step (1) with a compound C, adding ethylene glycol ethyl ether and potassium carbonate to perform heating reaction, cooling to room temperature, performing suction filtration, washing with alcohol, drying, taking dichloromethane as a solvent, performing silica gel column chromatography, and concentrating the filtrate to obtain a solid, wherein the solid is separated out to obtain the organic iridium complex shown in the formula I.
Further, in the step (1), the ethylene glycol ether in the aqueous ethylene glycol ether solution was 20 times by mass of the compound a, and the water in the aqueous ethylene glycol ether solution was 5.15 times by mass of the compound a.
Further, in the step (1), the molar ratio of the compound A to iridium trichloride trihydrate is 3: 1.
Further, in step (2), the molar ratio of the above compound C to the bridging ligand B is 3: 1.
Further, in the step (1), the reaction temperature is 100-130 ℃, and the reaction time is 20-24 h; preferably, the reaction temperature is 120 ℃ and the reaction time is 24 h.
Further, in the step (2), the reaction temperature is 100-130 ℃, and the reaction time is 20-24 h; preferably, the reaction temperature is 120 ℃ and the reaction time is 24 h.
Another object of the embodiments of the present invention is to provide an application of the above organic iridium complex in the preparation of organic electroluminescent devices.
It is another object of an embodiment of the present invention to provide an optoelectronic device, including a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, the organic layer including the above-mentioned organic iridium complex.
Preferably, the organic layer includes a light emitting layer; the light-emitting layer comprises a host material and a doping material; the doping material partially or entirely contains the organic iridium complex.
Preferably, the mass ratio of the host material to the doping material is (90-99.5): (0.5-10).
Specifically, the first electrode is an anode, the type of which is not particularly limited, and may be a conventional anode known to those skilled in the art, and more preferably is one of ITO (indium tin oxide), tin oxide, zinc oxide, and indium oxide, and the thickness of the first electrode is 10 to 500 nm. The second electrode is a cathode, the kind of which is not particularly limited, and is a conventional cathode known to those skilled in the art, and more preferably one of Al, Li, Na, K, Mg, Ca, Au, Ag, and Pb, and the thickness of the second electrode is 100 to 1000 nm.
The main material is preferably one or more of 4, 4'-N, N' -biphenyl dicarbazole (CBP), octahydroxyquinoline (Alq3), metal phenoxybenzothiazole compounds, polyfluorene, aromatic condensed rings and zinc complexes. The thickness of the light emitting layer is 10 to 500 nm.
In addition, the organic layer may further include other functional layers, and the other functional layers may be specifically selected from one or more of the following functional layers: a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a hole injection-hole transport functional layer (i.e., having both hole injection and hole transport functions), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and an electron transport-electron injection functional layer (i.e., having both electron transport and electron injection functions).
The kind of each functional layer is not particularly limited, and may be a conventional functional layer known to those skilled in the art.
Preferably: the hole injection layer is one of 2-TNATA (namely N1- (2-naphthyl) -N4, N4-di (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenyl benzene-1, 4-diamine), phthalocyanine and porphyrin compounds, starburst triarylamine, a conductive polymer, an N-type semiconductive organic complex and a metal organic complex, and the thickness of the hole injection layer is 10-500 nm.
The hole transport layer is one of NPB (namely N, N '-diphenyl-N, N' - (1-naphthyl) -1, 1 '-biphenyl-4, 4' -diamine), TPD (namely N, N '-diphenyl-N, N' - (3-methylphenyl) -1, 1 '-biphenyl-4, 4' -diamine), PAPB (namely N, N '-bis (phenanthrene-9-yl) -N, N' -diphenyl benzidine) arylamine carbazole compound and indolocarbazole compound, and the thickness of the hole transport layer is 10-500 nm.
The hole blocking layer is one of BAlq, BCP and BPhen, and the thickness of the hole blocking layer is 10-500 nm.
The electron transport layer is one of Alq3, coumarin No. 6, triazole derivatives, azole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives and anthrone derivatives, and the thickness of the electron transport layer is 10-500 nm.
The electron injection layer is LiF, CsF or Li2O、Al2O3And MgO with a thickness of 0.1-10 nm.
In the embodiment of the present invention, the light emitting layer and other various functional layers may be formed by vapor deposition.
The above-mentioned photoelectric device may be an organic electroluminescent device, an organic solar cell, electronic paper, an organic photoreceptor, an organic thin film transistor, or the like, but is not limited thereto.
Compared with the prior art, the embodiment of the invention has the beneficial effects that:
the benzofuran-containing organic iridium complex provided by the embodiment of the invention is prepared by combining metal iridium with a specific heterocyclic ligand, and after the obtained organic iridium metal complex is used for photoelectric devices such as organic electroluminescent devices and the like, the driving voltage of the photoelectric devices can be reduced, the current efficiency and the power efficiency of the photoelectric devices can be obviously improved, and the service life of the photoelectric devices can be prolonged. In addition, the preparation method of the organic iridium complex provided by the embodiment of the invention has the characteristics of simple synthesis steps, easiness in purification and high yield of target products, and is suitable for popularization and application.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
Complex example 1
The embodiment of the complex provides an organic iridium complex containing benzofuran, the chemical structural formula of the complex is formula K001 in the invention, and the reaction route of the preparation method of the organic iridium complex is as follows:
the specific preparation method comprises the following steps:
(1) weighing compound A001(67.72mmo1, 20g) under nitrogen protection system, placing into a reaction flask, and adding IrCl3·3H2O (22.57mmo1, 7.96g) is put into a reaction system, a mixed solution of 400mL of ethylene glycol ether and 133mL of purified water is added, the temperature is raised to 120 ℃ (reflux) under the protection of nitrogen for reaction for 24 hours, the system is cooled to room temperature after the reaction is stopped, red precipitate is separated out, the precipitate is filtered by suction, water, absolute ethyl alcohol and petroleum ether are sequentially washed, and the mixture is put into a vacuum drying oven for drying at 65 ℃ to obtain orange red powdery bridging ligand B001(14.1g, the yield is 76.52%, the theoretical value of Mw is 1632.23, and the test value is 1632.64);
(2) under the protection of nitrogen, orange red powder bridging ligand B001(8.58mmol, 14g) is weighed, compound CC003 acetylacetone 5.92g is added, 400mL of ethylene glycol ethyl ether and 11.85g of potassium carbonate are added into the system, the mixture is stirred for 24 hours at 120 ℃ (reflux) under the protection of nitrogen, the mixture is filtered, washed by alcohol, dried, dichloromethane is used as a solvent, silica gel column chromatography is carried out, and the filtrate is concentrated and precipitated to obtain the final red organic iridium complex K001(10.2g, the yield is 67.59%).
The detection and analysis of the organic iridium complex have the following specific results:
HPLC purity: is more than 99 percent.
Mass spectrum: calculated value 880.19, test value 879.97;
elemental analysis:
calculated value C: 64.15 percent; h: 3.55 percent; n: 3.18 percent; o: 7.27 percent; ir: 21.84 percent;
test value C: 64.16 percent; h: 3.54 percent; n: 3.19 percent; o: 7.27 percent; ir: 21.83 percent.
By comparing the calculated value with the tested value, the measured value is basically consistent with the theoretical value, thereby proving that the organic iridium complex with the structural formula of K001 can be successfully synthesized by the complex example.
Complex example 2
The embodiment of the complex provides an organic iridium complex containing benzofuran, the chemical structural formula of the complex is shown as formula K035 in the summary of the invention, and the reaction route of the preparation method of the organic iridium complex is as follows:
the specific preparation method comprises the following steps:
(1) weighing compound A035(61.85mmo1, 20g) under nitrogen protection, placing into a reaction flask, and adding IrCl3·3H2O (20.62mmo1, 7.27g) is put into a reaction system, a mixed solution of 400mL of ethylene glycol ether and 133mL of purified water is added, the temperature is raised to 120 ℃ (reflux) under the protection of nitrogen, the reaction is carried out for 24 hours, and the reaction is stoppedCooling the system to room temperature, separating out orange-red precipitate, filtering the precipitate, sequentially washing with water, absolute ethyl alcohol and petroleum ether, and drying in a vacuum drying oven at 65 ℃ to obtain orange-red powdery bridging ligand B035(13.6g, yield 75.62%, Mw theoretical value: 1744.35, test value: 1744.85);
(2) under the protection of nitrogen, orange red powdery bridging ligand B035(7.62mmo l, 13.3g) is weighed, compound C (C035) 3-methylacetoacetone 2.61g is added, 400mL of ethylene glycol ethyl ether and 10.53g of potassium carbonate are added into the system, the mixture is stirred for 18 hours at 120 ℃ (reflux) under the protection of nitrogen, the mixture is filtered, washed by alcohol, dried, dichloromethane is used as a solvent, silica gel column chromatography is carried out, and solid is concentrated and separated out from the filtrate to obtain the final red organic iridium complex K035(10.0g, the yield is 69.04%).
The detection and analysis of the organic iridium complex have the following specific results:
HPLC purity: is more than 99.5 percent.
Mass spectrum: calculated value 950.10, test value 950.26;
elemental analysis:
calculated value C: 65.74 percent; h: 4.35 percent; n: 2.95 percent; o: 6.74 percent; ir: 20.23 percent;
test value C: 65.74 percent; h: 4.37 percent; n: 2.94 percent; o: 6.74 percent; ir: 20.24 percent.
By comparing the calculated value with the tested value, the measured value is basically consistent with the theoretical value, thereby proving that the organic iridium complex with the structural formula of K035 can be successfully synthesized by the complex embodiment.
Complex example 3
The embodiment of the complex provides an organic iridium complex containing benzofuran, the chemical structural formula of the complex is shown as formula K049 in the summary of the invention, and the reaction route of the preparation method of the organic iridium complex is as follows:
the specific preparation method comprises the following steps:
(1) weighing compound A049(56.91mmo1, 20g) in a reaction flask under the protection of nitrogen, and adding IrCl3·3H2O (18.97mmo1, 6.69g) is put into a reaction system, a mixed solution of 400mL of ethylene glycol ether and 133mL of purified water is added, the temperature is raised to 120 ℃ (reflux) under the protection of nitrogen for 24 hours, the system is cooled to room temperature after the reaction is stopped, a dark red precipitate is separated out, the precipitate is filtered by suction, water, absolute ethyl alcohol and petroleum ether are sequentially washed, and the mixture is put into a vacuum drying oven for drying at 65 ℃, so that dark red powdery bridging ligand B049(12.8g, the yield is 72.67%, the theoretical value of Mw is 1856.48, and the test value is 1857.06) is obtained;
(2) weighing dark red powdery bridging ligand B049(6.73mmo l, 12.5g) under a nitrogen protection system, adding compound C (C049) heptane 3, 5-diketone 2.59g, adding 400m L ethylene glycol ethyl ether and 10.53g potassium carbonate into the system, stirring for 26 hours at 120 ℃ (reflux) under the protection of nitrogen, carrying out suction filtration, washing with alcohol, drying, using dichloromethane as a solvent, carrying out silica gel column chromatography, concentrating the filtrate, and precipitating a solid to obtain a final red organic iridium complex K049(8.5g, yield 61.89%).
The detection and analysis of the organic iridium complex have the following specific results:
HPLC purity: is more than 99.5 percent.
Mass spectrum: calculated value 1020.24, test value 1020.34;
elemental analysis:
calculated value C: 67.10 percent; h: 5.04 percent; n: 2.75 percent; o: 6.27 percent; ir: 18.84 percent;
test value C: 67.12 percent; h: 5.05 percent; n: 2.76 percent; o: 6.25 percent; ir: 18.85 percent.
By comparing the calculated value with the tested value, the measured value is basically consistent with the theoretical value, thereby proving that the organic iridium complex with the structural formula of K049 can be successfully synthesized by the complex example.
Complex example 4
The embodiment of the complex provides an organic iridium complex containing benzofuran, the chemical structural formula of the complex is formula K060 in the invention, and the reaction route of the preparation method of the organic iridium complex is as follows:
the specific preparation method comprises the following steps:
(1) weighing compound A060(64.65mmo1, 20g) under the protection of nitrogen, filling into a reaction bottle, and adding IrCl3·3H2Adding O (21.55mmo1, 7.6g) into a reaction system, adding a mixed solution of 400mL of ethylene glycol ether and 133mL of purified water, heating to 120 ℃ (refluxing) under the protection of nitrogen, reacting for 16 hours, cooling the system to room temperature after the reaction is stopped, separating out bright red precipitate, carrying out suction filtration on the precipitate, sequentially washing with water, absolute ethyl alcohol and petroleum ether, and drying in a vacuum drying oven at 65 ℃ to obtain red powdery bridging ligand B060(13.7g, the yield is 75.29%, the theoretical value of Mw is 1688.29, and the test value is 1688.75);
(2) under the protection of nitrogen, red powdery bridging ligand B060(7.99mmol, 13.5g) is weighed, compound C (C060) acetylacetone 2.4g is added, 400mL of ethylene glycol ethyl ether and 11.05g of potassium carbonate are added into the system, the mixture is stirred for 20 hours at 120 ℃ (reflux) under the protection of nitrogen, the mixture is filtered, washed by alcohol, dried, dichloromethane is used as a solvent, silica gel column chromatography is carried out, and the filtrate is concentrated and precipitated to obtain the final red organic iridium complex K060(10.2g, the yield is 70.26%).
The detection and analysis of the organic iridium complex have the following specific results:
HPLC purity: is more than 99.5 percent.
Mass spectrum: calculated value 908.03, test value 908.22;
elemental analysis:
calculated value C: 64.81 percent; h: 3.89 percent; n: 3.09%; o: 7.05 percent; ir: 21.17 percent;
test value C: 64.82 percent; h: 3.91 percent; n: 3.08 percent; o: 7.06 percent; ir: 21.18 percent.
By comparing the calculated value with the test value, the measured value is basically consistent with the theoretical value, thereby proving that the organic iridium complex with the structural formula of K060 can be successfully synthesized by the complex example.
Complex example 5
The embodiment of the complex provides an organic iridium complex containing benzofuran, the chemical structural formula of the complex is shown as formula K067 in the summary of the invention, and the reaction route of the preparation method of the organic iridium complex is as follows:
the specific preparation method comprises the following steps:
(1) weighing compound A067(59.63mmo1, 20g) into a reaction flask under the protection of nitrogen, and adding IrCl3·3H2Adding O (19.88mmo1, 7.01g) into a reaction system, adding a mixed solution of 400mL of ethylene glycol ethyl ether and 133mL of purified water, heating to 120 ℃ (refluxing) under the protection of nitrogen, reacting for 18 hours, cooling the system to room temperature after the reaction is stopped, separating out a mauve precipitate, carrying out suction filtration on the precipitate, sequentially washing with water, absolute ethyl alcohol and petroleum ether, and drying in a vacuum drying oven at 65 ℃ to obtain red powdery bridging ligand B067(11.5g, the yield is 64.54%, the theoretical value of Mw is 1792.35, and the test value is 1792.88);
(2) under the protection of nitrogen, red powdery bridging ligand B067(6.14mmol, 11.0g) is weighed, compound C (C067)2, 6-dimethyl-4-phenyl heptane-3, 5-diketone 4.28g is added, 400mL of ethylene glycol ethyl ether and 8.48g of potassium carbonate are added into the system, the mixture is stirred for 16 hours at 120 ℃ (reflux) under the protection of nitrogen, the mixture is filtered, washed by alcohol, dried, dichloromethane is used as a solvent, silica gel column chromatography is carried out, and solid is concentrated and separated out from the filtrate to obtain the final red organic iridium complex K067(8.3g, the yield is 61.93%).
The detection and analysis of the organic iridium complex have the following specific results:
HPLC purity: is more than 99.5 percent.
Mass spectrometry test: a theoretical value of 1125.28; the test value was 1125.28.
Mass spectrum: calculated value 1092.30, test value 1092.34;
elemental analysis:
calculated value C: 69.27 percent; h: 4.71 percent; n: 2.56 percent; o: 5.86 percent; ir: 17.60 percent;
test value C: 69.28 percent; h: 4.71 percent; n: 2.55 percent; o: 5.89 percent; ir: 17.61 percent.
By comparing the calculated value with the tested value, the measured value is basically consistent with the theoretical value, thereby proving that the organic iridium complex with the structural formula of K067 can be successfully synthesized by the complex example.
Complex example 6
The embodiment of the complex provides an organic iridium complex containing benzofuran, the chemical structural formula of the complex is shown as formula K081 in the summary of the invention, and the reaction route of the preparation method of the organic iridium complex is as follows:
the specific preparation method comprises the following steps:
(1) weighing compound A081(64.65mmo1, 20g) into a reaction bottle under the protection of nitrogen, and adding IrCl3·3H2Adding O (21.55mmo1, 7.6g) into a reaction system, adding a mixed solution of 400mL of ethylene glycol ethyl ether and 133mL of purified water, heating to 120 ℃ (refluxing) under the protection of nitrogen, reacting for 20 hours, cooling the system to room temperature after the reaction is stopped, separating out red precipitate, carrying out suction filtration on the precipitate, sequentially washing with water, absolute ethyl alcohol and petroleum ether, and drying in a vacuum drying oven at 65 ℃ to obtain a red powdery bridging ligand B081(11.6g, the yield is 63.75%, the theoretical value of Mw is 1688.29, and the test value is 1688.75);
(2) under the protection of nitrogen, red powdery bridging ligand B081(6.51mmol, 11.0g) is weighed, 4.15g of compound C (C081)3, 7-diethylnonane-4, 6-dione is added, 400mL of ethylene glycol ethyl ether and 9.0g of potassium carbonate are added into the system, the mixture is stirred for 18 hours at 120 ℃ (reflux) under the protection of nitrogen, the mixture is filtered, washed with alcohol, dried, dichloromethane is used as a solvent, silica gel column chromatography is carried out, and solid is concentrated and precipitated to obtain the final red compound K081(9.1g, the yield is 68.47%).
The detection and analysis of the organic iridium complex have the following specific results:
HPLC purity: is more than 99.5 percent.
Mass spectrum: calculated value 1020.24, test value 1020.34;
elemental analysis:
calculated value C: 67.10 percent; h: 5.04 percent; n: 2.75 percent; o: 6.27 percent; ir: 18.84 percent;
test value C: 67.12 percent; h: 5.06 percent; n: 2.72 percent; o: 6.28 percent; ir: 18.83 percent.
By comparing the calculated value with the tested value, the measured value is basically consistent with the theoretical value, thereby proving that the organic iridium complex with the structural formula of K081 can be successfully synthesized by the complex example.
Examples 7 to 20 of the complexes
Because the synthetic route and the principle of the preparation method of other organic iridium complexes with the structural general formula of formula I in the invention content are the same as those of the listed complex example 1, the compound A and the compound C only need to be respectively replaced by compounds corresponding to corresponding ligand structures in target products, and the corresponding organic iridium complexes can be obtained by correspondingly adjusting the material dosage according to corresponding stoichiometric ratio, so that the method is not exhaustive, and a plurality of organic iridium complexes are selected as the complex examples 7-20 in the invention, and are specifically shown in the following table 1.
TABLE 1
The embodiment of the invention also provides a photoelectric device prepared by using the organic iridium complex provided by the embodiment, and particularly, the photoelectric device is an organic electroluminescent device, wherein the organic electroluminescent device comprises a first electrode, a second electrode and at least one organic layer arranged between the first electrode and the second electrode.
The organic layer may include at least one layer selected from a hole injection layer, a hole transport layer, a composite layer of hole injection and hole transport technical layers, an electron blocking layer, an emission layer, a hole blocking layer, an electron transport layer, an electron injection layer, an electron transport layer and a composite layer of electron injection technical layers, and at least one layer may or may not include the organic iridium complex.
Specifically, the light-emitting layer includes a host material and a dopant material; wherein, the host material can be 4, 4'-N, N' -biphenyl dicarbazole (CBP), but is not limited thereto; the doping material can be selected from the organic iridium complexes.
In practical applications, the method for manufacturing the organic electroluminescent device can refer to device example 1 below.
Device example 1
The device embodiment 1 provides an organic electroluminescent device, and a manufacturing method thereof includes the steps of:
(1) coating with a thickness of
The ITO glass substrate is put in distilled water for cleaning for 2 times, ultrasonically cleaned for 30 minutes, repeatedly cleaned for 2 times by distilled water, ultrasonically cleaned for 10 minutes, after the cleaning of the distilled water is finished, isopropanol, acetone and methanol solvents are ultrasonically cleaned in sequence (each time, each time is cleaned for 10 minutes), dried, transferred into a plasma cleaning machine, cleaned for 5 minutes and sent into an evaporation plating machine;
(2) using ITO as anode, evaporating to form film on it
Then sequentially evaporating
Host substance 4, 4'-N, N' -biphenylA mixture of dicarbazole (CBP) and the above-mentioned organic iridium complex K001 (wherein the weight ratio of 4, 4'-N, N' -biphenyldicarbazole and the organic iridium complex K001 is 95:5), an electron transport layer "Alq 3"
Electron injection layer
Cathode electrode
And the organic electroluminescent device can be prepared.
Device examples 2 to 20
An organic electroluminescent device is prepared by referring to the preparation method provided in device example 1, except that the organic iridium complex M001 (doping material) in device example 1 is replaced with the organic iridium complexes K035, K049, K060, K067, K081, K008, K009, K021, K037, K046, K065, K071, K075, K082, K090, K093, K101, K111, and K117 prepared in the above examples 2 to 20, respectively, so as to prepare the corresponding organic electroluminescent device.
Comparative device example 1
An organic electroluminescent device was fabricated by referring to the fabrication method provided in device example 1 above, except that the organic iridium complex M001 (dopant material) in device example 1 above was replaced with the existing iridium metal complex ir (pq)2acac, wherein, Ir (pq)2The structural formula of acac is as follows:
experimental example:
the performance and the light emitting characteristics of the organic electroluminescent devices obtained in the device examples 1 to 20 and the device comparative example 1 were respectively tested under the same luminance conditions by using a KEITHLEY model 2400 source measurement unit and a CS-2000 spectroradiometer to evaluate the driving voltage, the current efficiency, the power efficiency and the light emitting lifetime (T95) of the organic electroluminescent device, and the specific test results are shown in table 2.
TABLE 2
As can be seen from Table 2 above, the results are shown in Ir (pq) as compared to that provided in comparative example 1 of the device2The organic electroluminescent device prepared by using the organic iridium complex provided by the embodiment of the invention as the doping material can effectively reduce the driving voltage of a photoelectric device, and can remarkably improve the current efficiency, the power efficiency and the service life of the organic electroluminescent device.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. An organic iridium complex containing benzofuran is characterized in that the structural general formula of the organic iridium complex is shown as formula I:
in the formula, R1、R2Each independently represents a mono, di, or unsubstituted group; r3、R4Each independently represents a mono, di, tri, tetra or unsubstituted substituent; r5、R6、R7Each independently represents a single or no substituent;
and R is1、R2、R3、R4、R5、R6、R7Each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstitutedAt least one of a C6-C18 aryl group, a substituted or unsubstituted C4-C12 aromatic heterocyclic group.
2. The benzofuran-containing organic iridium complex as claimed in claim 1, wherein the halogen is any one of fluorine, chlorine, bromine and iodine.
3. The benzofuran-containing organic iridium complex as claimed in claim 1, wherein alkyl is a straight-chain alkyl group or a branched-chain alkyl group;
the cycloalkyl is any one of monocycloalkyl, polycycloalkyl and spiroalkyl;
aryl is a monocyclic group or a polycyclic system; wherein the polycyclic ring system comprises a plurality of rings shared by two adjacent rings with two carbons, wherein at least one ring is aromatic, and the other rings are one or more of cycloalkyl, cycloalkenyl, aryl and heteroaryl;
the aromatic heterocyclic group is any one of furan, thiophene and pyridine.
4. The benzofuran-containing organic iridium complex as claimed in claim 3, wherein the alkyl group is any one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl;
the cycloalkyl is any one of cyclopropyl, cyclopentyl, cyclohexyl and adamantylamine;
the aryl is any one of benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene and pyrene.
5. The benzofuran-containing organic iridium complex of claim 3, wherein carbon atoms of a cycloalkyl group are substituted with at least one heteroatom; the heteroatom is at least one of N, O, S, Si, Se and Ge.
6. The benzofuran-containing organic iridium complex as claimed in claim 1, wherein R is1、R2、R3、R4、R5、R6、R7Each independently is at least one of the groups represented by the following structural formula:
in the formula (I), the compound is shown in the specification,
is the position of attachment of the group.
7. The benzofuran-containing organic iridium complex as claimed in any one of claims 1 to 6, wherein the chemical structural formula of the organic iridium complex is any one of formula K001 to formula K117:
8. a method for preparing an organic iridium complex according to any one of claims 1 to 7, comprising the steps of:
taking a compound A with a structural general formula of A, and a compound C with a structural general formula of C:
reacting the compound A with iridium trichloride to obtain a bridged ligand B with a structural general formula of formula B:
and reacting the bridging ligand B, the compound C, ethylene glycol ethyl ether and potassium carbonate to obtain the organic iridium complex.
9. An optoelectronic device comprising a first electrode, a second electrode and at least one organic layer disposed between the first electrode and the second electrode, wherein the organic layer comprises an organic iridium complex according to any one of claims 1 to 7.
10. The optoelectronic device according to claim 9, wherein the organic layer comprises a light-emitting layer; the light-emitting layer comprises a host material and a doping material; the doping material partially or entirely contains the organic iridium complex.
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