An organic compound containing phenylfluorene and an organic light-emitting device

Abstract

The present invention provides an organic compound containing phenylfluorene and an organic light-emitting device, relating to the technical field of organic optoelectronic materials. The compound of the present invention has a high glass transition temperature, controls the crystallinity of the material, and can adjust the HOMO energy level of the molecule, better matching with the adjacent functional layer, enabling better combination of electrons and holes, enhancing the hole transport efficiency, thereby improving the hole transport performance and thermal stability of the organic light-emitting device. When applied to an organic light-emitting device, it can effectively improve the luminous efficiency and service life of the device. It has good industrialization prospects and can be widely applied in fields such as panel display, lighting source, flexible OLED, electronic paper, organic solar cell, organic photoreceptor, signboard, signal lamp, etc.

Description

Technical Field

[0001] The present invention relates to the technical field of organic optoelectronic materials, and particularly to an organic compound containing phenylfluorene and an organic light-emitting device thereof. Background Art

[0002] Organic Light-Emitting Diodes (OLEDs) are also known as organic light-emitting semiconductors. OLED display technology has the characteristics of energy saving, fast response speed, stable color, strong environmental adaptability, no radiation, light weight, thin thickness, and relatively simple device manufacturing process. A more significant feature of OLED compared with previous display technologies is that it can manufacture bent or curled display screens. Therefore, the development of suitable organic thin-film materials has always been the research focus of the OLED industry.

[0003] Generally, the materials used for OLEDs include light-emitting materials, auxiliary materials, electrode materials, and covering layer materials. Among them, the auxiliary materials mainly include charge carrier transport materials, charge carrier injection materials, and charge carrier blocking materials. Different auxiliary materials play different functions and roles in the device. Therefore, different functional requirements are usually imposed on different auxiliary materials.

[0004] The hole transport material mainly transports holes. In an OLED, the function of the hole transport layer containing the hole transport material is to improve the hole transport efficiency in the device and block electrons in the light-emitting layer to achieve the maximum recombination of charge carriers. The hole transport material for OLEDs is first required to have a high hole mobility, the triplet energy level of the molecule should be higher than the excitation energy of the light-emitting layer, it should avoid forming exciplexes with the light-emitting layer, and it needs to have good film-forming properties, high thermal stability, and an appropriate highest occupied molecular orbital (HOMO) energy level to ensure the effective injection and transport of holes between various interfaces. Although the aging mechanism of OLEDs has not been fully understood yet, some studies have shown that the change in the physical morphology of the organic layer is one of the factors affecting the aging of OLEDs. For example, the melting and crystallization of the organic layer caused by the heat generated during device operation will not only destroy the uniformity of the film but also damage the good interfacial contact between the hole transport layer and the anode as well as the organic layer, resulting in a decrease in the efficiency and lifespan of the device.

[0005] Therefore, the current research focus of hole transport materials is on how to improve the film-forming properties, thermal stability, and the light-emitting efficiency of the device. Therefore, it is very necessary to develop a compound with excellent performance that can be used in organic light-emitting devices. Summary of the Invention

[0006] The object of the present invention is to provide an organic compound containing phenylfluorene and an organic light-emitting device based on the prior art with the goal of industrialization. The organic light-emitting device prepared using the organic compound containing phenylfluorene is applied to the hole transport region to develop an organic light-emitting device with high efficiency and long lifespan. The general formula of its molecular structure is shown in Formula I:

[0007]

[0008] Wherein, the Ar 1 is selected from the group shown in Formula b-1, and the Ar 2 is selected from the group shown in Formula a-1, Formula a-2 or Formula b-1:

[0009]

[0010] The R b and R p are the same as or different from each other. At least one of R b and R p is selected from the group represented by A-1 or A-2, and the rest are independently selected from any one of hydrogen, deuterium, cyano, halogen, trifluoromethyl, substituted or unsubstituted silyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C7 cycloalkyl;

[0011]

[0012] The R a are the same as or different from each other and are independently selected from any one of hydrogen, deuterium, cyano, halogen, C1-C6 alkyl, phenyl, and deuterated phenyl;

[0013] The a 1 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15; the a 2 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11;

[0014] The R c and R d are independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C25 aryl, or R c and R d can be connected to form a substituted or unsubstituted phenylfluorene ring or a substituted or unsubstituted aliphatic ring;

[0015] The b 1 is selected from 1, 2 or 3; when b 1 is greater than 1, each R b is the same as or different from each other, and adjacent Rb can be bonded together to form a benzene ring or a naphthalene ring; the b 2 is selected from 1, 2, 3 or 4; when b 2 is greater than 1, each R b is the same or different, and adjacent R b can be bonded together to form a benzene ring or a naphthalene ring;

[0016] the p 1 is selected from 1, 2, 3, 4 or 5; when p 1 is greater than 1, each R p is the same or different, and adjacent R p can be bonded together to form a cyclic structure;

[0017] the p 2 is selected from 1, 2, 3, 4, 5, 6 or 7; when p 2 is greater than 1, each R p is the same or different, and adjacent R p can be bonded together to form a cyclic structure;

[0018] the R 1 、R 2 、R 3 、R 4 is independently selected from hydrogen, deuterium, cyano, halogen, trifluoromethyl, substituted or unsubstituted silyl, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or any two adjacent R 1 are combined with each other to form a substituted or unsubstituted benzene ring or naphthalene ring, or any two adjacent R 2 are combined with each other to form a substituted or unsubstituted benzene ring or naphthalene ring, or any two adjacent R 3 are combined with each other to form a substituted or unsubstituted benzene ring or naphthalene ring, or any two adjacent R 4 are combined with each other to form a substituted or unsubstituted benzene ring or naphthalene ring;

[0019] the n 1 is selected from 0, 1, 2, 3 or 4; the n 2 is selected from 0, 1, 2, 3 or 4; the n 3 is selected from 0, 1, 2, 3 or 4; the n 4 is selected from 0, 1, 2, 3, 4 or 5;

[0020] the L 0Selected from a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted terphenyl, a substituted or unsubstituted phenylene-naphthylene, a substituted or unsubstituted naphthylene-naphthylene, a substituted or unsubstituted anthracene, a substituted or unsubstituted phenanthrene, a substituted or unsubstituted triphenylene;

[0021] Said L 1 , L 2 Independently selected from a single bond, a substituted or unsubstituted C6-C25 arylene;

[0022] Said * is a connecting bond.

[0023] The present invention also provides an organic light-emitting device, comprising an anode, a cathode, and an organic layer, wherein the organic layer is located between the anode and the cathode or outside one or more electrodes of the anode and the cathode, and the organic layer contains any one or a combination of at least two of the organic compounds containing phenylfluorene according to the present invention.

[0024] Advantages of the present invention:

[0025] The present invention provides an organic compound containing phenylfluorene and an organic light-emitting device thereof. The compound of the present invention has a triarylamine as the center, and 9-phenylfluorene is connected to the N of the triarylamine. At the same time, an adamantyl group is introduced at a specific position of the compound, reducing the symmetry of the compound, increasing the glass transition temperature of the material, controlling the crystallinity of the material, and the compound of the present invention can adjust the HOMO energy level of the molecule, better match with the adjacent functional layer, enable better combination of electrons and holes, enhance the hole transport efficiency, thereby improving the hole transport performance and thermal stability of the organic light-emitting device. When applied to an organic light-emitting device, it can effectively improve the luminous efficiency and service life of the device. Detailed embodiments

[0026] The technical solutions of the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts belong to the protection scope of the present invention.

[0027] In this specification, when the position of the substituent on the ring is not fixed, it means that it can be connected to any one of the corresponding optional sites of the ring.

[0028] For example, Can represent Can represent Can represent And so on.

[0029] The halogen in the present invention refers to fluorine, chlorine, bromine and iodine.

[0030] The alkyl group in the present invention refers to the hydrocarbon group formed by removing one hydrogen atom from an alkane molecule, which can be a straight-chain alkyl group or a branched-chain alkyl group, preferably having 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. The straight-chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, etc., but are not limited thereto; the branched-chain alkyl groups include isopropyl, isobutyl, sec-butyl, tert-butyl, isomeric groups of n-pentyl, isomeric groups of n-hexyl, isomeric groups of n-heptyl, isomeric groups of n-octyl, isomeric groups of n-nonyl, isomeric groups of n-decyl, etc., but are not limited thereto. The above alkyl groups are preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl.

[0031] The chain alkyl groups with more than three carbon atoms in the present invention include their isomers. For example, propyl includes n-propyl and isopropyl, and butyl includes n-butyl, sec-butyl, isobutyl, and tert-butyl. And so on.

[0032] The "substituted or unsubstituted silyl group" in the present invention refers to the —Si(R k ) 3 group, where each R k is the same or different and is selected from the following groups: hydrogen, deuterium, tritium, cyano group, halogen, nitro group, substituted or unsubstituted C1-C30 alkyl group, substituted or unsubstituted C1-C30 alkenyl group, substituted or unsubstituted C3-C30 cycloalkyl group, substituted or unsubstituted C6-C60 aryl group, substituted or unsubstituted C2-C60 heteroaryl group, substituted or unsubstituted fused ring group of C3-C30 alicyclic ring and C6-C60 aromatic ring, substituted or unsubstituted fused ring group of C3-C30 alicyclic ring and C2-C60 heteroaryl ring. Preferably, each R k is the same or different and is selected from the following groups: hydrogen, deuterium, tritium, cyano group, halogen, nitro group, substituted or unsubstituted C1-C30 alkyl group, substituted or unsubstituted C3-C30 cycloalkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 20, preferably 1 to 15, more preferably 1 to 10, and most preferably 1 to 8. The number of carbon atoms of the cycloalkyl group is preferably 3 to 20, preferably 3 to 15, more preferably 3 to 10, and most preferably 3 to 7. Preferably, each R kSame or different and selected from the following groups: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl. Preferred substituted silyls specifically include trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, etc., but are not limited thereto. The above silyls are preferably trimethylsilyl, triethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, diphenylmethylsilyl, phenyldimethylsilyl.

[0033] The cycloalkyl group described in the present invention refers to a hydrocarbon group formed by removing one hydrogen atom from a cycloalkane molecule, preferably having 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, particularly preferably 3 to 6 carbon atoms. Examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, camphenyl, norbornyl, etc., but are not limited thereto. The above cycloalkyl groups are preferably cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, norbornyl.

[0034] The aryl group described in the present invention refers to the general name of a monovalent group remaining after removing one hydrogen atom from the aromatic nucleus carbon of an aromatic compound molecule. It can be a monocyclic aryl group, a polycyclic aryl group or a fused-ring aryl group, preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic aryl group refers to an aryl group having only one aromatic ring in the molecule, such as phenyl, etc., but is not limited thereto; the polycyclic aryl group refers to an aryl group having two or more independent aromatic rings in the molecule, such as biphenyl, terphenyl, etc., but is not limited thereto; the fused-ring aryl group refers to an aryl group having two or more aromatic rings and fused to each other by sharing two adjacent carbon atoms, such as naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylenyl, fluoranthenyl, spirobifluorenyl, etc., but is not limited thereto. The above aryl groups are preferably phenyl, biphenyl, terphenyl, naphthyl (preferably 2-naphthyl), anthryl (preferably 2-anthryl), phenanthryl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylenyl, spirobifluorenyl.

[0035] As used herein, the term "arylene" refers to the general name of a divalent group remaining after removing two hydrogen atoms from the aromatic nucleus carbon of an aromatic compound molecule. It can be a monocyclic arylene, polycyclic arylene, or fused-ring arylene, preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic arylene includes, but is not limited to, phenylene, etc.; the polycyclic arylene includes, but is not limited to, biphenylene, terphenylen, etc.; the fused-ring arylene includes, but is not limited to, naphthylene, anthrylene, phenanthrylene, fluorenylene, pyrenylene, triphenylene, fluoranthenylene, phenylfluorenylene, etc. The above arylene is preferably phenylene, biphenylene, terphenylen, naphthylene, fluorenylene, phenylfluorenylene.

[0036] As used herein, the term "substituted...", such as substituted alkyl, substituted silyl, substituted cycloalkyl, substituted alkenyl, substituted aryl, substituted arylene, etc., means that it is mono-substituted or multi-substituted by a group independently selected from deuterium, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C15 heteroaryl, substituted or unsubstituted amino group, substituted or unsubstituted silyl, etc., but not limited thereto. Preferably, it is mono-substituted or multi-substituted by a group selected from deuterium, methyl, ethyl, isopropyl, tert-butyl, trimethylsilyl, triphenylsilyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, benzophenanthrenyl, perylenyl, pyrenyl, benzyl, tolyl, fluorenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, diphenylamino group, dimethylamino group, carbazolyl, 9-phenylcarbazolyl, acridinyl, furyl, thienyl, benzofuryl, benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuryl, dibenzothienyl, phenothiazinyl, phenoxazinyl, indolyl. In addition, the above substituents can also be substituted by one or more deuterium, halogen atoms, cyano group, alkyl, cycloalkyl, and aryl substituents as described above.

[0037] Unless otherwise specified, the term "ring" as used herein refers to a fused ring composed of an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof, which includes saturated or unsaturated rings.

[0038] As used herein, the term "bonded to form a cyclic structure" means that two groups are connected to each other by a chemical bond and optionally aromatized. Examples are as follows:

[0039]

[0040] In the present invention, the formed ring can be a five-membered ring, a six-membered ring or a fused ring, such as benzene, naphthalene, fluorene, cyclopentene, cyclopentane, cyclohexene, cyclohexane, benzocyclohexane, quinoline, isoquinoline, pyridine, pyrimidine, dibenzothiophene, dibenzofuran, phenanthrene or pyrene, but not limited thereto.

[0041] In the present invention, the at least one includes one, two, three, four or more.

[0042] The present invention provides an organic compound containing phenylfluorene, and its molecular structure general formula is shown in Formula I:

[0043]

[0044] Wherein, the Ar 1 is selected from the group shown in Formula b-1, and the Ar 2 is selected from the group shown in Formula a-1, Formula a-2 or Formula b-1:

[0045]

[0046] The R b , R p are the same as or different from each other, at least one of R b and R p is selected from the group represented by A-1 or A-2, and the rest are independently selected from any one of hydrogen, deuterium, cyano, halogen, trifluoromethyl, substituted or unsubstituted silyl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C7 cycloalkyl;

[0047]

[0048] The R a are the same as or different from each other, and are independently selected from any one of hydrogen, deuterium, cyano, halogen, C1-C6 alkyl, phenyl, deuterated phenyl;

[0049] The a 1 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15; the a 2 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11;

[0050] The R c , R d are independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C25 aryl, or R c , R d can be connected to form a substituted or unsubstituted phenylfluorene ring or a substituted or unsubstituted aliphatic ring;

[0051] The said b 1 is selected from 1, 2 or 3; when b 1 is greater than 1, each R b is the same or different, and adjacent Rs b can be bonded together to form a benzene ring or a naphthalene ring; the said b 2 is selected from 1, 2, 3 or 4; when b 2 is greater than 1, each R b is the same or different, and adjacent Rs b can be bonded together to form a benzene ring or a naphthalene ring;

[0052] The said p 1 is selected from 1, 2, 3, 4 or 5; when p 1 is greater than 1, each R p is the same or different, and adjacent Rs p can be bonded together to form a cyclic structure;

[0053] The said p 2 is selected from 1, 2, 3, 4, 5, 6 or 7; when p 2 is greater than 1, each R p is the same or different, and adjacent Rs p can be bonded together to form a cyclic structure;

[0054] The said R 1 、R 2 、R 3 、R 4 are independently selected from hydrogen, deuterium, cyano, halogen, trifluoromethyl, substituted or unsubstituted silyl, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or any two adjacent Rs 1 are combined with each other to form a substituted or unsubstituted benzene ring or naphthalene ring, or any two adjacent Rs 2 are combined with each other to form a substituted or unsubstituted benzene ring or naphthalene ring, or any two adjacent Rs 3 are combined with each other to form a substituted or unsubstituted benzene ring or naphthalene ring, or any two adjacent Rs 4 are combined with each other to form a substituted or unsubstituted benzene ring or naphthalene ring;

[0055] The said n 1 is selected from 0, 1, 2, 3 or 4; the said n 2 is selected from 0, 1, 2, 3 or 4; the said n 3 is selected from 0, 1, 2, 3 or 4; the said n 4 is selected from 0, 1, 2, 3, 4 or 5;

[0056] The said L 0Selected from a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted terphenylene, a substituted or unsubstituted phenylene-naphthylene, a substituted or unsubstituted naphthylene-naphthylene, a substituted or unsubstituted anthracenylene, a substituted or unsubstituted phenanthrenylene, a substituted or unsubstituted triphenylene;

[0057] Said L 1 , L 2 are independently selected from a single bond and a substituted or unsubstituted C6-C25 arylene;

[0058] Said * is a connecting bond;

[0059] Wherein, "substituted..." in the above "substituted or unsubstituted..." means being substituted by one or more substituents independently selected from the group consisting of deuterium, cyano, halogen, trifluoromethyl, silyl, C1-C15 alkyl, C3-C15 cycloalkyl, and C6-C25 aryl.

[0060] Preferably, one, two, three, four or more of all Rs in formula I b and R p are selected from the groups represented by A-1 or A-2.

[0061] Preferably, at least one (one, two, three, four or more) of all Rs in formula I p is selected from the groups represented by A-1 or A-2.

[0062] Preferably, at least one (one, two, three, four or more) of all Rs in formula I b is selected from the groups represented by A-1 or A-2.

[0063] Most preferably, at least one (one, two, three, four or more) of all Rs in formula I p is selected from the groups represented by A-1.

[0064] Preferably, A-1 is selected from one of the following groups:

[0065]

[0066] A-2 is selected from one of the following groups:

[0067]

[0068] Preferably, formula a-1 or formula a-2 is selected from any one of the following groups:

[0069]

[0070] The R p are the same as or different from each other and are independently selected from hydrogen, deuterium, cyano, halogen, or one of the following substituted or unsubstituted groups: silyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, triphenylenyl, one of Formula A-1 and Formula A-2; wherein the substituents in the "substituted or unsubstituted" are selected from deuterium, cyano, halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, camphyl, norbornyl, trimethylsilyl, triphenylsilyl, phenyl, biphenyl, naphthyl, one or more of them, and when substituted by multiple substituents, the multiple substituents are the same as or different from each other;

[0071] The p 1 is selected from 1, 2, 3, 4, or 5; the p 2 is selected from 1, 2, 3, 4, 5, 6, or 7; the p 3 is selected from 1, 2, or 3; the p 4 is selected from 1, 2, 3, or 4; the p 5 is selected from 1 or 2; the p 6 is selected from 1, 2, 3, 4, 5, or 6.

[0072] Further preferably, the Formula a-1 or Formula a-2 is selected from any one of the following groups:

[0073]

[0074]

[0075] , and the above groups may be further substituted by one or more, one or more of deuterium, cyano, halogen, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl.

[0076] Most preferably, the Formula a-1 or Formula a-2 is selected from any one of the following groups:

[0077]

[0078]

[0079] , and the above groups may be further substituted by one or more, one or more of deuterium, cyano, halogen, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl.

[0080] Preferably, the formula a-1 or formula a-2 is selected from those containing a substituted or unsubstituted adamantyl group, or a substituted or unsubstituted norbornyl group among the groups shown above.

[0081] Preferably, the formula b-1 is selected from any one of the groups shown below:

[0082]

[0083]

[0084] The Rs b are the same as or different from each other and are independently selected from hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, deuterated isopropyl, deuterated tert-butyl, deuterated cyclohexyl, deuterated cyclopentyl, deuterated cyclobutyl, deuterated cyclopropyl, phenyl, deuterated phenyl, tolyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, naphthyl, deuterated naphthyl, methylfluorenyl, deuterated methylfluorenyl, trimethylsilyl, triphenylsilyl, one of formula A-1 and formula A-2, or two adjacent groups are bonded together to form a benzene ring;

[0085] The b 1 is selected from 1, 2 or 3; the b 2 is selected from 1, 2, 3 or 4; the b 3 is selected from 1, 2, 3, 4 or 5; the b 4 is selected from 1, 2, 3, 4, 5, 6 or 7; the b 6 is selected from 1, 2, 3, 4, 5 or 6; the b 7 is selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9; the b 8 is selected from 1, 2, 3, 4, 5, 6, 7 or 8; the b 9 is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; the b 10 is selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11;

[0086] The Rs e are the same as or different from each other and are independently selected from hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, deuterated isopropyl, deuterated tert-butyl, deuterated cyclohexyl, deuterated cyclopentyl, deuterated cyclobutyl, deuterated cyclopropyl, phenyl, deuterated phenyl, tolyl, biphenyl, deuterated biphenyl, terphenyl, deuterated terphenyl, naphthyl, deuterated naphthyl, trimethylsilyl, triphenylsilyl, one of formula A-1 and formula A-2, or two adjacent groups are bonded together to form a benzene ring;

[0087] The e 1Selected from 1, 2, 3, 4 or 5; the e 2 Selected from 1, 2, 3 or 4; the e 3 Selected from 1, 2, 3, 4, 5 or 6; the e 4 Selected from 1, 2, 3, 4, 5, 6 or 7; the e 5 Selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9; the e 6 Selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.

[0088] More preferably, the formula b-1 is selected from any one of the following groups:

[0089]

[0090]

[0091] Preferably, the formula b-1 is selected from those containing a substituted or unsubstituted adamantyl group, or a substituted or unsubstituted norbornyl group among the groups shown above.

[0092] Preferably, the L 1 、L 2 Independently selected from a single bond or one of the following groups:

[0093]

[0094] The R q Is selected from any one of hydrogen, deuterium, a halogen atom, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, and a substituted or unsubstituted C6-C30 aryl group;

[0095] The q 1 Is selected from 0, 1, 2, 3 or 4; the q 2 Is selected from 0, 1, 2, 3, 4, 5 or 6; the q 3 Is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0096] More preferably, the L 1 、L 2 Independently selected from a single bond or one of the following groups:

[0097]

[0098] Most preferably, the L 1 、L 2 Independently selected from a single bond or one of the following groups:

[0099]

[0100] The R 1 , R 2 , R 3 , R 4 are independently selected from one of hydrogen, deuterium, cyano, halogen, and a substituted or unsubstituted group as follows: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, camphyl, norbornyl, silyl, phenyl, biphenyl, naphthyl, anthryl, phenanthryl, triphenylenyl; wherein the substituent in the "substituted or unsubstituted" is selected from one or more of deuterium, cyano, halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, camphyl, norbornyl, trimethylsilyl, triphenylsilyl, phenyl, biphenyl, naphthyl, and in the case of being substituted by multiple substituents, the multiple substituents are the same or different from each other; or any two adjacent R 1 are combined with each other to form a substituted or unsubstituted benzene ring, or any two adjacent R 2 are combined with each other to form a substituted or unsubstituted benzene ring, or any two adjacent R 3 are combined with each other to form a substituted or unsubstituted benzene ring, or any two adjacent R 4 are combined with each other to form a substituted or unsubstituted benzene ring.

[0101] Most preferably, the organic compound containing phenylfluorene is selected from any one of the following chemical structures:

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117] The preparation method of the organic compound containing phenylfluorene described in Formula I of the present invention can be prepared by conventional coupling reactions in the art. For example, it can be prepared through the following synthetic route, but the present invention is not limited thereto:

[0118]

[0119] Under a nitrogen atmosphere, amine compound a and halogen compound b undergo Buchwald reaction to obtain intermediate A, and then Buchwald reaction with halogen compound c, and react at the corresponding catalyst, organic base, ligand, solution and corresponding temperature to obtain the corresponding compound of Formula I, where X 0 、X 1 are selected from Cl, Br or I.

[0120] The present invention has no particular limitation on the sources of the raw materials used in the above various reactions, and commercially available product raw materials can be used or prepared by methods well-known to those skilled in the art. The present invention has no special limitation on the above reactions, and conventional reactions well-known to those skilled in the art can be used. The compound synthesis steps of the present invention are few and the method is simple, which is beneficial to industrial production.

[0121] The present invention also provides an organic light-emitting device, including an anode, a cathode, and an organic layer. The organic layer is located between the anode and the cathode or outside one or more of the electrodes of the anode and the cathode, and the organic layer contains any one or a combination of at least two of the organic compounds containing phenylfluorene described in the present invention.

[0122] Preferably, the organic layer includes a hole transport region, and the hole transport region contains any one or a combination of at least two of the organic compounds containing phenylfluorene described in the present invention.

[0123] Preferably, the hole transport region includes a hole transport layer, and the hole transport layer contains any one or a combination of at least two of the organic compounds containing phenylfluorene described in the present invention.

[0124] Preferably, the hole transport layer includes a hole transport layer and a light-emission assisting layer (second hole transport layer), the light-emission assisting layer is located between the hole transport layer and the light-emitting layer, and at least one of the hole transport layer and the light-emission assisting layer contains any one or at least two combinations of the phenylfluorene-containing organic compounds of the present invention.

[0125] Preferably, the organic layer includes a cover layer, and the cover layer contains any one or at least two combinations of the phenylfluorene-containing organic compounds of the present invention.

[0126] Preferably, the cover layer of the present invention can be a single-layer structure, a two-layer structure or a multi-layer structure, and at least one of the cover layer materials of the present invention is selected from the phenylfluorene-containing organic compounds of the present invention, or contains conventional cover layer materials well-known to those skilled in the art.

[0127] The light-emitting device of the present invention is usually formed on a substrate. As long as the above substrate does not change when forming the electrodes and forming the organic layers, for example, substrates such as glass, plastic, polymer film, and silicon. When the substrate is opaque, the electrode opposite thereto is preferably transparent or semi-transparent.

[0128] Anode materials are usually substances with a large work function in order to enable holes to be smoothly injected into the organic layer. Specific examples of anode materials include metals such as vanadium, chromium, copper, zinc, and gold or their alloys; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO 2 :Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylenedioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, etc., but not limited thereto. The anode can be formed into a laminated structure of two or more layers, such as ITO / Ag / ITO. Preferably, the anode of the present invention uses a transparent ITO substrate.

[0129] The hole injection layer is a layer for injecting holes from the electrode. As the hole injection substance, it is preferably capable of transporting holes, having a hole injection effect from the anode and an excellent hole injection effect on the light-emitting layer or light-emitting material. The HOMO of the preferred hole injection substance is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of hole injection substances include metal porphyrins, oligothiophenes, arylamine-based organic compounds, hexanitrile hexaazatriphenylene-based organic compounds, quinacridone-based organic compounds, perylene-based organic compounds, anthraquinone, and polyaniline and polythiophene-based conductive polymers, etc., but not limited thereto.

[0130] The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer. The hole transport layer may include a first hole transport layer material and a second hole transport layer material. As a hole transport substance, it can receive holes from the anode or the hole injection layer and transfer them to the light-emitting layer, and has a large hole mobility. As a specific example, there are arylamine-based organic compounds, conductive polymers, and block copolymers that have both a conjugated part and a non-conjugated part, but are not limited thereto. Preferably, the hole transport layer is selected from any one or a combination of at least two of the organic compounds containing phenylfluorene described in the present invention.

[0131] The electron blocking layer is a layer that can prevent the holes injected from the hole injection layer from passing through the light-emitting layer and entering the electron injection layer, thereby improving the lifespan and efficiency of the device. When necessary, it can be formed of a known material at an appropriate part between the light-emitting layer and the electron injection layer.

[0132] The light-emitting substance of the light-emitting layer is a substance that can receive holes and electrons from the hole transport layer and the electron transport layer respectively and combine them to emit light in the visible light region. Preferably, it is a substance with high quantum efficiency for fluorescence or phosphorescence. As a specific example, there are aluminum 8-hydroxyquinoline complexes (Alq 3 ); carbazole-based compounds; distyrylbenzene compounds; BAlq; 10-hydroxybenzoquinoline metal compounds; benzoxazole, benzothiazole, and benzimidazole-based compounds; poly(p-phenylene vinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, etc., but are not limited thereto.

[0133] The light-emitting layer may contain a host material and a dopant material. The host material includes aromatic condensed ring derivatives or heterocyclic compounds, etc. Specifically, as aromatic condensed ring derivatives, there are anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and as heterocyclic compounds, there are carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, etc., but are not limited thereto.

[0134] The dopant material includes aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, etc., but is not limited thereto. As metal complexes, there are iridium complexes, platinum complexes, etc., but are not limited thereto. Preferably, the dopant material described in the present invention uses iridium complexes.

[0135] As the doping ratio of the light-emitting layer host material and the light-emitting layer guest material, the optimum may vary depending on the materials used. Generally, the doping mass percentage of the light-emitting layer guest material is 0.01% to 20%, preferably 0.1% to 15%, and more preferably 1% to 10%.

[0136] The hole blocking layer is a layer that prevents holes from reaching the cathode, and generally can be formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives or triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, etc., but not limited thereto.

[0137] The electron transport layer is a layer with the function of transporting electrons, which plays the role of injecting electrons and balancing carriers. The electron transport layer may include a first electron transport layer material and a second electron transport layer material. The electron transport materials described in the present invention may be selected from well-known oxadiazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethane and its derivatives, fluorenone derivatives, biphenylquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, but not limited thereto. It may be a single structure composed of a single substance, or a single-layer structure or a multi-layer structure formed by different substances.

[0138] The electron injection layer is a layer that injects electrons from the electrode, preferably has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light-emitting layer or the light-emitting material, prevents the excitons generated in the light-emitting layer from migrating to the hole injection layer, and has excellent thin film forming ability. Specifically, there are alkali metal compounds such as lithium oxide (Li 2 O), lithium borate (LiBO 2 ), cesium carbonate (Cs 2 CO 3 ), potassium silicate (K 2 SiO 3 ), etc., alkali metal fluorides (MF, where M is Li, Na, K, Rb, Cs). If Al is used as the cathode material, the optimal thickness of these materials is usually less than 1.0 nm. Preferably, the electron injection layer described in the present invention may be selected from LiF.

[0139] The cathode material is usually a material with a small work function in order to facilitate the injection of electrons into the organic layer. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or their alloys; multi-layer structure materials such as LiF / Al or LiO 2 / Al, etc., but not limited thereto.

[0140] The cover layer is to reduce the total emission loss and waveguide loss in the OLED device and improve the light extraction efficiency. The cover layer material of the present invention may adopt Alq 3 , TPBi or any one or at least two combinations of the organic compounds containing phenylfluorene described in the present invention.

[0141] The preparation and formation methods of each layer in the organic light-emitting device are not particularly limited, and any one of vacuum evaporation, spin coating, chemical vapor deposition, blade coating, laser thermal transfer printing, electrospray coating, slot die coating, dip coating can be used. In the present invention, vacuum evaporation is preferably adopted.

[0142] The organic light-emitting device of the present invention can be widely applied to the fields of information display technology, lighting source, flexible OLED, electronic paper, organic solar cell, organic photoreceptor or organic thin film transistor, signboard, signal lamp, etc. In terms of information display, it is widely used in various information displays, such as mobile phones, tablet computers, TVs, wearable devices, VR, smart watches, digital cameras, vehicle displays, and taillights.

[0143] The present invention is more specifically explained by the following examples, but it is not intended to limit the present invention thereby. Based on this description, those of ordinary skill in the art will be able to implement the present invention and prepare other compounds and devices according to the present invention within the entire disclosed scope without creative labor.

[0144] Preparation and Characterization of Compounds

[0145] Description of raw materials, reagents, and characterization equipment:

[0146] The present invention has no particular limitation on the sources of raw materials used in the following examples, and they can be commercially available products or prepared by methods well-known to those skilled in the art.

[0147] Mass spectrometry was performed using a Waters G2-Si quadrupole time-of-flight high-resolution mass spectrometer from the UK, with chloroform as the solvent;

[0148] Elemental analysis was performed using a Vario EL cube type organic elemental analyzer from Elementar, Germany, with a sample mass of 5 - 10 mg.

[0149] Synthesis Example 1: Preparation of Compound 1

[0150]

[0151] Synthesis of Intermediate A-1

[0152] Under nitrogen protection, toluene (300 ml), a-1 (10.46 g, 50.00 mmol), b-1 (19.87 g, 50.00 mmol), palladium acetate (0.17 g, 0.75 mmol), sodium tert-butoxide (9.61 g, 100.00 mmol) and tri-tert-butylphosphine (3 mL of 0.50 M toluene solution) were added to the reaction bottle in sequence, the mixture was stirred, heated under reflux for 3 hours, and after the reaction was completed, the reaction solution was cooled to room temperature, water was added, extracted with dichloromethane, the organic phase was collected, dried over anhydrous magnesium sulfate, filtered, the solvent was removed by distillation under reduced pressure, and recrystallized with toluene: ethanol (10:1) to obtain intermediate A-1 (22.60 g, 86%). The solid purity was ≥99.83% by HPLC. Mass spectrum m / z: 525.2441 (theoretical value: 525.2457).

[0153] Synthesis of compound 1

[0154] Under nitrogen protection, toluene (250 ml), intermediate A-1 (15.77 g, 30.00 mmol), c-1 (8.74 g, 30.00 mmol), Pd 2 (dba) 3 (0.27g, 0.30mmol), sodium tert-butoxide (5.77g, 60.00mmol) and BINAP (0.30g, 0.48mmol), stirred the mixture, heated under reflux for 4 hours, after the reaction was completed, cooled the reaction solution to room temperature, added water, extracted with dichloromethane, collected the organic phase, dried with anhydrous magnesium sulfate, filtered, distilled under reduced pressure to remove the solvent, recrystallized with toluene, and obtained compound 1 (18.11g, 82%), HPLC detected the solid purity ≧99.96%. Mass spectrum m / z: 735.3879 (theoretical value: 735.3865). Theoretical element content (%) C 56 H 49 N: C, 91.39; H, 6.71; N, 1.90. Measured element content (%): C, 91.35; H, 6.74; N, 1.91.

[0155] Synthesis Example 2: Preparation of Compound 25

[0156]

[0157] According to the method of Synthesis Example 1, c-1 was replaced with an equal molar amount of c-25 to obtain compound 25 (17.32 g). The solid purity was ≥ 99.92% as determined by HPLC. Mass spectrum m / z: 739.4133 (theoretical value: 739.4116). Theoretical element content (%) C 56 H 45 D 4N: C, 90.89; H, 7.22; N, 1.89. Measured elemental content (%): C, 90.86; H, 7.21; N, 1.84.

[0158] Synthesis Example 3: Preparation of Compound 45

[0159]

[0160] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-45 and c-1 with an equimolar amount of c-45 to obtain Compound 45 (19.25 g). The solid purity detected by HPLC is ≥99.98%. Mass spectrometry m / z: 811.4160 (theoretical value: 811.4178). Theoretical elemental content (%) C 62 H 53 N: C, 91.70; H, 6.58; N, 1.72. Measured elemental content (%): C, 91.73; H, 6.56; N, 1.71.

[0161] Synthesis Example 4: Preparation of Compound 53

[0162]

[0163] According to the method of Synthesis Example 1, replace c-1 with an equimolar amount of c-53 to obtain Compound 53 (21.32 g). The solid purity detected by HPLC is ≥99.93%. Mass spectrometry m / z: 887.4473 (theoretical value: 887.4491). Theoretical elemental content (%) C 68 H 57 N: C, 91.95; H, 6.47; N, 1.58. Measured elemental content (%): C, 91.97; H, 6.49; N, 1.54.

[0164] Synthesis Example 5: Preparation of Compound 70

[0165]

[0166] According to the method of Synthesis Example 1, replace c-1 with an equimolar amount of c-70 to obtain Compound 70 (18.63 g). The solid purity detected by HPLC is ≥99.97%. Mass spectrometry m / z: 785.4039 (theoretical value: 785.4022). Theoretical elemental content (%) C 60 H 51 N: C, 91.68; H, 6.54; N, 1.78. Measured elemental content (%): C, 91.66; H, 6.58; N, 1.76.

[0167] Synthesis Example 6: Preparation of Compound 76

[0168]

[0169] According to the method of Synthesis Example 1, replace b-1 with an equimolar amount of b-76 and c-1 with an equimolar amount of c-76 to obtain Compound 76 (21.56 g), and the solid purity detected by HPLC is ≥ 99.94%. Mass spectrometry m / z: 897.5256 (theoretical value: 897.5274). Theoretical elemental content (%) C 68 H 67 N: C, 90.92; H, 7.52; N, 1.56. Measured elemental content (%): C, 90.96; H, 7.52; N, 1.51.

[0170] Synthesis Example 7: Preparation of Compound 99

[0171]

[0172] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-45, b-1 with an equimolar amount of b-99, and c-1 with an equimolar amount of c-99 to obtain Compound 99 (20.74 g), and the solid purity detected by HPLC is ≥ 99.91%. Mass spectrometry m / z: 885.4352 (theoretical value: 885.4335). Theoretical elemental content (%) C 68 H 55 N: C, 92.16; H, 6.26; N, 1.58. Measured elemental content (%): C, 92.12; H, 6.29; N, 1.59.

[0173] Synthesis Example 8: Preparation of Compound 114

[0174]

[0175] According to the method of Synthesis Example 1, replace c-1 with an equimolar amount of c-114 to obtain Compound 114 (17.89 g), and the solid purity detected by HPLC is ≥ 99.96%. Mass spectrometry m / z: 735.3841 (theoretical value: 735.3865). Theoretical elemental content (%) C 56 H 49 N: C, 91.39; H, 6.71; N, 1.90. Measured elemental content (%): C, 91.34; H, 6.72; N, 1.94.

[0176] Synthesis Example 9: Preparation of Compound 134

[0177]

[0178] According to the method of Synthesis Example 1, a-1 was replaced with an equimolar amount of a-134, b-1 was replaced with an equimolar amount of b-134, and c-1 was replaced with an equimolar amount of c-134 to obtain Compound 134 (19.25 g), and the solid purity detected by HPLC was ≧99.98%. Mass spectrometry m / z: 811.4195 (theoretical value: 811.4178). Theoretical elemental content (%) C 62 H 53 N: C, 91.70; H, 6.58; N, 1.72. Measured elemental content (%): C, 91.74; H, 6.53; N, 1.73.

[0179] Synthesis Example 10: Preparation of Compound 158

[0180]

[0181] According to the method of Synthesis Example 1, a-1 was replaced with an equimolar amount of a-134, and b-1 was replaced with an equimolar amount of b-158 to obtain Compound 158 (20.17 g), and the solid purity detected by HPLC was ≧99.93%. Mass spectrometry m / z: 861.4320 (theoretical value: 861.4335). Theoretical elemental content (%) C 66 H 55 N: C, 91.95; H, 6.43; N, 1.62. Measured elemental content (%): C, 91.91; H, 6.45; N, 1.64.

[0182] Synthesis Example 11: Preparation of Compound 167

[0183]

[0184] According to the method of Synthesis Example 1, a-1 was replaced with an equimolar amount of a-134, and b-1 was replaced with an equimolar amount of b-167 to obtain Compound 167 (18.87 g), and the solid purity detected by HPLC was ≧99.95%. Mass spectrometry m / z: 785.4039 (theoretical value: 785.4022). Theoretical elemental content (%) C 60 H 51 N: C, 91.68; H, 6.54; N, 1.78. Measured elemental content (%): C, 91.66; H, 6.58; N, 1.76.

[0185] Synthesis Example 12: Preparation of Compound 171

[0186]

[0187] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-134 and b-1 with an equimolar amount of b-171 to obtain Compound 171 (17.98 g), and the solid purity detected by HPLC is ≧99.98%. Mass spectrometry m / z: 739.4101 (theoretical value: 739.4116). Theoretical elemental content (%) C 56 H 45 D 4 N: C, 90.89; H, 7.22; N, 1.89. Measured elemental content (%): C, 90.87; H, 7.26; N, 1.87.

[0188] Synthesis Example 13: Preparation of Compound 179

[0189]

[0190] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-134 and b-1 with an equimolar amount of b-179 to obtain Compound 179 (21.44 g), and the solid purity detected by HPLC is ≧99.92%. Mass spectrometry m / z: 927.4821 (theoretical value: 927.4804). Theoretical elemental content (%) C 71 H 61 N: C, 91.87; H, 6.62; N, 1.51. Measured elemental content (%): C, 91.83; H, 6.64; N, 1.53.

[0191] Synthesis Example 14: Preparation of Compound 186

[0192]

[0193] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-134 and b-1 with an equimolar amount of b-186 to obtain Compound 186 (18.88 g), and the solid purity detected by HPLC is ≧99.97%. Mass spectrometry m / z: 827.4475 (theoretical value: 827.4491). Theoretical elemental content (%) C 63 H 57 N: C, 91.37; H, 6.94; N, 1.69. Measured elemental content (%): C, 91.35; H, 6.97; N, 1.68.

[0194] Synthesis Example 15: Preparation of Compound 201

[0195]

[0196] According to the method of Synthesis Example 1, b-1 was replaced with an equimolar amount of b-201 to obtain Compound 201 (19.25 g), and the solid purity detected by HPLC was ≧99.96%. Mass spectrometry m / z: 811.4194 (theoretical value: 811.4178). Theoretical elemental content (%) C 62 H 53 N: C, 91.70; H, 6.58; N, 1.72. Measured elemental content (%): C, 91.73; H, 6.54; N, 1.74.

[0197] Synthesis Example 16: Preparation of Compound 219

[0198]

[0199] According to the method of Synthesis Example 1, b-1 was replaced with an equimolar amount of b-219, and c-1 was replaced with an equimolar amount of c-219 to obtain Compound 219 (18.85 g), and the solid purity detected by HPLC was ≧99.93%. Mass spectrometry m / z: 815.4410 (theoretical value: 815.4429). Theoretical elemental content (%) C 62 H 49 D 4 N: C, 91.24; H, 7.04; N, 1.72. Measured elemental content (%): C, 91.21; H, 7.08; N, 1.71.

[0200] Synthesis Example 17: Preparation of Compound 238

[0201]

[0202] According to the method of Synthesis Example 1, b-1 was replaced with an equimolar amount of b-238, and c-1 was replaced with an equimolar amount of c-238 to obtain Compound 238 (19.00 g), and the solid purity detected by HPLC was ≧99.98%. Mass spectrometry m / z: 811.4196 (theoretical value: 811.4178). Theoretical elemental content (%) C 62 H 53 N: C, 91.70; H, 6.58; N, 1.72. Measured elemental content (%): C, 91.75; H, 6.54; N, 1.74.

[0203] Synthesis Example 18: Preparation of Compound 250

[0204]

[0205] According to the method of Synthesis Example 1, a-1 was replaced with an equimolar amount of a-134, and b-1 was replaced with an equimolar amount of b-250 to obtain Compound 250 (21.03 g), and the solid purity detected by HPLC was ≧99.91%. Mass spectrometry m / z: 827.4419 (theoretical value: 909.4335). Theoretical elemental content (%) C 70 H 55 N: C, 92.37; H, 6.09; N, 1.54. Measured elemental content (%): C, 92.39; H, 6.04; N, 1.58.

[0206] Synthesis Example 19: Preparation of Compound 253

[0207]

[0208] According to the method of Synthesis Example 1, a-1 was replaced with an equimolar amount of a-253, b-1 was replaced with an equimolar amount of b-253, and c-1 was replaced with an equimolar amount of c-45 to obtain Compound 253 (23.08 g), and the solid purity detected by HPLC was ≧99.96%. Mass spectrometry m / z: 1011.4821 (theoretical value: 1011.4804). Theoretical elemental content (%) C 78 H 61 N: C, 92.54; H, 6.07; N, 1.38. Measured elemental content (%): C, 92.59; H, 6.04; N, 1.36.

[0209] Synthesis Example 20: Preparation of Compound 260

[0210]

[0211] According to the method of Synthesis Example 1, a-1 was replaced with an equimolar amount of a-134, and b-1 was replaced with an equimolar amount of b-260 to obtain Compound 260 (21.05 g), and the solid purity detected by HPLC was ≧99.94%. Mass spectrometry m / z: 887.4472 (theoretical value: 887.4491). Theoretical elemental content (%) C 68 H 57 N: C, 91.95; H, 6.47; N, 1.58. Measured elemental content (%): C, 91.98; H, 6.48; N, 1.54.

[0212] Synthesis Example 21: Preparation of Compound 282

[0213]

[0214] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-134 and b-1 with an equimolar amount of b-282 to obtain Compound 282 (20.36 g), and the solid purity detected by HPLC is ≧99.92%. Mass spectrometry m / z: 869.4760 (theoretical value: 869.4775). Theoretical elemental content (%) C 66 H 39 D 12 N: C, 91.10; H, 7.29; N, 1.61. Measured elemental content (%): C, 91.13; H, 7.24; N, 1.63.

[0215] Synthesis Example 22: Preparation of Compound 289

[0216]

[0217] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-134 and b-1 with an equimolar amount of b-289 to obtain Compound 289 (23.00 g), and the solid purity detected by HPLC is ≧99.98%. Mass spectrometry m / z: 969.5290 (theoretical value: 969.5274). Theoretical elemental content (%) C 74 H 67 N: C, 91.60; H, 6.96; N, 1.44. Measured elemental content (%): C, 91.63; H, 6.92; N, 1.45.

[0218] Synthesis Example 23: Preparation of Compound 308

[0219]

[0220] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-134, b-1 with an equimolar amount of b-308, and c-1 with an equimolar amount of c-308 to obtain Compound 308 (18.01 g), and the solid purity detected by HPLC is ≧99.96%. Mass spectrometry m / z: 740.4162 (theoretical value: 740.4179). Theoretical elemental content (%) C 56 H 44 D 5 N: C, 90.77; H, 7.34; N, 1.89. Measured elemental content (%): C, 90.75; H, 7.38; N, 1.87.

[0221] Synthesis Example 24: Preparation of Compound 355

[0222]

[0223] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-134, b-1 with an equimolar amount of b-308, and c-1 with an equimolar amount of c-355 to obtain Compound 355 (19.49 g), and the solid purity detected by HPLC is ≧99.94%. Mass spectrometry m / z: 811.4193 (theoretical value: 811.4178). Theoretical elemental content (%) C 62 H 53 N: C, 91.70; H, 6.58; N, 1.72. Measured elemental content (%): C, 91.74; H, 6.55; N, 1.71.

[0224] Synthesis Example 25: Preparation of Compound 371

[0225]

[0226] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-253, b-1 with an equimolar amount of b-371, and c-1 with an equimolar amount of c-371 to obtain Compound 371 (21.86 g), and the solid purity detected by HPLC is ≧99.91%. Mass spectrometry m / z: 933.4317 (theoretical value: 933.4335). Theoretical elemental content (%) C 72 H 55 N: C, 92.57; H, 5.93; N, 1.50. Measured elemental content (%): C, 92.52; H, 5.92; N, 1.55.

[0227] Synthesis Example 26: Preparation of Compound 378

[0228]

[0229] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-134, b-1 with an equimolar amount of b-308, and c-1 with an equimolar amount of c-378 to obtain Compound 378 (20.43 g), and the solid purity detected by HPLC is ≧99.97%. Mass spectrometry m / z: 861.4352 (theoretical value: 861.4335). Theoretical elemental content (%) C 66 H 55 N: C, 91.95; H, 6.43; N, 1.62. Measured elemental content (%): C, 91.92; H, 6.47; N, 1.60.

[0230] Synthesis Example 27: Preparation of Compound 394

[0231]

[0232] According to the method of Synthesis Example 1, a-1 was replaced with an equimolar amount of a-394, b-1 was replaced with an equimolar amount of b-371, and c-1 was replaced with an equimolar amount of c-394 to obtain Compound 394 (21.91 g), and the solid purity detected by HPLC was ≧99.93%. Mass spectrometry m / z: 935.4474 (theoretical value: 935.4491). Theoretical elemental content (%) C 72 H 57 N: C, 92.37; H, 6.14; N, 1.50. Measured elemental content (%): C, 92.32; H, 6.16; N, 1.53.

[0233] Synthesis Example 28: Preparation of Compound 400

[0234]

[0235] According to the method of Synthesis Example 1, a-1 was replaced with an equimolar amount of a-134, and b-1 was replaced with an equimolar amount of b-308 to obtain Compound 400 (20.62 g), and the solid purity detected by HPLC was ≧99.95%. Mass spectrometry m / z: 869.4980 (theoretical value: 869.4961). Theoretical elemental content (%) C 66 H 63 N: C, 91.09; H, 7.30; N, 1.61. Measured elemental content (%): C, 91.04; H, 7.32; N, 1.64.

[0236] Synthesis Example 29: Preparation of Compound 422

[0237]

[0238] According to the method of Synthesis Example 1, a-1 was replaced with an equimolar amount of a-134, b-1 was replaced with an equimolar amount of b-371, and c-1 was replaced with an equimolar amount of c-45 to obtain Compound 422 (24.41 g), and the solid purity detected by HPLC was ≧99.97%. Mass spectrometry m / z: 1069.5569 (theoretical value: 1069.5587). Theoretical elemental content (%) C 82 H 71 N: C, 92.01; H, 6.69; N, 1.31. Measured elemental content (%): C, 92.03; H, 6.64; N, 1.34.

[0239] Synthesis Example 30: Preparation of Compound 429

[0240]

[0241] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-134, b-1 with an equimolar amount of b-308, and c-1 with an equimolar amount of c-429 to obtain Compound 429 (20.48 g), and the solid purity detected by HPLC is ≧99.94%. Mass spectrometry m / z: 807.4251 (theoretical value: 807.4260). Theoretical elemental content (%) C 59 H 57 NSi: C, 87.68; H, 7.11; N, 1.73. Measured elemental content (%): C, 87.71; H, 7.09; N, 1.70.

[0242] Synthesis Example 31: Preparation of Compound 434

[0243]

[0244] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-434 and c-1 with an equimolar amount of c-434 to obtain Compound 434 (17.12 g), and the solid purity detected by HPLC is ≧99.92%. Mass spectrometry m / z: 695.3569 (theoretical value: 695.3552). Theoretical elemental content (%) C 53 H 45 N: C, 91.47; H, 6.52; N, 2.01. Measured elemental content (%): C, 91.42; H, 6.56; N, 2.02.

[0245] Synthesis Example 32: Preparation of Compound 454

[0246]

[0247] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-45, b-1 with an equimolar amount of b-454, and c-1 with an equimolar amount of c-454 to obtain Compound 454 (18.76 g), and the solid purity detected by HPLC is ≧99.94%. Mass spectrometry m / z: 771.3847 (theoretical value: 771.3865). Theoretical elemental content (%) C 59 H 49 N: C, 91.79; H, 6.40; N, 1.81. Measured elemental content (%): C, 91.73; H, 6.44; N, 1.83.

[0248] Synthesis Example 33: Preparation of Compound 477

[0249]

[0250] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-134, b-1 with an equimolar amount of b-477, and c-1 with an equimolar amount of c-477 to obtain Compound 477 (21.58 g), and the solid purity detected by HPLC is ≧99.98%. Mass spectrometry m / z: 898.4318 (theoretical value: 898.4335). Theoretical elemental content (%) C 69 H 46 D 5 N: C, 92.17; H, 6.28; N, 1.56. Measured elemental content (%): C, 92.19; H, 6.24; N, 1.57.

[0251] Synthesis Example 34: Preparation of Compound 480

[0252]

[0253] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-134, b-1 with an equimolar amount of b-480, and c-1 with an equimolar amount of c-480 to obtain Compound 480 (19.85 g), and the solid purity detected by HPLC is ≧99.93%. Mass spectrometry m / z: 847.4196 (theoretical value: 847.4178). Theoretical elemental content (%) C 65 H 53 N: C, 92.05; H, 6.30; N, 1.65. Measured elemental content (%): C, 92.08; H, 6.32; N, 1.60.

[0254] Synthesis Example 35: Preparation of Compound 489

[0255]

[0256] According to the method of Synthesis Example 1, replace a-1 with an equimolar amount of a-134, b-1 with an equimolar amount of b-489, and c-1 with an equimolar amount of c-489 to obtain Compound 489 (18.96 g), and the solid purity detected by HPLC is ≧99.96%. Mass spectrometry m / z: 799.4162 (theoretical value: 799.4178). Theoretical elemental content (%) C 61 H 53 N: C, 91.57; H, 6.68; N, 1.75. Measured elemental content (%): C, 91.54; H, 6.66; N, 1.79.

[0257] Synthesis Example 36: Preparation of Compound 495

[0258]

[0259] According to the method of Synthesis Example 1, a-1 was replaced with an equimolar amount of a-134, b-1 was replaced with an equimolar amount of b-495, and c-1 was replaced with an equimolar amount of c-489 to obtain Compound 495 (17.88 g), and the solid purity detected by HPLC was ≥99.91%. Mass spectrometry m / z: 763.4191 (theoretical value: 763.4178). Theoretical elemental content (%) C 58 H 53 N: C, 91.17; H, 6.99; N, 1.83. Measured elemental content (%): C, 91.15; H, 6.96; N, 1.88. [Comparative Example 1-3] Device Preparation Example:

[0260] Comparative Example 1: An organic light-emitting device was prepared by vacuum thermal evaporation. The experimental steps were as follows: The ITO substrate was washed 3 times in distilled water, ultrasonically washed for 15 minutes. After the distilled water washing was completed, it was ultrasonically washed in solvents such as isopropanol, acetone, and methanol in sequence, and then dried at 120 °C and sent to an evaporation machine.

[0261] On the prepared ITO transparent electrode, a hole injection layer HAT-CN / 20 nm, a first hole transport layer TAPC / 100 nm, a second hole transport layer HT-1 / 20 nm, a host H-1: doped with FIrpic (95%: 5% mixture) / 20 nm were evaporated by layer-by-layer vacuum evaporation, and then an electron transport layer TMPYPB and Liq (doping ratio of 1:1) / 35 nm, an electron injection layer LiF / 1 nm, and a cathode Al / 120 nm were evaporated. And the device was sealed in a glove box, thus preparing an organic light-emitting device. After the production of the organic light-emitting device was completed according to the above steps, the optoelectronic properties of the device were measured. The molecular structural formulas of the related materials are shown as follows:

[0262]

[0263] Comparative Example 2: The second hole transport layer material HT-1 in Comparative Example 1 was replaced with HT-2, and the organic light-emitting device of Comparative Example 2 was manufactured in the same manner as Comparative Example 1.

[0264] Comparative Example 3: The second hole transport layer material HT-1 in Comparative Example 1 was replaced with HT-3, and the organic light-emitting device of Comparative Example 3 was manufactured in the same manner as Comparative Example 1.

[0265] [Application Examples 1-36]

[0266] Application Examples 1 - 36: The second hole transport layer material HT-1 of the organic light-emitting device was successively replaced with Compound 1, 25, 45, 53, 70, 76, 99, 114, 134, 158, 167, 171, 179, 186, 201, 219, 238, 250, 253, 260, 282, 289, 308, 355, 371, 378, 394, 400, 422, 429, 434, 454, 477, 480, 489, 495 of the present invention, and all other steps were the same as those in Comparative Example 1.

[0267] A combined IVL test system was formed by a test software, a computer, a K2400 digital source meter produced by Keithley Corporation in the United States, and a PR788 spectral scanning luminance meter produced by PhotoResearch Corporation in the United States to test the luminous efficiency of the organic light-emitting device. The lifetime was tested using an M6000 OLED lifetime test system produced by McScience Corporation. The test environment was an atmospheric environment, and the temperature was room temperature. The test results of the luminous characteristics of the obtained organic light-emitting devices are shown in Table 1. Table 1 shows the test results of the luminous characteristics of the compounds prepared in the examples of the present invention and the light-emitting devices prepared from the comparative substances.

[0268] [Table 1] Test of the Luminous Characteristics of the Light-Emitting Device

[0269]

[0270]

[0271] It can be seen from the results in Table 1 that the organic compounds containing phenylfluorene of the present invention are applied to the organic light-emitting device, especially as the second hole transport layer material. Compared with Comparative Examples 1 - 3, the luminous efficiency and service life of the organic light-emitting device are significantly improved, and it is an organic light-emitting material with good performance.

[0272] It should be noted that the present invention has been specifically described with individual embodiments. However, without departing from the principle of the present invention, those of ordinary skill in the art can make various improvements in form or details to the present invention, and these improvements also fall within the protection scope of the present invention.

Claims

1. An organic compound containing phenylfluorene, characterized in that the molecular structure is shown in Formula I: Among them, the Ar 1 is selected from any one of the groups shown below: The R b are the same as or different from each other and are independently selected from the group consisting of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, deuterated isopropyl, deuterated tert-butyl, phenyl, deuterated phenyl, tolyl, methylfluorenyl, deuterated methylfluorenyl, trimethylsilyl, formula A-1, and formula A-2; The said b 1 is selected from 1, 2 or 3; the said b 2 is selected from 1, 2, 3 or 4; the said b 3 is selected from 1, 2, 3, 4 or 5; the said b 6 is selected from 1, 2, 3, 4, 5 or 6; The R e are the same as or different from each other and are independently selected from the group consisting of hydrogen, deuterium, methyl, ethyl, n-propyl, n-butyl, isopropyl, tert-butyl, deuterated isopropyl, and deuterated tert-butyl; The said e 1 is selected from 1, 2, 3, 4 or 5; the said e 2 is selected from 1, 2, 3 or 4; the said e 3 is selected from 1, 2, 3, 4, 5 or 6; the said e 4 is selected from 1, 2, 3, 4, 5, 6 or 7; The Ar 2 is selected from any one of the groups shown below: The R p are the same as or different from each other and are independently selected from hydrogen, deuterium, trimethylsilyl, triethylsilyl, formula A-1, formula A-2, or one of the following substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, phenyl; The p 1 is selected from 1, 2, 3, 4 or 5; the p 2 is selected from 1, 2, 3, 4, 5, 6 or 7; the p 3 is selected from 1, 2 or 3; Said R b 、R p are the same as or different from each other, and one of all Rs in formula I b is selected from the groups represented by A-1 or A-2, and / or one of all Rs in formula I p is selected from the groups represented by A-1 or A-2; The R a are the same as or different from each other and are independently selected from any one of hydrogen, deuterium, methyl, ethyl, propyl, and butyl; The said a 1 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15; the said a 2 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11; The R 1 is independently selected from one or more of hydrogen and deuterium; The R 2 , R 3 are independently selected from one of the following groups: hydrogen, deuterium, substituted or unsubstituted methyl, ethyl, propyl, butyl; or any two adjacent R 2 groups combine with each other to form a substituted or unsubstituted benzene ring, or any two adjacent R 3 groups combine with each other to form a substituted or unsubstituted benzene ring; The R 4 is independently selected from one of hydrogen, deuterium, and the following substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, phenyl; The said n 1 is selected from 0, 1, 2, 3 or 4; the said n 2 is selected from 0, 1, 2, 3 or 4; the said n 3 is selected from 0, 1, 2, 3 or 4; the said n 4 is selected from 0, 1, 2, 3, 4 or 5; The L 0 is selected from one of a single bond, a substituted or unsubstituted phenylene group; The said L 1 Selected from a single bond or one of the groups shown below: The said L 2 is independently selected from a single bond or one of the groups shown below: The R q is any one selected from hydrogen and deuterium; Said q 1 selected from 0, 1, 2, 3 or 4; wherein * is a linking bond; wherein, in the above "substituted or unsubstituted...", "substituted..." means independently selected deuterium substitution.

2. The organic compound containing phenylfluorene according to claim 1, characterized in that The R p is one selected from the groups represented by A-1 or A-2.

3. The organic compound containing phenylfluorene according to claim 1, characterized in that A-1 is selected from one of the following groups: A-2 is selected from one of the following groups:

4. The organic compound containing phenylfluorene according to claim 1, characterized in that The Ar 2 is selected from any one of the following groups: The R p are the same as or different from each other and are independently selected from hydrogen, deuterium, formula A-1, formula A-2, or one of the following substituted or unsubstituted groups: methyl, ethyl, propyl, butyl.

5. The organic compound containing phenylfluorene according to claim 1, characterized in that The Ar 1 is selected from any one of the following groups:

6. The organic compound containing phenylfluorene according to claim 1, characterized in that The said L 1 , L 2 are independently selected from a single bond or one of the groups shown below:

7. An organic compound containing phenylfluorene, characterized in that the organic compound containing phenylfluorene is selected from any one of the following chemical structures:

8. An organic light-emitting device, comprising an anode, a cathode, and an organic layer, the organic layer is located between the anode and the cathode or outside one or more electrodes of the anode and the cathode, the organic layer includes a hole transport region, the hole transport region includes a hole transport layer, and the hole transport layer contains any one or a combination of at least two of the organic compounds containing phenylfluorene described in any one of claims 1 to 7.

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