Patent Application
20210101883
The present invention relates to an organic compound and, more particularly, to an organic electroluminescence device using the organic compound.
Organic electroluminescence (organic EL) devices, i.e., organic light-emitting diodes (OLEDs) that make use of organic compounds, are becoming increasingly desirable than before. The devices make use of thin organic films that emit light when voltage is applied across the device. They are becoming an interesting technology for use in applications such as flat panel displays, illumination, or backlighting.
One of the organic compounds, denoted ET2 hereinafter, has the following structure:
As used herein, “top” means furthest away from the substrate, while “bottom” means closest to the substrate. Where a second layer is described as formed on or onto a first layer, the second layer is formed further away from substrate. There may be other layers between the second layer and the first layer, unless it is specified that the second layer is “in contact with” the first layer. For example, a cathode may be described as formed onto an anode, even though there are various organic layers in between.
An organic compound is represented by the following formula:
wherein X and Y independently represent a divalent bridge selected from the group consisting of O, S, NAr1 and CR2R3;
wherein ring A represents a monocyclic aromatic group or a polycyclic aromatic group having at least two fused rings;
wherein L represents a single bond or an aromatic linker;
wherein R1 to R3 independently represent no substitution or mono to the maximum allowable substitution, each of the substituents is selected from the group consisting of alkyl, aryl, aralkyl, heteroaryl, and combinations thereof; and
wherein each of Ar1, Ar2 and Ar3 is selected from the group consisting of aryl, heteroaryl, and combinations thereof.
The present invention further discloses an organic EL device. The organic EL device may comprise an anode, a cathode and one or more organic layers formed between the anode and the cathode. At least one of the organic layers comprises the organic compound of formula (1).
Plural embodiments of the present disclosure are disclosed through drawings. For the purpose of clear illustration, many practical details will be illustrated along with the description below. It should be understood that, however, these practical details should not limit the present disclosure. In other words, in embodiments of the present disclosure, these practical details are not necessary. In addition, for the purpose of simplifying the drawings, some conventional structures and components are simply and schematically depicted in the figures.
It is to be understood that although particular phrases used herein, such as “first”, “second”, “third”, and so on, are used to describe different components, members, regions, layers, and/or sections, these components, members, regions, layers, and/or sections should not be limited by these terms. These phrases are used to distinguish one component, member, region, layer, or section from another component, member, region, layer, or section. In this way, a first component, member, region, layer, and/or section to be described below may be referred to as a second component, member, region, layer, and/or section, without departing from the spirit and scope of the present disclosure.
Spatially relative phrases, such as “onto”, “on”, “under”, “below”, “underlying”, “beneath”, “above”, and so on used herein, are used for facilitating description of a relation between one component or feature and another component or feature depicted in the drawings. Therefore, it can be understood that, in addition to directions depicted in the drawings, the spatially relative terms mean to include all different orientations during usage or operations of the device. For example, it is assumed that a device in a figure is reversed upside down, a component described as being “under”, “below”, or “beneath” another component or feature is oriented “onto” or “on” the other component or feature. Therefore, these exemplary terms “under” and “below” may include orientations above and below. The device may be otherwise oriented (e.g., turned by 90 degrees, or other orientations), and the spatially relative terms used herein should be explained accordingly.
Accordingly, it may be understood that when a component or a layer is referred to as being “onto”, “on”, “connected to”, or “coupled to” another component or another layer, it may be immediately on the other component or layer, or connected to or coupled to the other component or layer, or there may be one or more intermediate components or intermediate layers. Further, it can be understood that when a component or a layer is referred to as being “between” two components or two layers, it may be the only component or layer between the two components or layers, or there may be one or more intermediate components or intermediate layers.
Terminologies used herein are only for the purpose of describing particular embodiments, but not limiting the present disclosure. The singular form of “a” and “the” used herein may also include the plural form, unless otherwise indicated in the context. Accordingly, it can be understood that when there terms “include” or “comprise” are used in the specification, it clearly illustrates the existence of a specified feature, bulk, step, operation, component, and/or member, while not excluding the existence or addition of one or more features, bulks, steps, operations, components, members and/or groups thereof. “And/or” used herein includes any and all combinations of one or more related terms that are listed. When a leading word, such as “at least one of”, is added ahead of a component list, it is to describe the entire component list, but not individual components among the list.
The terms “substituted” and “substitution” refer to a substituent bonded to the relevant position, e.g., a carbon or nitrogen. When R1 represents no substitution, R1, for example, can be a hydrogen for available valencies of ring atoms, as in carbon atoms for benzene and the nitrogen atom in pyrrole, or simply represents nothing for ring atoms with fully filled valencies, e.g., the nitrogen atom in pyridine. The maximum number of substitutions possible in a ring structure will depend on the total number of available valencies in the ring atoms. A polycyclic aromatic group may have two or more rings possible for being substituted. In this case, a long straight line may be drawn to pass through each of the rings in a formula. The following formula may be an example:
Generally, an organic EL device comprises at least one organic layer disposed between and electrically connected to an anode and a cathode. When an external voltage is applied across the organic EL device, electrons and holes are injected from the cathode and the anode, respectively. Electrons will be injected from a cathode into a LUMO (lowest unoccupied molecular orbital) and holes will be injected from an anode into a HOMO (highest occupied molecular orbital). Subsequently, the electrons recombine with holes in the light emitting layer to form excitons and then emit light. When luminescent molecules absorb energy to achieve an excited state, the exciton may either be in a singlet state or a triplet state, depending on how the spins of the electrons and holes have been combined.
The term “hydrogen” refers to a —H radical.
The terms “halogen” and “halide” are used interchangeably and refer to fluorine, chlorine, bromine, or iodine.
The term “trifluoromethyl” refers to a —CF3 radical.
The term “cyano” refers to a —C═N radical.
The term “nitro” refers to a —NO2 radical.
The term “silyl” refers to a —Si(Ra)3 radical, wherein each Rs can be same or different. Ra can be hydrogen or a substituent selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. Preferred Rs is selected from the group consisting of alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
As used herein, “a first integer to a second integer” indicates a group comprising at least a first integer, a second integer, and all integers therebetween. For example, “1 to 4 atoms” indicates a group comprising 1, 2, 3 and 4 atoms; and “an integer of 0 to 3” indicates a group comprising 0, 1, 2, and 3.
As used herein, “combinations thereof” indicates that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can envision from the applicable list. For example, a monocyclic aromatic group and a polycyclic aromatic group can be combined by being joined through a direct bond, or can be combined to have two carbons common to two adjoining rings (the rings are “fused”); a halogen and alkyl can be combined to form a halogenated alkyl substituent; a halogen, alkyl, and aryl can be combined to form a halogenated arylalkyl; and an alkyl and deuterium can be combined to form a partial or fully deuterated alkyl group. In one instance, the term substitution includes a combination of two to four of the listed groups. In another instance, the term substitution includes a combination of two to three groups. In yet another instance, the term substitution includes a combination of two groups. Preferred combinations of substituent groups are those that contain up to fifty atoms that are not hydrogen or deuterium, or those which include up to forty atoms that are not hydrogen or deuterium, or those that include up to thirty atoms that are not hydrogen or deuterium. In many instances, a preferred combination of substituent groups will include up to twenty atoms that are not hydrogen or deuterium.
The term “alkyl” refers to and includes both straight and branched chain alkyl radicals. Preferred alkyl groups are those containing 30 or fewer carbon atoms, preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 12 carbon atoms. Suitable alkyl groups include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, and the like. Additionally, the alkyl group is optionally substituted.
The term “cycloalkyl” as used herein contemplates cyclic alkyl radicals. Preferred cycloalkyl groups are those containing 3 to 10 ring carbon atoms and includes cyclopropyl, cyclopentyl, cyclohexyl, adamantyl, and the like. Additionally, the cycloalkyl group may be optionally substituted.
The term “alkenyl” as used herein contemplates both straight and branched chain alkene radicals. Preferred alkenyl groups are those containing two to fifteen carbon atoms. Additionally, the alkenyl group may be optionally substituted.
The term “alkynyl” as used herein contemplates both straight and branched chain alkyne radicals. Preferred alkynyl groups are those containing two to fifteen carbon atoms. Additionally, the alkynyl group may be optionally substituted.
The term “heterocyclic group” as used herein contemplates aromatic and non-aromatic cyclic radicals. Hetero-aromatic cyclic radicals also means heteroaryl. Preferred hetero-non-aromatic cyclic groups are those containing 3 to 7 ring atoms which includes at least one hetero atom, and includes cyclic amines such as morpholino, piperidino, pyrrolidino, and the like, and cyclic ethers, such as tetrahydrofuran, tetrahydropyran, and the like. Additionally, the heterocyclic group may be optionally substituted.
The term “aryl” or “aromatic group” as used herein contemplates a monocyclic aromatic group, a polycyclic aromatic group, and combinations thereof. The polycyclic aromatic group may have two, three, four or more rings in which two carbons are common to two adjoining rings (the rings are “fused”) wherein at least one of the fused rings is an aromatic hydrocarbyl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. Unless otherwise specified, preferred aryl groups are those containing 30 or fewer carbon atoms, preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and most preferably 6 to 12 carbon atoms. Especially preferred is an aryl group having 6 carbons, 10 carbons or 12 carbons. Suitable aryl groups include phenyl, biphenyl, triphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene, preferably phenyl, biphenyl, triphenyl, triphenylene, fluorene, and naphthalene. Additionally, the aryl group is optionally substituted.
The term “arylene” or “arenediyl” as used herein contemplates a substituent of an organic compound that is derived from an aromatic hydrocarbon (arene) that has had a hydrogen atom removed from two ring carbon atoms, such as phenylene. Unless otherwise specified, preferred arylene groups are those containing 30 or fewer carbon atoms, preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and most preferably 6 to 12 carbon atoms. Especially preferred is an arylene group having 6 carbons, 10 carbons or 12 carbons. Additionally, the arylene group is optionally substituted.
The terms “aralkyl” or “arylalkyl” are used interchangeably and refer to an alkyl group that is substituted with an aryl group. Preferred aralkyl groups are those containing 30 or fewer carbon atoms, preferably 6 to 30 carbon atoms, more preferably 7 to 30 carbon atoms, and most preferably 7 to 13 carbon atoms. Additionally, the aralkyl group is optionally substituted.
The term “heteroaryl” as used herein contemplates a monocyclic aromatic group and a polycyclic aromatic group that both include at least one heteroatom. The heteroatoms include, but are not limited to O, S, N, P, B, Si, and Se. In many instances, O, S, Se, N or Si are the preferred heteroatoms. Hetero-monocyclic aromatic groups are preferably single rings with 5 or 6 ring atoms, and the ring can have from one to six heteroatoms. The hetero-polycyclic aromatic groups can have two or more rings in which two atoms are common to two adjoining rings (the rings are “fused”) wherein at least one of the rings is a heteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl, heterocycles, and/or heteroaryls. The hetero-polycyclic aromatic groups can have from one to six heteroatoms per ring of the polycyclic aromatic group. Preferred heteroaryl groups are those containing 30 or fewer carbon atoms, preferably 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and most preferably 3 to 12 carbon atoms. Suitable heteroaryl groups include but not limited to dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1,2-azaborine, 1,3-azaborine, 1,4-azaborine, borazine, and aza-analogs thereof. Additionally, the heteroaryl group is optionally substituted.
The terms alkyl, aralkyl, heteroaryl, aryl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, alkoxy, and heterocyclic group, as used herein, are independently unsubstituted, or independently substituted, with one or more general substituents selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In many instances, the general substituents are selected from the group consisting of deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In some instances, the preferred general substituents are selected from the group consisting of hydrogen, halogen, trifluoromethyl, cyano, nitro, silyl, and combinations thereof.
In yet other instances, the more preferred general substituents are selected from the group consisting of hydrogen, alkyl, aralkyl, heteroaryl and combinations thereof.
The term “acyl” refers to a substituted carbonyl radical (C(O)—Rs).
The term “ester” refers to a substituted oxycarbonyl (—O—C(O)—Rs or —C(O)—O—Rs) radical.
The term “ether” refers to an —ORs radical.
The terms “sulfanyl” or “thio-ether” are used interchangeably and refer to a —SRs radical.
The term “sulfinyl” refers to a —S(O)—Rs radical.
The term “sulfonyl” refers to a —SO2—Rs radical.
The term “phosphino” refers to a —P(Rs)3 radical, wherein each Rs can be same or different.
It is to be understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuryl, hydrocarbyl, aromatic linker, arylene) or as if it were the whole molecule (e.g., benzene, naphthalene, dibenzofuran, hydrocarbon, aromatic compound, aromatic hydrocarbon). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.
In one embodiment, an organic compound is represented by the following formula:
wherein X and Y independently represent a divalent bridge selected from the group consisting of O, S, NAr1 and CR2R3;
wherein ring A represents a monocyclic aromatic group or a polycyclic aromatic group having at least two fused rings;
wherein L represents a single bond or an aromatic linker;
wherein R1 to R3 independently represent no substitution or mono to the maximum allowable substitution, each of the substituents is selected from the group consisting of alkyl, aryl, aralkyl, heteroaryl, and combinations thereof; and
wherein each of Ar1, Ar2 and Ar3 is selected from the group consisting of aryl, heteroaryl, and combinations thereof.
In selected embodiments, the organic compound is represented by one of the following formulae:
In some embodiments, Ar2 and Ar3 are independently selected from the group consisting of biphenyl, terphenyl, quaterphenyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, naphtyl, anthracyl, phenanthryl, chrysenyl, triphenylenyl, pyrenyl, and combinations thereof.
In some embodiments, Ar2 and Ar3 are independently selected from the group consisting of:
combinations thereof.
In some embodiments, each of the R1 to R3 represents no substitution or is a substituent selected from the group consisting of alkyl having 20 or fewer carbon atoms, aryl having 30 or fewer carbon atoms, aralkyl having 30 or fewer carbon atoms, heteroaryl having 30 or fewer carbon atoms, and combinations thereof.
In some embodiments, R1 may represent no substitution or mono, di, tri, tetra, penta, hexa, hepta, or octa substitutions. L may represent a single bond or an aromatic linker selected from the group consisting of alkyl, aryl, aralkyl, heteroaryl, and combinations thereof. L may also represent an aromatic linker of arylene. Alternatively, L may represent a substituted or unsubstituted divalent arylene having 6 to 30 ring carbon atoms.
X and Y may independently represent a divalent bridge selected from the group consisting of O, S, NAr1 and CR2R3; m represents an integer of 0 to 8. Ring A may represent a fused ring hydrocarbon unit with one, two rings. L may represent a single bond, a substituted or unsubstituted divalent arylene group having 6 to 30 ring carbon atoms. R1 to R3 may be independently selected from the group consisting of a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.
In formula (1), Ar1 may represent a substituted or unsubstituted aryl group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms. Ar2 and Ar3 may independently represent a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms.
Ar may represent a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. R1 to R8 may be independently selected from the group consisting of a hydrogen atom, a halide, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms; a substituted or unsubstituted arylamine group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heteroarylamine group having 5 to 30 ring carbon atoms. The alkyl group, aralkyl group, aryl group, heteroaryl group, arylamine group, or heteroarylamine group is substituted by, for example, a halogen, an alkyl group, an aryl group, or a heteroaryl group.
In one embodiment, a first organic EL device using the organic compound of formula (1) is disclosed.
Referring to
As the electron transporting material 360C of the first organic EL device 510 of
In one embodiment, a second organic EL device using the organic compound of formula (1) is disclosed.
Referring to
Referring to
In formula (1), Ar1, Ar2 or Ar3 may represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted benzofluorene group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted triphenylenyl group.
The organic compound of the present invention may also be represented by one of the following formulae:
The same definition as described in the paragraph [0010] to paragraph [0065].
In selected embodiments, Ar2 and Ar3 are independently selected from the group consisting of biphenyl, terphenyl, quaterphenyl, fluorenyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, naphtyl, anthracyl, phenanthryl, chrysenyl, triphenylenyl, pyrenyl, and combinations thereof.
In selected embodiments, Ar2 and Ar3 are independently selected from the group consisting of:
and combinations thereof.
The organic compound of the present invention may be one of the following compounds:
Referring to
The electron transport layer (ETL) 360E of
To those organic EL devices of
The I-V-B (at 1000 nits) test reports of those organic EL devices of
According to Table 1, in the first organic EL device 510, the organic compound of formula (1) comprised as an electron transport material 360C of
A method of producing the first organic EL device 510 of
Before vapor deposition of the organic layers, cleaned ITO substrates may be further treated by UV and ozone. All pre-treatment processes for ITO substrate are under clean room (class 100), so that an anode 310 may be formed.
One or more organic layers 320, 330, 340 (
Referring to
On the emissive layer 340, a compound HB3 may be a hole blocking material (HBM) to form a hole blocking layer 350 having a thickness of about 10 nm. 2-(naphthalen-1-yl)-9-(4-(1-(4-(10-(naphthalene-2-yl)anthracen-9-yl)-phenyl)-1H-benzo[d]imidazol-2-yl)phenyl)-1,10-phenanthroline (ET2) may be applied as an electron transporting material to co-deposit with 40% 8-hydroxyquinolato-lithium (LiQ), thereby forming an electron transporting layer (ETL) 360 of the organic EL device 510 or 400. The electron transporting layer (ETL) 360 may have a thickness of about 35 nm.
Table 2 shows the layer thickness and materials of the organic EL device 510 (
The organic compounds ET2, HB3, D1, NPB and HAT-CN for producing the organic EL device 400 or 510 in this invention may have the formulas as follows:
Referring to
In any above-mentioned compounds used in each layer of an organic EL device, the hydrogen atoms can be partially or fully deuterated. Thus, any specifically listed substituent, such as, without limitation, methyl, phenyl, pyridyl, etc. may be undeuterated, partially deuterated, and fully deuterated versions thereof. Similarly, classes of substituents such as, without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc. also may be undeuterated, partially deuterated, and fully deuterated versions thereof.
In one embodiment, a second organic EL device using the organic compound of formula (1) is disclosed. The method of producing the second organic EL device 520 of
Table 3 shows the layer thickness and materials of the organic EL device 520 (
To those organic EL devices of
The I-V-B (at 1000 nits) test reports of those organic EL devices of
According to Table 4, in the second organic EL device 520, the organic compound of formula (1) comprised as a hole blocking layer 350C of
Referring to
Detailed preparation of the organic compounds of the present invention will be clarified by exemplary embodiments below, but the present invention is not limited thereto. EXAMPLES 1 to 15 show the preparation of the organic compounds of the present invention.
At 0° C., 2M aqueous solution of sulfuric acid (105 ml, 210.3 mmol) was dropped into acetic anhydride (580 ml), and then the mixture was stirred at this temperature for 1 hr. 5-bromo-7,7-dimethyl-7H-benzo[c]fluorine (40 g, 123.7 mmol), periodic acid (9.3 g, 40.8 mmol) and iodine (19.8 g, 77.9 mmol) were add into the mixture slowly. Keeping the mixture was stirred at 0° C. for 1 hr. The mixture was allowed to warm to room temperature for 1 hr. After that, the mixture was heated to 90° C. slowly and stirred overnight. After the reaction finished, the mixture was poured into ice water and extracted with ethyl acetate, and the organic layer was removed under reduced pressure and the crude product was purified by column chromatography, yielding 28 g of 5-bromo-9-iodo-7,7-dimethyl-7H-benzo[c]fluorene as pale yellow syrup (50.9%).
A mixture of 5-bromo-9-iodo-7,7-dimethyl-7H-benzo[c]fluorene (28 g, 62.3 mmol), biphenyl-2-ylboronicacid (9.8 g, 49.8 mmol), 2M aqueous solution of sodium carbonate (65 ml), ethanol (140 ml), and toluene (420 ml) was degassed by bubbling nitrogen gas for 15 minutes followed by addition of palladium tetrakis (1.4 g, 1.22 mmol) and 2-(dicyclohexylphosphino)biphenyl (0.9 g, 2.44 mmol). The mixture was heated to reflux overnight. Upon cooling to room temperature, the mixture was extracted with ethyl acetate (3 times) and washed with water. The organic layer was dried with anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by column chromatography on silica, yielding 15 g of 9-([1,1′-biphenyl]-2-yl)-5-bromo-7,7-dimethyl-7H-benzo[c]fluorine as colorless syrup (51%).
A mixture of 9-([1,1′-biphenyl]-2-yl)-5-bromo-7,7-dimethyl-7H-benzo[c] fluorene (15 g, 31.5 mmol) and dichlromethane (630 ml) was cooled to −15° C. and followed by addition of iron chloride (25 g, 157.5 mmol) dissolving in nitromethane (30 ml). After the reaction was finished, the mixture quenched with methanol and washed with water. The organic layer was dried with anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by column chromatography on silica, yielding 13 g of 14-bromo-16,16-dimethyl-16H-benzo[6,7]indeno[1,2-b]triphenylene as pale yellow solid (87%).
A mixture of 14-bromo-16,16-dimethyl-16H-benzo[6,7]indeno [1,2-b]triphenylene (11.6 g, 24.6 mmol), bis(pinacolato)diboron (11.2 g, 44.4 mmol), potassium acetate (7.3 g, 73.8 mmol), and 1,4-dioxane (61 ml) was degassed by bubbling nitrogen gas for 15 minutes followed by addition of palladium tetrakis (0.6 g, 0.5 mmol) and 2-(dicyclohexylphosphino)biphenyl (0.4 g, 1 mmol). The mixture was heated to reflux for 4 hr. Upon cooling to room temperature, the mixture was filtered with Celite. The filtrate was evaporated under reduced pressure and added with ethyl acetate and hexane to obtain solid. The precipitated solid was filtered with suction, yielding 7.9 g of 2-(16,16-dimethyl-16H-benzo[6,7]indeno[1,2-b]triphenylen-14-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane as pale yellow solid (62%).
A mixture of 2-(16,16-dimethyl-16H-benzo[6,7]indeno[1,2-b]triphenylen-14-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (7.9 g, 15.2 mmol), 2,4-dibromo-1-nitrobenzene (4.6 g, 16.7 mmol), 2M aqueous solution of sodium carbonate (16 ml), ethanol (35 ml), and toluene (105 ml) was degassed by bubbling nitrogen gas for 15 minutes followed by addition of palladium tetrakis (1.4 g, 1.22 mmol) and 2-(dicyclohexylphosphino)biphenyl (0.9 g, 2.44 mmol). The mixture was heated to reflux overnight. Upon cooling to room temperature, the mixture was extracted with ethyl acetate (3 times) and washed with water. The organic layer was dried with anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by column chromatography on silica, yielding 4.9 g of 14-(5-bromo-2-nitrophenyl)-16,16-dimethyl-16H-benzo[6,7]indeno[1,2-b]triphenylene as yellow solid (54%).
A mixture of 14-(5-bromo-2-nitrophenyl)-16,16-dimethyl-16H-benzo [6,7]indeno[1,2-b]triphenylene(4.9 g, 8.2 mmol) and triethylphosphite (25 ml) heated to reflux for 12 hrs. After the reaction finished, triethylphosphite was removed under reduced pressure, and the crude product was purified by column chromatography, yielding 2.2 g of 4-bromo-20,20-dimethyl-1,20-dihydrobenzo[c]phenanthro[9′,10′:5,6]indeno[2,1-a]carbazole as pale yellow solid (49%).
At 0° C., a mixture of sodium hydride (0.1 g, 4.4 mmol) and dimethyl formamide (2 ml) was added the 20,20-dimethyl-1,20-dihydrobenzo[c]phenanthro[9′,10′:5,6]indeno[2,1-a]carb azole (2.2 g, 4 mmol) dissolved in dimethylformamide (6 ml) slowly. After addition is completed, the mixture was warmed to room temperature and kept stirring 30 minutes. The mixture of 2-(3-chlorophenyl)-4,6-diphenylpyrimidine (1.5 g, 4.4 mmol) and dimethylformamide (5 ml) was added and stirred overnight. After the reaction finished, the mixture was quenched with ice water slowly and filtered to get the crude. The crude was purified by column chromatography, yielding 1.8 g of 4-bromo-1-(3-(4,6-diphenylpyrimidin-2-yl)phenyl)-20,20-dimethyl-1,20-dihy drobenzo[c]phenanthro[9′,10′:5,6]indeno[2,1-a]carbazole as pale yellow solid (51%).
Synthesis of N-([1,1′-biphenyl]-2-yl)-1-(3-(4,6-diphenylpyrimidin-2-yl) phenyl)-20,20-dimethyl-N-(naphthalen-1-yl)-1,20-dihydrobenzo[c]phenanthro[9′,10′:5,6]indeno[2,1-a]carbazol-4-amine (Compound 8)
A mixture of 4-bromo-1-(3-(4,6-diphenylpyrimidin-2-yl)phenyl)-20,20-dimethyl-1,20-dihy drobenzo[c]phenanthro[9′,10′:5,6]indeno[2,1-a]carbazole (1.8 g, 2 mmol), N-([1,1′-biphenyl]-3-yl)naphthalen-1-amine (0.7 g, 2.2 mmol), Pd2(dba)3 (0.03 g, 0.04 mmol), 10% P(tBu) in toluene (0.1 ml), NaOtBu (0.3 g, 3 mmol) and toluene (10 ml) was degassed and placed under nitrogen, and then heated to reflux for 12 hrs. After the reaction finished, the mixture was allowed to cool to room temperature and was filtered with Celite. The filtrate was evaporated under reduced pressure and purified by column chromatography, yielding 1.1 g of N-([1,1′-biphenyl]-2-yl)-1-(3-(4,6-diphenylpyrimidin-2-yl)phenyl)-20,20-dimethyl-N-(naphthalen-1-yl)-1,20-dihydrobenzo[c]phenanthro[9′,10′:5,6]indeno[2,1-a]carbazol-4-amine (compound 8) as pale yellow solid (51%).
A mixture of 1-(4-([1,1′-biphenyl]-3-yl)-6-phenylpyrimidin-2-yl)-4-bromo-20,20-dimethyl-1,20-dihydrobenzo[c]phenanthro[9′,10′:5,6]indeno[2,1-a]carbazole (2.7 g, 3.2 mmol), N-([1,1′-biphenyl]-4-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl) dibenzo[b,d]furan-4-amine (g, 3.6 mmol), 2M aqueous solution of sodium carbonate (3 ml), ethanol (6 ml), and toluene (18 ml) was degassed by bubbling nitrogen gas for 15 minutes followed by addition of palladium tetrakis (0.07 g, 0.06 mmol) and 2-(dicyclohexylphosphino)biphenyl (0.04 g, 0.12 mmol). The mixture was heated to reflux overnight. Upon cooling to room temperature, the mixture was filtered to obtain solid. The solid was washed with water and methanol. The residue was purified by column chromatography on silica, yielding 2.3 g of N-(4-(1-(4-([1,1′-biphenyl]-3-yl)-6-phenylpyrimidin-2-yl)-20,20-dimethyl-1,20-dihydrobenzo[c]phenanthro[9′,10′:5,6]indeno[2,1-a]carbazol-4-yl)phenyl)-N-([1,1′-biphenyl]-4-yl)dibenzo[b,d]furan-4-amine (compound 34) as pale yellow solid (61%).
A mixture of 12-bromo-14,14-dimethyl-14H-indeno[1,2-b]triphenylene (10 g, 23.7 mmol), 2-chloroaniline (3.3 g, 26 mmol), Pd2(dba)3 (0.2 g, 0.24 mmol), (tBu)3PHBF4 (0.3 g, 0.95 mmol), NaOtBu (3.5 g, 35.6 mmol) and toluene (100 ml) was degassed and placed under nitrogen, and then heated to reflux. After the reaction finished, the mixture was filtered with Celite. The filtrate was evaporated under reduced pressure. The residue was washed with ethyl acetate and hexane, yielding 7.8 g of N-(2-chlorophenyl)-14,14-dimethyl-14H-indeno[1,2-b]triphenylen-12-amine as brown solid (70%).
A mixture of N-(2-chlorophenyl)-14,14-dimethyl-14H-indeno[1,2-b]triphenylen-12-amine (38.7 g, 82.3 mmol), Pd2(dba)3 (7.5 g, 8.2 mmol), (tBu)3PHBF4 (4.7 g, 16.5 mmol) potassium carbonate (28.4 g, 205.8 mmol), pivalic acid (2.5 g, 24.7 mmol) and 1-Methyl-2-pyrrolidone (230 ml) was heated to 130° C. After the reaction finished, the mixture filtered with Celite and removed the 1-Methyl-2-pyrrolidone under reduced pressure. The residue was washed with dichloromethane and ethyl acetate to obtain brown solid, yielding 29.1 g of 10,10-dimethyl-10,12-dihydrophenanthro[9′,10′:5,6]indeno[2,1-b]carbazole as grey solid (72%)
At ice bath, a mixture of 10,10-dimethyl-10,12-dihydrophenanthro[9′,10′:5,6]indeno[2,1-b]carbazole (1 g, 2.3 mmol) and dimethylformamide (10 ml) was added N-bromosuccinimide (0.4 g, 2.3 mmol) portion wise. After addition is completed, the mixture was warmed to room temperature and stirred overnight. Water was added into mixture after the reaction was finished. The mixture was filtered to obtain solid. The solid was washed with methanol, yielding 0.8 g of 15-bromo-10,10-dimethyl-10,12-dihydrophenanthro[9′,10′:5,6]indeno[2,1-b]carbazole as grey solid (67%)
At 0° C., a mixture of sodium hydride (0.5 g, 22 mmol) and dimethyl formamide (10 ml) was added the 15-bromo-10,10-dimethyl-10,12-dihydrophenanthro[9′,10′:5,6]indeno[2,1-b]carbazole (10.2 g, 20 mmol) dissolved in dimethylformamide (30 ml) slowly. After addition is completed, the mixture was warmed to room temperature and kept stirring 30 minutes. The mixture of 2-chloro-4,6-diphenyl-1,3,5-triazine (5.9 g, 22 mmol) and dimethylformamide (25 ml) was added and stirred overnight. After the reaction finished, the mixture was quenched with ice water slowly and filtered to get the crude. The crude was purified by column chromatography, yielding 8.9 g of 15-bromo-12-(4,6-diphenyl-1,3,5-triazin-2-yl)-10,10-dimethyl-10,12-dihydro phenanthro[9′,10′:5,6]indeno[2,1-b]carbazole as yellow solid (60%).
A mixture of 15-bromo-12-(4,6-diphenyl-1,3,5-triazin-2-yl)-10,10-dimethyl-10,12-dihydro phenanthro[9′,10′:5,6]indeno[2,1-b]carbazole (4 g, 5.3 mmol), N-([1,1′-biphenyl]-4-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)dibenzo[b,d]furan-4-amine (3.1 g, 5.9 mmol), 2M aqueous solution of sodium carbonate (6 ml), ethanol (12 ml), and toluene (36 ml) was degassed by bubbling nitrogen gas for 15 minutes followed by addition of palladium tetrakis (0.1 g, 0.1 mmol) and 2-(dicyclohexylphosphino)biphenyl (0.07 g, 0.2 mmol). The mixture was heated to reflux overnight. Upon cooling to room temperature, the mixture was filtered to obtain solid. The solid was washed with water and methanol. The residue was purified by column chromatography on silica, yielding 2.9 g N-([1,1′-biphenyl]-4-yl)-N-(4-(12-(4,6-diphenyl-1,3,5-triazin-2-yl)-10,10-dimethyl-10,12-dihydrophenanthro[9′,10′:5,6]indeno[2,1-b]carbazol-15-yl)phenyl)-[1,1′-biphenyl]-2-amine (compound 85) as yellow solid (53%).
A mixture of 3,7-dibromodibenzo[b,d]thiophene (20.9 g, 61.3 mmol),biphenyl-2-ylboronic acid (12.2 g, 61.3 mmol), sodium carbonate (13 g, 122.6 mmol), water (60 ml), ethanol (60 ml) and toluene (120 ml) was degassed by bubbling nitrogen gas for 15 minutes followed by addition of palladium tetrakis (1.4 g, 1.22 mmol) and 2-(dicyclohexylphosphino)biphenyl (0.9 g, 2.44 mmol). The mixture was heated to reflux overnight. Upon cooling to room temperature, the mixture was extracted with ethyl acetate (3 times) and washed with water. The organic layer was dried with anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by column chromatography on silica, yielding 12.4 g of 3-([1,1′-biphenyl]-2-yl)-7-bromodibenzo[b,d]thiophene as yellow solid (43%).
A mixture of 3-([1,1′-biphenyl]-2-yl)-7-bromodibenzo[b,d]thiophene (12.4 g, 26.3 mmol) and dichlromethane (525 ml) was cooled to −30° C. and followed by addition of iron chloride (21.3 g, 131.5 mmol) dissolving in nitromethane (26 ml). After the reaction was finished, the mixture quenched with methanol and washed with water. The organic layer was dried with anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by column chromatography on silica, yielding 3.1 g of 12-bromobenzo[b]triphenyleno[2,3-d]thiophene as dark-green solid (29%).
A mixture of 12-bromobenzo[b]triphenyleno[2,3-d]thiophene (3.1 g, 7.5 mmol), bis(pinacolato)diboron (3.4 g, 13.5 mmol), potassium acetate (2.2 g, 22.5 mmol), and 1,4-dioxane (18 ml) was degassed by bubbling nitrogen gas for 15 minutes followed by addition of palladium tetrakis (0.3 g, 0.3 mmol) and 2-(dicyclohexylphosphino)biphenyl (0.05 g, 0.15 mmol). The mixture was heated to reflux for 4 hr. Upon cooling to room temperature, the mixture was filtered with Celite. The filtrate was evaporated under reduced pressure and added with ethyl acetate and hexane to obtain solid. The precipitated solid was filtered with suction, yielding 2 g of 2-(benzo[b]triphenyleno[2,3-d]thiophen-12-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane as pale yellow solid (59%).
A mixture of 2-(benzo[b]triphenyleno[2,3-d]thiophen-12-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (6.9 g, 15.2 mmol), 2,4-dibromo-1-nitrobenzene (4.6 g, 16.7 mmol), 2M aqueous solution of sodium carbonate (16 ml), ethanol (35 ml), and toluene (105 ml) was degassed by bubbling nitrogen gas for 15 minutes followed by addition of palladium tetrakis (1.4 g, 1.22 mmol) and 2-(dicyclohexylphosphino)biphenyl (0.9 g, 2.44 mmol). The mixture was heated to reflux overnight. Upon cooling to room temperature, the mixture was extracted with ethyl acetate (3 times) and washed with water. The organic layer was dried with anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by column chromatography on silica, yielding 5 g of 12-(4-bromo-2-nitrophenyl)benzo[b]triphenyleno[2,3-d]thiophene as yellow solid (62%).
A mixture of 12-(4-bromo-2-nitrophenyl)benzo[b]triphenyleno[2,3-d]thiophene (4.3 g, 8.2 mmol) and triethylphosphite (25 ml) heated to reflux for 12 hrs. After the reaction finished, triethylphosphite was removed under reduced pressure, and the crude product was purified by column chromatography, yielding 1.9 g of 14-bromo-16H-triphenyleno[2′,3′:4,5]thieno[3,2-b]carbazole as yellow solid (47%).
At 0° C., a mixture of sodium hydride (0.5 g, 22 mmol) and dimethylformamide (10 ml) was added the 14-bromo-16H-triphenyleno[2′,3′:4,5]thieno[3,2-b]carbazole (10 g, 20 mmol) dissolved in dimethylformamide (30 ml) slowly. After addition is completed, the mixture was warmed to room temperature and kept stirring 30 minutes. The mixture of 4-chloro-2,6-diphenylpyrimidine (5.8 g, 22 mmol) and dimethylformamide (25 ml) was added and stirred overnight. After the reaction finished, the mixture was quenched with ice water slowly and filtered to get the crude. The crude was purified by column chromatography, yielding 7.8 g of 14-bromo-16-(2,6-diphenylpyrimidin-4-yl)-16H-triphenyleno[2′,3′:4,5]thieno[3,2-b]carbazole as pale yellow solid (49%).
A mixture of 14-bromo-16-(2,6-diphenylpyrimidin-4-yl)-16H-triphenyleno[2′,3′:4,5]thieno[3,2-b]carbazole (2.3 g, 3.2 mmol), N-(4-methoxyphenyl)-1H-phenalen-5-amine (1 g, 3.6 mmol), 2M aqueous solution of sodium carbonate (3 ml), ethanol (6 ml), and toluene (18 ml) was degassed by bubbling nitrogen gas for 15 minutes followed by addition of palladium tetrakis (0.07 g, 0.06 mmol) and 2-(dicyclohexylphosphino)biphenyl (0.04 g, 0.12 mmol). The mixture was heated to reflux overnight. Upon cooling to room temperature, the mixture was filtered to obtain solid. The solid was washed with water and methanol. The residue was purified by column chromatography on silica, yielding 1.8 g of 16-(2,6-diphenylpyrimidin-4-yl)-N-(4-methoxyphenyl)-N-(1H-phenalen-5-yl)-1 6H-triphenyleno[2,3′:4,5]thieno[3,2-b]carbazol-14-amine (compound 74) as pale yellow solid (62%).
According to the previous synthesis methods, series of intermediates and the product compounds are synthesized analogously, as follows.
