CN117586131A - Low refractive index organic compound, OLED (organic light emitting diode) with same and organic light emitting device - Google Patents

Low refractive index organic compound, OLED (organic light emitting diode) with same and organic light emitting device Download PDF

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CN117586131A
CN117586131A CN202311621496.XA CN202311621496A CN117586131A CN 117586131 A CN117586131 A CN 117586131A CN 202311621496 A CN202311621496 A CN 202311621496A CN 117586131 A CN117586131 A CN 117586131A
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refractive index
compound
organic
low refractive
organic compound
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张磊
申屠晓波
吴空物
孔祥贞
刘运起
章华星
叶绪兵
赵晓宇
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Zhejiang Huadisplay Optoelectronics Co Ltd
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Zhejiang Huadisplay Optoelectronics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • C07C211/56—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
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  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to the technical field of organic photoelectric material preparation, in particular to a low-refractive-index organic compound, an OLED (organic light-emitting diode) with the compound and an organic light-emitting device. The low refractive index organic compound can be applied to a covering layer of a device, improves light extraction efficiency, improves luminous efficiency of an organic luminous element, and has better effect than the existing common OLED device. Has good industrialization prospect.

Description

Low refractive index organic compound, OLED (organic light emitting diode) with same and organic light emitting device
Technical Field
The invention relates to the technical field of organic photoelectric material preparation, in particular to a low-refractive-index organic compound, an OLED (organic light emitting diode) with the compound and an organic light emitting device.
Background
Organic Light Emitting Diodes (OLEDs), also known as organic electroluminescent devices, are techniques in which an organic material emits light under the influence of an electric field by means of carrier injection and recombination, and which are capable of converting electrical energy into light energy through the organic luminescent material. At present, research is actively being conducted on the layer structure in the device structure, whether the development of an organic material having light emission characteristics such as three primary colors of light or the development of an organic material having charge transporting ability (possibility of becoming a semiconductor or superconductor) such as holes, electrons, or the like.
In a top-emitting OLED electroluminescent device, light is emitted from the top of the device, with a totally reflective anode and a semi-transmissive metal cathode on either side of the organic layer. The cathode metal materials are commonly used metals such as aluminum, magnesium, silver, ytterbium and the like or alloys thereof. Deviations between the total refractive index and the optimal refractive index of constituent elements and materials (e.g., glass substrate, organic material, and electrode material) of the organic light emitting device result in total reflection of some of the emitted light from the organic layer to the cathode at an angle, and only a portion of the light is utilized. Therefore, there is a need to develop a material for a more excellent cover layer.
Disclosure of Invention
In order to solve the technical problems, the invention provides a low refractive index organic compound, an OLED (organic light emitting diode) with the compound and a display or lighting device.
The invention provides a low refractive index organic compound, which is realized by the following technical scheme:
a low refractive index organic compound having a general structure represented by the following formula (I):
in the formula (I), R 1 -R 15 Each independently selected from hydrogen, deuterium, halogen, C1-C20 alkyl, C3-C20 cycloalkyl, C1-C20 haloalkyl, C6-C30 aryl, anda group of groups.
Preferably, said R 1 -R 15 Each independently selected from the group consisting of hydrogen, deuterium, F, C1-C10 alkyl, C3-C10 monocycloalkyl, C4-C10 bridged cycloalkyl, C1-C10 fluoroalkyl, C6-C18 non-condensed aryl, and combinations thereof.
Preferably, said R 1 -R 15 Each independently selected from hydrogen, F, methyl, t-butyl, trifluoromethyl, cyclohexane, norbornyl, phenyl, biphenyl, or o-terphenyl; the R is 1 -R 15 Not both phenyl.
According to one or more embodiments, the present invention provides a low refractive index organic compound selected from any one of the chemical structures shown below:
。
the invention also provides application of the low-refractive-index organic compound in preparation of an organic electroluminescent device. The application is as a cover layer material for organic electroluminescent devices.
The invention also provides an organic electroluminescent device, which comprises:
a substrate layer;
a first electrode over the substrate;
an organic light emitting functional layer over the first electrode;
a second electrode over the organic light emitting functional layer;
a cover layer over the second electrode; the cover layer comprises a low refractive index organic compound as described above.
Preferably, the organic light emitting functional layer includes one or more of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer, and an electron injection layer.
Preferably, the cover layer further comprises a high refractive index compound. The refractive index n of the high refractive index compound at the wavelength of 460nm is 1.95-2.30, the refractive index n at the wavelength of 530nm is 1.90-2.05, and the refractive index n at the wavelength of 620nm is 1.80-2.00.
Preferably, the refractive index n of the low refractive index organic compound satisfies the following condition:
refractive index n between 450-650nm wavelength 450-650 <1.60, and an extinction coefficient between 450-650nm wavelength of below 0.1;
difference n between refractive index of 460nm and refractive index of 530 460 -n 530 <0.1；
Difference n between refractive index of 510nm and refractive index of 620 510 -n 620 <0.05。
Preferably, the thickness of the cover layer is 40-80nm.
The invention also provides a composition which comprises the low-refraction organic compound with the structure shown in the formula (I).
The present invention also provides a formulation comprising a low refractive index organic compound of the structure as shown in formula (I) above or a composition as described above and at least one solvent. The solvent is not particularly limited, and for example, an unsaturated hydrocarbon solvent such as toluene, xylene, mesitylene, tetrahydronaphthalene, decalin, bicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, a halogenated saturated hydrocarbon solvent such as carbon tetrachloride, chloroform, methylene chloride, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, a halogenated unsaturated hydrocarbon solvent such as chlorobenzene, dichlorobenzene, trichlorobenzene, an ether solvent such as tetrahydrofuran, tetrahydropyran, an ester solvent such as an alkyl benzoate, and the like, which are known to those skilled in the art, can be used.
The invention also provides a display or lighting device comprising one or more of the organic electroluminescent devices as described above.
In summary, compared with the prior art, the invention has the following beneficial effects:
the low refractive index organic compound has ultraviolet absorption characteristics, can reduce light refraction loss of an organic light-emitting device, improves the luminous efficiency of the organic light-emitting device, and has good industrial application prospect.
Detailed Description
The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is shown, however, only some, but not all embodiments of the invention are shown. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.
The halogen atom of the present invention may be, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
The alkyl groups of the present invention may be straight chain, branched or cyclic. The number of carbon atoms of the alkyl group is 1 to 20. The alkyl group may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, etc., but is not limited thereto.
The cycloalkane group according to the present invention represents any functional group or substituent derived from an alicyclic ring. Saturated cyclic alkyl groups having 3 to 20 ring-forming carbon atoms. The cycloalkyl group may be a single ring, a bridged ring, a spiro ring, or a condensed ring, and for example, may be cyclohexane, bishexane, adamantane, norbornyl, or the like, but is not limited thereto.
The aryl group refers to a generic term that a monovalent group remains after one hydrogen atom is removed from the aromatic nucleus carbon of an aromatic hydrocarbon molecule, and may be a monocyclic aryl group or a condensed ring aryl group, and examples thereof include, but are not limited to, phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, and the like.
Throughout this specification, unless explicitly stated to the contrary, the word "comprise" or variations such as "comprises" or "comprising", will be understood to imply the inclusion of other elements but not the exclusion of any other element. Furthermore, it will be understood that throughout the specification, when an element such as a layer, film, region or substrate is referred to as being "on" or "over" another element, it can be "directly on" the other element or intervening elements may also be present. In addition, "on … …" or "above … …" means above the target portion, and not necessarily above in the direction of gravity.
An object of the present invention is to provide an organic electroluminescent device comprising: a substrate layer; a first electrode over the substrate; an organic light emitting functional layer over the first electrode; a second electrode over the organic light emitting functional layer; and a cover layer over the second electrode, the cover layer comprising one or more of the compounds represented by the general formula (I) above.
In a preferred embodiment of the present invention, there is provided an OLED comprising a substrate, an anode, a cathode, an organic light emitting functional layer, a capping layer, wherein the organic light emitting functional layer may comprise a light emitting layer, a hole transporting layer, a hole injecting layer, an electron transporting layer, an electron injecting layer, etc., and may also comprise only the light emitting layer and one or more other layers; wherein the cover layer comprises one or more of the compounds shown in the general formula (I). Optionally, a protective layer and/or an encapsulation layer is also provided on top of the cover layer.
The substrate of the present invention may be any substrate used in a typical organic light emitting device. The flexible PI film can be a glass or transparent plastic substrate, a substrate made of an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strength, thermal stability, transparency, surface smoothness and waterproofness, and the use direction is different according to the different properties of the substrates.
As the material of the hole injection layer, the hole transport layer, and the electron injection layer, any material can be selected from known materials for use in an OLED device.
As a guest material capable of generating blue fluorescence, green fluorescence, and blue-green fluorescence, it is necessary to have not only extremely high fluorescence quantum emission efficiency but also an appropriate energy level, and to efficiently absorb excitation energy of a host material to emit light.
The present invention will be specifically described with reference to the following examples. All starting materials and solvents were commercially available unless specified, and the solvents were used as such and were not further processed.
Examples:
example 1: synthesis of Compound 005
The synthetic route is as follows:
。
(1) Into a reaction flask were added 005-1 (10 mmoL), 005-2 (25 mmoL), sodium t-butoxide (10 mmoL), 200mL of toluene, and after nitrogen substitution, pd2 (dba) 3 (5X 10) -2 mmoL)、Sphos(5×10 -2 mmoL), heating to 100-120 ℃, refluxing and reacting for 6 hours, and stopping the reaction. Cooling to 30-40deg.C, adding 200mL of water, and layering. After washing twice, toluene was concentrated, 100mL of n-heptane was added, and the mixture was slurried. Intermediate product 005-3 was obtained.
(2) Into a reaction flask were added 005-3 (10 mmoL), 005-4 (25 mmoL), sodium t-butoxide (10 mmoL), 200mL of toluene, and after nitrogen substitution, pd2 (dba) 3 (5X 10) -2 mmoL)、Sphos(5×10 -2 mmoL), heating to 100-120 ℃, refluxing and reacting for 6 hours, and stopping the reaction. Cooling to 30-40deg.C, adding 200mL of water, and layering. After washing twice, toluene was concentrated, 100mL of n-heptane was added, and the mixture was slurried. The final product 005 is obtained.
The structure of target product 005 was tested: LC-MS (m/z) (m+), theoretical value 533.16 and test value 533.52 were obtained by liquid chromatography-mass spectrometry analysis.
Example 2: synthesis of Compound 003
Referring to the synthesis procedure and reaction conditions of example 1, compound 003 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (M/z) (M+).
Example 3: synthesis of Compound 007
Referring to the synthesis procedure and reaction conditions of example 1, compound 007 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (m/z) (m+).
Example 4: synthesis of Compound 010
With reference to the synthesis procedure and reaction conditions of example 1, compound 010 was synthesized and LC-MS (m/z) (m+), which was obtained by liquid chromatography-mass spectrometry analysis, was found to have a theoretical value of 609.19 and a test value of 609.57.
Example 5: synthesis of Compound 011
Referring to the synthesis procedure and reaction conditions of example 1, compound 011 was synthesized by LC-MS (M/z) (m+), theoretical 541.20 and test 541.55, as determined by LC-MS (M/z) (m+).
Example 6: synthesis of Compound 016
Referring to the synthesis procedure and reaction conditions of example 1, compound 016 was synthesized by liquid chromatography-mass spectrometry analysis to give LC-MS (m/z) (m+):theoretical 541.20 and tested 541.58.
Example 7: synthesis of Compound 018
The synthetic route is as follows:
。
(1) Into a reaction flask were added 018-1 (10 mmoL), 018-2 (25 mmoL), sodium tert-butoxide (10 mmoL), 200mL of toluene, and after nitrogen substitution, pd2 (dba) 3 (5X 10) -2 mmoL)、Sphos(5×10 -2 mmoL), heating to 100-120 ℃, refluxing and reacting for 6 hours, and stopping the reaction. Cooling to 30-40deg.C, adding 200mL of water, and layering. After washing twice, toluene was concentrated, 100mL of n-heptane was added, and the mixture was slurried. Intermediate product 018-3 was obtained.
(2) Into a reaction flask were added 018-3 (10 mmoL), 018-4 (25 mmoL), sodium tert-butoxide (10 mmoL), 200mL of toluene, and after nitrogen substitution, pd2 (dba) 3 (5X 10) -2 mmoL)、Sphos(5×10 -2 mmoL), heating to 100-120 ℃, refluxing and reacting for 6 hours, and stopping the reaction. Cooling to 30-40deg.C, adding 200mL of water, and layering. After washing twice, toluene was concentrated, 100mL of n-heptane was added, and the mixture was slurried. The final product 018 is obtained.
Structure of test target product 018: LC-MS (m/z) (m+), theoretical value 453.25 and test value 453.57 were obtained by liquid chromatography-mass spectrometry analysis.
Example 8: synthesis of Compound 023
Referring to the synthesis procedure and reaction conditions of example 7, compound 023 was synthesized by liquid chromatography-mass spectrometry analysis to give LC-MS (m/z) (m+):theoretical 529.28 and test 529.60.
Example 9: synthesis of Compound 027
Referring to the synthesis procedure and reaction conditions of example 7, compound 027 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (m/z) (m+).
Example 10: synthesis of Compound 032
Referring to the synthesis procedure and reaction conditions of example 7, compound 032 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (m/z) (m+):theoretical 529.28 and test 529.60.
Example 11: synthesis of Compound 039
The synthetic route is as follows:
。
(1) Into a reaction flask were added 039-1 (10 mmoL), 039-2 (25 mmoL), sodium t-butoxide (10 mmoL), 200mL of toluene, and after nitrogen substitution, pd2 (dba) 3 (5X 10) -2 mmoL)、Sphos(5×10 -2 mmoL), heating to 100-120 ℃, refluxing and reacting for 6 hours, and stopping the reaction. Cooling to 30-40deg.C, adding 200mL of water, and layering. After washing twice, toluene was concentrated, 100mL of n-heptane was added, and the mixture was slurried. Intermediate product 039-3 was obtained.
(2) Into a reaction flask were added 039-3 (10 mmoL), 039-4 (25 mmoL), sodium t-butoxide (10 mmoL), 200mL of toluene, and after nitrogen substitution, pd2 (dba) 3 (5X 10) -2 mmoL)、Sphos(5×10 -2 mmoL), heating to 100-120 ℃, refluxing and reacting for 6 hours, and stopping the reaction. Cooling to 30-40deg.C, adding 200mL of water, and layering. After washing twice, toluene was concentrated, 100mL of n-heptane was added, and the mixture was slurried. The final product 039 is obtained.
Structure of test target product 039: LC-MS (m/z) (m+), theoretical value 549.25 and test value 549.67 were obtained by liquid chromatography-mass spectrometry analysis.
Example 12: synthesis of Compound 033
Referring to the synthesis procedure and reaction conditions of example 11, compound 033 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (M/z) (M+).
Example 13: synthesis of Compound 035
Referring to the synthesis procedure and reaction conditions of example 11, compound 035 was synthesized and LC-MS (M/z) (M+), which was obtained by liquid chromatography-mass spectrometry analysis, was 625.28 as a theoretical value and 625.54 as a test value.
Example 14: synthesis of Compound 036
Referring to the synthesis procedure and reaction conditions of example 11, compound 036 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (M/z) (M+).
Example 15: synthesis of Compound 037
Referring to the synthesis procedure and reaction conditions of example 11, compound 037 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (M/z) (M+).
Example 16: synthesis of Compound 041
Referring to the synthesis procedure and reaction conditions of example 11, compound 041 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (m/z) (m+).
Example 17: synthesis of Compound 045
Referring to the synthesis procedure and reaction conditions of example 11, compound 045 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (M/z) (M+).
Example 18: synthesis of Compound 047
The synthetic route is as follows:
。
(1) To the reaction flask were added 047-1 (10 mmoL), 047-2 (25 mmoL), sodium tert-butoxide (10 m)moL), 200mL of toluene, and after nitrogen substitution, pd2 (dba) 3 (5X 10) -2 mmoL)、Sphos(5×10 -2 mmoL), heating to 100-120 ℃, refluxing and reacting for 6 hours, and stopping the reaction. Cooling to 30-40deg.C, adding 200mL of water, and layering. After washing twice, toluene was concentrated, 100mL of n-heptane was added, and the mixture was slurried. Intermediate product 047-3 was obtained.
(2) To the reaction flask were added 047-3 (10 mmoL), 047-4 (25 mmoL), sodium t-butoxide (10 mmoL), 200mL of toluene, and after nitrogen substitution, pd2 (dba) 3 (5X 10) -2 mmoL)、Sphos(5×10 -2 mmoL), heating to 100-120 ℃, refluxing and reacting for 6 hours, and stopping the reaction. Cooling to 30-40deg.C, adding 200mL of water, and layering. After washing twice, toluene was concentrated, 100mL of n-heptane was added, and the mixture was slurried. The final product 047 was obtained.
Structure of test target product 047: LC-MS (m/z) (m+), theoretical value 585.34 and test value 585.78 were obtained by liquid chromatography-mass spectrometry analysis.
Example 19: synthesis of Compound 050
With reference to the synthesis procedure and reaction conditions of example 18, compound 050 was synthesized by liquid chromatography-mass spectrometry analysis to give LC-MS (M/z) (M+).
Example 20: synthesis of Compound 051
The synthetic route is as follows:
。
(1) 051-1 (10 mmoL), 051-2 (40 mmoL), sodium t-butoxide (10 mmoL), 200mL toluene were added to the flask, and after nitrogen substitution, pd2 (dba) 3 (5X 10) -2 mmoL)、Sphos(5×10 -2 mmoL), heating to 100-120 ℃, refluxing and reacting for 6 hours, and stopping the reaction. Cooling to 30-40deg.C, adding 200mL of water, and layering. After washing twice, toluene was concentrated, 100mL of n-heptane was added, and the mixture was slurried. The final product 051 is obtained.
Testing the target product 051 structure: LC-MS (m/z) (m+), theoretical value 491.36 and test value 491.74 were obtained by liquid chromatography-mass spectrometry analysis.
Example 21: synthesis of Compound 059
Referring to the synthesis procedure and reaction conditions of example 20, compound 059 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (m/z) (m+).
Example 22: synthesis of Compound 065
Referring to the synthesis procedure and reaction conditions of example 20, compound 065 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (m/z) (m+).
Example 23: synthesis of Compound 068
Referring to the synthesis procedure and reaction conditions of example 20, compound 068 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (M/z) (M+).
Example 24: synthesis of Compound 071
Referring to the synthesis procedure and reaction conditions of example 20, compound 071 was synthesized by liquid chromatography-mass spectrometry analysis to give LC-MS (M/z) (M+).
Example 25: synthesis of Compound 073
Referring to the synthesis procedure and reaction conditions of example 20, compound 073 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (M/z) (M+).
Example 26: synthesis of Compound 082
Referring to the synthesis procedure and reaction conditions of example 20, compound 082 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (M/z) (M+).
Example 27: synthesis of Compound 083
Referring to the synthesis procedure and reaction conditions of example 20, compound 083 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (m/z) (m+):theoretical 561.34 and test 561.76.
Example 28: synthesis of Compound 084
Referring to the synthesis procedure and reaction conditions of example 20, compound 084 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (M/z) (M+).
Example 29: synthesis of Compound 086
Referring to the synthesis procedure and reaction conditions of example 20, compound 086 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (M/z) (M+).
Example 30: synthesis of Compound 087
Referring to the synthesis procedure and reaction conditions of example 20, compound 087 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (M/z) (M+).
Example 31: synthesis of Compound 090
Referring to the synthesis procedure and reaction conditions of example 20, compound 090 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (m/z) (m+):theoretical 561.34 and test 561.80.
Example 32: synthesis of Compound 092
Referring to the synthesis procedure and reaction conditions of example 20, compound 092 was synthesized by liquid chromatography-mass spectrometry analysis to give LC-MS (M/z) (M+).
Example 33: synthesis of Compound 093
Referring to the synthesis procedure and reaction conditions of example 20, compound 093 was synthesized by liquid chromatography-mass spectrometry analysis to give LC-MS (M/z) (M+).
Example 34: synthesis of Compound 098
The synthetic route is as follows:
。
(1) Into a reaction flask were added 098-1 (10 mmoL), 098-2 (40 mmoL), sodium t-butoxide (10 mmoL), 200mL of toluene, and after nitrogen substitution, pd2 (dba) 3 (5X 10) -2 mmoL)、Sphos(5×10 -2 mmoL), heat up toReflux reaction is carried out for 6 hours at 100-120 ℃, and the reaction is stopped. Cooling to 30-40deg.C, adding 200mL of water, and layering. After washing twice, toluene was concentrated, 100mL of n-heptane was added, and the mixture was slurried. The final product 098 is obtained.
Test target product 098 structure: LC-MS (m/z) (m+), theoretical value 527.36 and test value 527.72 were obtained by liquid chromatography-mass spectrometry analysis.
Example 35: synthesis of Compound 103
Referring to the synthesis procedure and reaction conditions of example 34, compound 103 was synthesized by liquid chromatography-mass spectrometry analysis to give LC-MS (M/z) (M+).
Example 36: synthesis of Compound 109
Referring to the synthesis procedure and reaction conditions of example 34, compound 109 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (M/z) (M+).
Example 37: synthesis of Compound 113
Referring to the synthesis procedure and reaction conditions of example 34, compound 113 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (m/z) (m+).
Example 38: synthesis of Compound 115
Referring to the synthesis procedure and reaction conditions of example 34, compound 115 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (m/z) (m+).
Example 39: synthesis of Compound 117
Referring to the synthesis procedure and reaction conditions of example 34, compound 117 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (M/z) (M+).
Example 40: synthesis of Compound 126
Referring to the synthesis procedure and reaction conditions of example 34, compound 126 was synthesized by liquid chromatography-mass spectrometry analysis to give LC-MS (M/z) (M+).
Example 41: synthesis of Compound 127
Referring to the synthesis procedure and reaction conditions of example 34, compound 127 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (M/z) (M+).
Example 42: synthesis of Compound 128
Referring to the synthesis procedure and reaction conditions of example 34, compound 128 was synthesized by liquid chromatography-mass spectrometry analysis to give LC-MS (M/z) (M+).
Example 43: synthesis of Compound 130
Referring to the synthesis procedure and reaction conditions of example 34, compound 130 was synthesized by liquid chromatography-mass spectrometry analysis to give LC-MS (M/z) (M+).
Example 44: synthesis of Compound 131
Referring to the synthesis procedure and reaction conditions of example 34, compound 131 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (m/z) (m+).
Example 45: synthesis of Compound 133
Referring to the synthesis procedure and reaction conditions of example 34, compound 133 was synthesized and analyzed by liquid chromatography-mass spectrometry to give LC-MS (M/z) (M+).
Example 46: synthesis of Compound 136
Referring to the synthesis procedure and reaction conditions of example 34, compound 136 was synthesized by liquid chromatography-mass spectrometry analysis to give LC-MS (M/z) (M+).
Performance test one: characterization of refractive index of the material: in order to measure the optical properties of the compound, a single-layer film was produced by vapor deposition of a compound 005 having a thickness of 50nm on a glass substrate (0.7T) after washing in ethanol, deionized water, and acetone, respectively, for 10 minutes, and this was designated as example 1. A single-layer film was produced in the same manner as in example 1, except that each of the compounds shown in table 1 was used instead of the compound 005. The compounds prepared in examples 1-46 of the present invention and the compounds of comparative examples 1-2 were measured for n (refractive index) at different wavelengths using an ellipsometer from the company j.a. woollam. The optical properties of the compounds of the examples and comparative examples are shown in table 1. The structural formula of the compound of comparative examples 1-2 used is shown below:
TABLE 1 refractive indices of Compounds at different wavelengths
In Table 1, the values of n in the blue region and the red region of comparative examples 1-2 were in the range of 1.736-1.977 and 1.695-1.837, respectively, whereas the compounds produced in examples 1-46 of the present invention had refractive indices significantly lower in the blue region, the green region and the red region than in the comparative examples.
The following examples of the application of the low refractive index organic compounds of the present invention to OLED devices are provided to further illustrate the beneficial effects of the compounds of the present invention. The materials used in the examples were purchased commercially or synthesized by themselves.
Manufacturing of OLED device:
as a reference preparation mode of an embodiment of a device, the invention is to vapor-deposit 50-500nm ITO/Ag/ITO as an anode on an alkali-free glass substrate, sequentially laminate a vapor-deposited hole injection layer (5-20 nm), a hole transport layer (50-120 nm), a light-emitting auxiliary layer (5-120 nm), a light-emitting layer (20-50 nm), an electron transport layer (20-80 nm) and an electron injection layer (0.5-10 nm), prepare a semitransparent cathode by co-vapor-depositing Mg and Ag (weight ratio 1:9, 10-50 nm), and vapor-deposit a cover layer compound. And finally, encapsulating the light-emitting device by using an epoxy resin adhesive in a nitrogen atmosphere.
In a preferred embodiment, the OLED device provided by the present invention has the structure: the alkali-free glass substrate was first washed with an ultrasonic cleaner using isopropyl alcohol for 15 minutes, and then subjected to a UV ozone washing treatment in air for 30 minutes. The treated substrate was first vapor-deposited with ITO/Ag/ITO 100nm as an anode, then with a hole injection layer (HT: PD,10nm, 2%), a hole transport layer (HT, 100 nm), a light emission auxiliary layer (BP, 5 nm), a blue light emitting layer (host material: dopant material=compound BH: compound BD (weight ratio 97:3, 30 nm)), an electron transport layer (compound ET: liq=1:1, 30 nm), and an electron injection layer (LiF, 0.5 nm) were sequentially stacked and vapor-deposited, and then Mg and Ag (weight ratio 1:9, 10 nm) were co-vapor-deposited to form a semitransparent cathode, and then with vapor-deposited compound Ref 01 (45 nm) as a high refractive coating and vapor-deposited compound 005 (20 nm) as a low refractive coating. Let it be application example 1, device structure: ITO: ITO/HT: PD (2%, 10 nm)/HT (100 nm)/BP (5 nm)/BH: BD (97:3, 30 nm)/ET: liq (50:50)/LiF (0.5 nm)/Mg: ag (1:9, 10 nm)/Ref 01 (45 nm)/Compound 005 (20 nm).
It should be noted that the high refractive coating material used in the present application example is merely exemplary, and is not a specific limitation of the present invention, and the high refractive coating material may be selected from known or unknown materials, and the high refractive coating material Ref 01 of the present invention may be replaced conventionally.
The molecular structural formula of the related material is shown as follows:
application examples 2 to 46 and comparative application examples 1 to 2 were prepared with reference to the method provided in application example 1 described above, except that the compounds listed in table 2 were used as the cover layer materials instead of the cover layer materials used in application example 1, respectively.
Performance evaluation of OLED device:
testing the currents of the OLED device under different voltages by using a Keithley 2365A digital nanovoltmeter, and dividing the currents by the light emitting areas to obtain the current densities of the OLED device under different voltages; testing the brightness and radiant energy density of the OLED device under different voltages by using a Konicaminolta CS-2000 spectroradiometer; according to the current density and brightness of the OLED device under different voltages, the OLED device is obtainedAt the same current density (10 mA/cm 2 ) BI=E/CIEy refers to Blue Index in Blue light, and is also a parameter for measuring the luminous efficiency of Blue light, E refers to current efficiency, and CIEy refers to an ordinate color point obtained by bringing the device luminous half-width wavelength into CIE1930 software. The test data are shown in table 2.
TABLE 2 coating material application example device and electronic luminescence characteristics table
As can be seen from table 2, application examples 1 to 46 have higher BI light emitting efficiency as compared with comparative application examples 1 and 2. The improvement in performance of each application example is based on the combination of the specific low refractive index organic compound material and the organic compound with higher refractive index; the low refractive index organic compound material provided by the invention can improve the interface effect of the inner layer of the device, can also improve the light extraction effect of the organic layer, has excellent coordination, and can obviously improve the luminous efficiency of the device.
The present embodiment is only for explanation of the present invention and is not to be construed as limiting the present invention, and modifications to the present embodiment, which may not creatively contribute to the present invention as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present invention.

Claims (13)

1. A low refractive index organic compound, characterized in that the low refractive index organic compound has a structure represented by the following formula (I):
，
in the formula (I), R 1 -R 15 Each independently selected from the group consisting of hydrogen, deuterium, halogen, C1-C20 alkyl, C3-C20 cycloalkyl, C1-C20 haloalkyl, C6-C30 aryl, and combinations thereof.
2. The low refractive index organic compound according to claim 1, wherein the R 1 -R 15 Each independently selected from the group consisting of hydrogen, deuterium, F, C1-C10 alkyl, C1-C10 fluoroalkyl, C6-C10 monocycloalkyl, C4-C10 bridged cycloalkyl, C6-C18 non-fused aryl, and combinations thereof.
3. The low refractive index organic compound according to claim 1, wherein in the formula (I), R 1 -R 15 Each independently selected from hydrogen, methyl, trifluoromethyl, t-butyl, cyclohexane, norbornyl, phenyl, biphenyl, or o-terphenyl; the R is 1 -R 15 Not both phenyl.
4. The low refractive index organic compound according to claim 1, wherein the low refractive index organic compound is selected from any one of the chemical structures shown below:
。
5. use of the low refractive index organic compound according to any one of claims 1 to 4 for the preparation of an organic electroluminescent device.
6. The use according to claim 5, wherein said low refractive index organic compound is used for the cover layer.
7. An organic electroluminescent device, characterized in that the organic electroluminescent device comprises:
a substrate layer;
a first electrode over the substrate layer;
an organic light emitting functional layer over the first electrode;
a second electrode over the organic light emitting functional layer;
a cover layer over the second electrode; the cover layer comprising the low refractive index organic compound according to any one of claims 1 to 4.
8. An organic electroluminescent device according to claim 7, wherein the cover layer further comprises a high refractive index organic compound, wherein the high refractive index compound has a refractive index n of 1.95-2.30 at a wavelength of 460nm, a refractive index n of 1.90-2.05 at a wavelength of 530nm, and a refractive index n of 1.80-2.00 at a wavelength of 620 nm.
9. An organic electroluminescent device as claimed in claim 7, wherein the refractive index n of the low refractive index organic compound satisfies the following condition:
refractive index n between 450-650nm wavelength 450-650 <1.60, and an extinction coefficient between 450-650nm wavelength of below 0.1;
difference n between refractive index of 460nm and refractive index of 530 460 -n 530 <0.1；
Difference n between refractive index of 510nm and refractive index of 620 510 -n 620 <0.05。
10. An organic electroluminescent device as claimed in claim 7, wherein the thickness of the cover layer is 40-80nm.
11. A formulation comprising the low refractive index organic compound according to any one of claims 1 to 4 and at least one solvent.
12. Use of an organic electroluminescent device as claimed in any one of claims 7 to 10 in a display or lighting apparatus.
13. A display or lighting device, characterized in that the device comprises an organic electroluminescent device as claimed in any one of claims 7-10.
CN202311621496.XA 2023-11-30 2023-11-30 Low refractive index organic compound, OLED (organic light emitting diode) with same and organic light emitting device Pending CN117586131A (en)

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