Patent Application
20240315132
The present disclosure relates to a novel organic compound and an organic electroluminescent device using same and, more specifically, to a compound having excellent electron injection and transport potentials, and an organic electroluminescent device that includes same in at least one organic layer and thus exhibits an improvement in luminous efficiency, driving voltage, and lifespan as well as progressive driving voltage.
In the structure of an organic electroluminescence device (hereinafter referred to as “EL device”), application of a voltage between the two electrodes injects holes from the anode and electrons from the cathode into the organic layer. When the injected holes and electrons are combined with each other, excitons are generated and then return to a ground state, emitting light. Materials used in the organic layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their functions.
Also, the material used in the light-emitting layer of the organic EL device can be divided into blue, green, and red light-emitting materials. In addition, yellow and orange light-emitting materials may be used for implementing colors closer to natural colors. Furthermore, a host/dopant system may be used as a light-emitting material in order to increase the color purity and enhance the light-emitting efficiency through energy transfer. Dopant materials may be divided into phosphorescent dopants accounted for by organic materials and phosphorescent dopants accounted for by metal complex compounds bearing heavy atoms such as Ir and Pt. The development of such a phosphorescent material can theoretically improve luminous efficiency up to four times, compared to fluorescence. Thus, attention has been focused on phosphorescent host materials as well as phosphorescent dopants.
Until now, NPB, BCP, Alq3, and the like represented by the following chemical formulas are widely known for use in hole injection, hole transport, hole block, and electron transport layers, and anthracene derivatives have been reported as fluorescent dopant/host materials in the light-emitting layer. With respect to phosphorescent materials, which are advantageous in terms of luminous efficiency over other luminescent materials, Ir-bearing metal complex compounds, such as Firpic, Ir(ppy)3, (acac)Ir(btp)2, etc., are used as blue, green, and red dopant materials. So far, CBP has shown excellent properties as a phosphorescent host material.
However, conventional materials, although advantageous in terms of emission properties, have low glass transition temperatures and very poor thermal stability, so they are not satisfactory in terms of lifespan for organic EL devices. Therefore, there is a need for the development of high-performance organic layer materials.
The present disclosure aims to provide a novel organic compound that is superb in terms of all of electron injection and transport potential, electrochemical stability, and thermal stability and can be used as an organic layer material in an organic EL device, specifically as an electron transport layer material or an N-type charge generation layer material.
Also, the present disclosure aims to provide an organic EL device including the aforementioned novel organic composition, which exhibits a low driving voltage and high luminous efficiency and has an improved lifespan.
In order to achieve the aims, the present disclosure provides an organic compound represented by the following Chemical Formula 1:
Also, the present disclosure provides an organic electroluminescent device including: an anode; a cathode, and at least one organic layer disposed between the anode and the cathode, wherein the at least one organic layer includes the organic compound described above. In this regard, the organic layer including the compound may be an electron transport layer.
Furthermore, the present disclosure provides an organic electroluminescent device including an anode and a cathode spaced apart from each other; a plurality of light-emitting units interposed between the anode and the cathode; and an N- and a P-type charge generation layer disposed between adjacent light-emitting units, wherein each light-emitting unit includes a hole transport layer, a light-emitting layer, and an electron transport layer and the N-type charge generation layer includes the compound described above.
With excellency in electron transport and emission potentials, electrochemical stability, and thermal stability, the compound of the present disclosure can be used as a material for an organic layer in an organic EL device. Particularly, when used as a material for any one of an electron transport layer, an electron transport auxiliary layer, and an N-type charge generation layer, the compound of the present disclosure allows for the fabrication of an organic EL device that superb emission performance, low driving voltage, high luminous efficiency, and prolonged lifespan characteristics, compared to conventional materials.
Below, a detailed description will be given of the present disclosure.
The present disclosure provides a novel compound that is superb in terms of electron injection and transport potential, electrochemical stability, and thermal stability and can be used as an electron transport auxiliary layer material or an N-type charge generation layer material that can improve luminous efficiency, lifespan, driving voltage, and progressive driving voltage characteristics in an organic EL device.
In detail, the compound represented by Chemical Formula 1 has the phenanthroline moiety-based structure in which various heteroaryl groups [particularly, electron withdrawing groups (EWG) with high electron absorptivity] or phosphine oxide or silyl group are introduced into the carbon at position 4 directly or via a linker while alkyl group or cycloalkyl group are introduced into the carbon atoms at positions 2 and 9. Here, numbering for the carbon/nitrogen atoms in the phenanthroline moiety is as follows:
In the compound of the present disclosure, the phenanthroline moiety bears nitrogen atoms (N) of the sp2 hybrid orbital relatively rich in electron. Specifically, structured to bear two adjacent nitrogen atoms, the phenanthroline moiety can form a covalent bond with a neighboring hydrogen atom (H) or a coordination bond with an alkali metal or alkaline earth metal, such as Li or Yb. When the phenanthroline moiety-based compound of Chemical Formula 1 is applied to an electron transport layer or an N-type charge generation layer, the phenanthroline moiety traps an alkali metal or alkaline earth metal dope therein to increase the intramolecular electron density, thereby enhancing electron injection and transport potentials. For example, when the compound of the present disclosure is applied to an N-type charge generation layer in an OLED, the nitrogen atoms of the phenanthroline moiety may bind to the dopant alkali metal or alkaline earth metal in the N-type charge generation layer to form a gap state. Specifically, even though used as a host material alone without being mixed with a different host material, the compound of the present disclosure can smoothly transport electrons from the N-type charge generation layer to the electron transport layer due to the gap state. In addition, even when applied to the electron transport layer in an OLED, the compound of the present disclosure can smoothly transport electron toward the light-emitting layer. Therefore, the use of the compound of the present disclosure as a material for an N-type charge generation layer or an electron transport layer allows the organic EL device to decrease in driving voltage, increase in luminous efficiency, and enjoy a prolonged lifespan.
Moreover, having high electron absorptivity, the phenanthroline moiety of the compound can serve as an electron withdrawing group (EWG). In the phenanthroline moiety, a heteroaryl [specifically an electron withdrawing group (EWG) with high electron absorptivity], phosphine oxide, or silyl group is introduced into the carbon atom at position 4 directly or via a linker. Particularly, the compound of the present disclosure having an electron withdrawing group (EWG) with high electron absorptivity introduced into the carbon atom at position 4 exhibits improved electron mobility, enabling the maximization of electron injection and transport potentials. Therefore, the application of the compound of the present disclosure to an EL device guarantees low deriving voltage, high current efficiency, and prolonged lifespan characteristics and enhances a progressive deriving voltage characteristic, thus preventing the device from increasing in consumption power and decreasing in lifespan.
With the introduction of the substituents such as an alkyl group, a cycloalkyl group, etc., into the carbon atoms at the active sites positions 2 and 9, the phenanthroline moiety can be increased in thermal stability due to the blockage of the active sites. However, the compound having an aryl introduced into position 2 and/or 9 of the phenanthroline moiety increases in sublimation temperature because its large molecular weight. In this regard, an excess of high heat for sublimating the compound upon the fabrication of an organic EL device may damage the device. Thus, it is preferred that an alkyl group or cycloalkyl group, particularly a short alkyl group or cycloalkyl group, rather than an aryl, is introduced into the carbon atom at position 2 and/or 9 in the phenanthroline moiety. Such compounds of the present disclosure have the active sites blocked therein through a minimal increase of molecular weight and thus can increase in thermal stability without deteriorating the device. In addition, the compound of the present disclosure is lower in sublimation temperature than compounds having aryl groups introduced into the carbon atoms at positions 2 and 9 in the phenanthroline moiety. Hence, the compounds of the present disclosure can prevent the deterioration of the devices upon the fabrication thereof while increasing in thermal stability.
As described above, the compound represented by Chemical Formula 1 according to the present disclosure is superb in terms of electron injection and transport potential. Thus, the compounds of the present disclosure can be used as a material for an organic layer, preferably for an electron transport layer in an organic EL device. In addition, the compound of the present disclosure may be used as a material for an N-type charge generation layer in tandem organic EL devices. As such, the compound of the present disclosure, represented by Chemical Formula 1, when applied as a material for an electron transport layer or N-type charge generation layer in an organic EL device, can improve deriving voltage, luminous efficiency, and lifespan characteristics in the organic EL device and prevent the increase of a progressive driving voltage, and furthermore the performance of a full-color organic light-emitting panel to which the organic EL device is applied can be maximized.
In the compound represented by Chemical Formula 1, R1 and R2 are same or different and are each independently selected from the group consisting of a hydrogen atom, a deuterium atom (D), an alkyl group of C1-C60, a cycloalkyl group of C3-C60, and a heteroaryl group having 5 to 60 nuclear atoms, wherein a case where both of R1 and R2 are a hydrogen atom is excluded. In contrast to the compound wherein R1 and R2 both are a hydrogen atom, the compound of Chemical Formula 1 exhibits improved thermal stability as either or both of the active sites of the phenanthroline moiety are blocked. In addition, the compound of Chemical Formula 1, unlike the compound wherein R1 and R2 are both aryl groups, can improve in thermal stability without deteriorating the device because the molecular weight is minimally increased, along with the blockage of the active sites.
In an embodiment, at least one of R1 and R2 may be an alkyl group of C1-C60.
In another embodiment, R1 and R2, which are same or different, may each be independently an alkyl group of C1-C20.
In a further embodiment, R1 and R2, which are same or different, may each be an alkyl group of C1-C6. Specifically, the alkyl group of C1-C6 may be selected from the group consisting of methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, and t-butyl group.
The alkyl group, the cycloalkyl group, the aryl group, and the heteroaryl group of R1 and R2 may remain unsubstituted or may each independently be substituted with at least one substituent selected from the group consisting of a deuterium atom, a halogen group, a hydroxy group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazino group, a hydrazono group, an alkyl group of C1-C60, an alkenyl group of C2-C60, an alkynyl group of C2-C60, a cycloalkyl group of C3-C60, a heterocycloalkyl group having 3 to 60 nuclear atoms, a cycloalkenyl group of C3-C60, a heterocycloalkenyl group having 3 to 60 nuclear atoms, an aryl group of C6-C60, a heteroaryl group having 5 to 60 nuclear atoms, an alkyloxy group of C1-C60, an aryloxy group of C6-C60, an alkylsilyl group of C1-C60, an arylsilyl group of C6-C60, an alkylboron group of C1-C40, an arylboron group of C6-C60, an aryl phosphine group of C6-C60, an aryl phosphine oxide group of C6-C60, and an arylamine group of C6-C60, and when the substituents are plural in number, the substituents are the same as or different from each other. Here, the heterocycloalkyl group and the heteroaryl each bear at least one heteroatom selected from the group consisting of N, S, O, and Se.
According to R1 and R2, the compound represented by Chemical Formula 1 may be a compound represented by any one of the following Chemical Formulas 2 to 5, but with no limitations thereto:
According to an embodiment, R2 in the compounds of Chemical Formulas 2 to 5 may be an alkyl group of C1-C6 and specifically, may be selected from the group consisting of methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, and t-butyl group. In this regard, R2 may be identical to the substituents of Chemical Formula 2-5, which correspond to R1 in Chemical Formula 1.
In Chemical Formula 1, L1 is selected from the group consisting of a single bond, an arylene group of C6-C60, and a heteroarylene group having 5 to 60 nuclear atoms and specifically may be a single bond or may be selected from the group consisting of an arylene group of C6-C30 and a heteroarylene group having 5 to 30 nuclear atoms.
The arylene group and the heteroarylene group of L1 may remain unsubstituted or may each independently be substituted with at least one substituent selected from the group consisting of a deuterium atom, a halogen group, a hydroxy group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazino group, a hydrazono group, an alkyl group of C1-C60, an alkenyl group of C2-C60, an alkynyl group of C2-C60, a cycloalkyl group of C3-C60, a heterocycloalkyl group having 3 to 60 nuclear atoms, a cycloalkenyl group of C3-C60, a heterocycloalkenyl group having 3 to 60 nuclear atoms, an aryl group of C6-C60, a heteroaryl group having 5 to 60 nuclear atoms, an alkyloxy group of C1-C60, an aryloxy group of C6-C60, an alkylsilyl group of C1-C60, an arylsilyl group of C6-C60, an alkylboron group of C1-C40, an arylboron group of C6-C60, an aryl phosphine group of C6-C60, an aryl phosphine oxide group of C6-C60, and an arylamine group of C6-C60, and when the substituents are plural in number, the substituents are the same as or different from each other.
In an embodiment, L1 may be an arylene group of C6-C60.
In another embodiment, L1 may be a linker represented by the following Chemical Formula L:
In another embodiment, L1 may be selected from the group consisting of the following linkers L1 to L4. In this regard, the phenanthroline moiety and the substituent Ar1 in the compound of the present disclosure are bonded at para or meta positions or at para-para or meta-meta positions to the linker. With such a framework, the compound of the present discloses forms a plate-like structure and induces stacking between molecules, thereby increasing in electron mobility and thus having better electron transport properties. In addition, the compound of the present disclosure can significantly increase in physical, electrochemical, and thermal stability because the compound has minimal interaction between the phenanthroline moiety and the substituent Ar1, increased molecular structural stability, and minimal intramolecular steric hindrance. Moreover, compared to compounds in which the phenanthroline moiety and the substituent Ar1 are bonded at the ortho positions or at the ortho-ortho position, the compound of the present disclosure is effective for suppressing the crystallization of the organic layer and thus can greatly enhance the durability and lifespan characteristics of the organic EL device.
Hydrogen atoms on the linkers L1-L4 may be replaced by at least one substituent such as a deuterium atom (D), a halogen group, a cyano group, a nitro group, an alkyl group of C1-C12, an aryl group of C6-C10, a heteroaryl group having 5-9 nuclear atoms, etc.
In Chemical Formula 1, Ar1 is selected from the group consisting of an aryl group of 5 to 60 nuclear atoms, —P(═O)(R3)(R4), and —Si(R5)(R6)(R7).
In an embodiment, Ar1 may be a heteroaryl group having 5 to 60 nuclear atoms. Particularly when Ar1 is an electron withdrawing group (EWG) with high electron absorptivity, the compound of Chemical Formula 1 has further improved electron motility, exhibiting maximal electron injection and transport potential. In addition, an organic layer (e.g., N-type charge generation layer) in an OLED using the compound of Chemical Formula 1 wherein Ar1 is an EWG allows for smoother electron injection, compared to the compound of Chemical Formula 1 wherein Ar1 is —P(═O)(R3)(R4) or —Si(R5)(R6)(R7), when an adjacent organic layer (e.g., electron transport layer) has a deep LUMO value. Having a deeper LUMO value than that in an OLED using the compound of Chemical Formula 1 according to the present disclosure, an organic layer (e.g., electron transport layer) in an OLED using a compound wherein the EWG is a triazine or pyrimidine group may be difficult in terms of electron migration. Therefore, Ar1 is preferably a heteroaryl group having 5 to 60 nuclear atoms (specifically a heteroaryl group having 5 to 30 nuclear atoms), with the exclusion of triazine and pyrimidine groups. Examples of the EWG include, but are not limited to, the substituents represented by the following Chemical Formulas S1 to S6.
R3 to R7, which are same or different, are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen group, a hydroxy group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazino group, a hydrazono group, an alkyl group of C1-C60, an alkenyl group of C2-C60, an alkynyl group of C2-C60, a cycloalkyl group of C3-C60, a heterocycloalkyl group having 3 to 60 nuclear atoms, a cycloalkenyl group of C3-C60, a heterocycloalkenyl group having 3 to 60 nuclear atoms, an aryl group of C6-C60, a heteroaryl group having 5 to 60 nuclear atoms, an alkyloxy group of C1-C60, an aryloxy group of C6-C60, an alkylsilyl group of C1-C60, an arylsilyl group of C6-C60, an alkylboron group of C1-C40, an arylboron group of C6-C60, an aryl phosphine group of C6-C60, an aryl phosphine oxide group of C6-C60, and an arylamine group of C6-C60. Specifically, R3 to R7, which are same or different, may each be independently selected from the group consisting of a deuterium atom, a halogen group, a hydroxy group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazino group, a hydrazono group, an alkyl group of C1-C20, an alkynyl group of C2-C20, a cycloalkyl group of C3-C20, a heterocycloalkyl group having 3 to 30 nuclear atoms, a cycloalkenyl group of C3-C20, a heterocycloalkenyl group having 3 to 30 nuclear atoms, an aryl group of C6-C30, a heteroaryl group having 5 to 30 nuclear atoms, an alkyloxy group of C1-C30, and an aryloxy group of C6-C30.
In an embodiment, R3 to R7, which are same or different, may each be independently an aryl group of C6-C30, and specifically an aryl group of C6-C30. Examples of the aryl group include phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthryl group, anthryl group, naphthacenyl group, pyrenyl group, and chrysenyl group, but are not limited thereto.
The aryl group and the heteroaryl group of Ar1 and the hydrazino group, the hydrazone group, the alkyl group, the alkenyl group, the alkynyl group, the cycloalkyl group, the heterocycloalkyl group, the cycloalkenyl group, the heterocycloalkenyl group, the aryl group, the heteroaryl group, the alkylpoxy group, the aryloxy group, the alkylsilyl group, the arylsilyl group, the alkylboron group, the arylboron group, the aryl phosphine group, the aryl phosphine oxide group, the and aryl amine group of R3 to R7 may each be independently unsubstituted, or substituted with a substituent selected from the group consisting of a deuterium atom, a halogen group, a hydroxy group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazino group, a hydrazono group, an alkyl group of C1-C60, an alkenyl group of C2-C60, an alkynyl group of C2-C60, a cycloalkyl group of C3-C60, a heterocycloalkyl group having 3 to 60 nuclear atoms, a cycloalkenyl group of C3-C60, a heterocycloalkenyl group having 3 to 60 nuclear atoms, an aryl group of C6-C60, a heteroaryl group having 5 to 60 nuclear atoms, an alkyloxy group of C1-C60, an aryloxy group of C6-C60, an alkylsilyl group of C1-C60, an arylsilyl group of C6-C60, an alkylboron group of C1-C40, an arylboron group of C6-C60, an aryl phosphine group of C6-C60, an aryl phosphine oxide group of C6-C60, and when the substituents are plural in number, the substituents are the same as or different from each other.
In detail, Ar1 may be a substituent represented by any one selected from the group consisting of the following Chemical Formulas S1 to S8, but with no limitations thereto:
Particularly, the substituents of Chemical Formulas S1 to S6 may be embodied into substituents represented by the following Chemical Formulas SS1 to SS9, but with no limitations thereto:
The compound represented by Chemical Formula 1 according to the present disclosure may be embodied into that represented by any one of the following Chemical Formulas 6 to 11, but with no limitations thereto:
The compound according to the present disclosure, represented by Chemical Formula 1, may be embodied into any one of the following Compounds A-1 to A-28, B-1 to B-24, C-1 to C-24, D-1 to D-24, E-1 to E-24, and F-1 to F-24. However, the compound according to the present disclosure, represented by Chemical Formula 1, is not limited thereto.
As used herein, the term “alkyl group” refers to a monovalent substituent derived from a linear or branched saturated hydrocarbon of 1 to 40 carbon atoms. Its examples include methyl, ethyl, propyl, isobutyl, isopropyl, sec-butyl, pentyl, iso-amyl, and hexyl, but are not limited thereto.
As used herein, the term “alkenyl” refers to a monovalent substituent derived from a linear or branched unsaturated hydrocarbon of 2 to 40 carbon atoms bearing one or more carbon-carbon double bonds. Examples thereof include vinyl, allyl, isopropenyl, and 2-butenyl, but are not limited thereto.
The term “alkynyl”, as used herein, refers to a monovalent substituent derived from a linear or branched unsaturated hydrocarbon of 2 to 40 carbon atoms bearing one or more carbon-carbon triple bonds. Examples thereof include ethynyl and 2-propynyl, but are not limited thereto.
As used herein, the term “cycloalkyl group” means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon of 3 to 40 carbon atoms. Examples of the cycloalkyl group include cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine, but are not limited thereto.
As used herein, the term “heterocycloalkyl group” means a monovalent substituent derived from a non-aromatic hydrocarbon of 3 to 40 nuclear atoms bearing, as ring members, one or more, preferably one to three heteroatoms such as N, O, S, or Se. Examples of the heterocycloalkyl group include, but are not limited to, morpholine and piperazine.
The term, “aryl”, as used herein, means a monovalent substituent derived from an aromatic hydrocarbon of 6 to 60 carbon atoms composed of a single ring or a combination of two or more rings. Further, the aryl may also include a form in which two or more rings are simply pendant to or fused with each other. Examples of the aryl include phenyl, naphthyl, phenanthryl, and anthryl, but are not limited thereto.
The term “heteroaryl”, as used herein, refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon of 5 to 60 nuclear atoms, bearing, as ring members, one or more, preferably one to three heteroatoms, such as N, O, S, or Se. In addition, the heteroaryl may also include a form in which two or more rings are simply pendant to or fused with each other, and further a fused form with an aryl group. Examples of the heteroaryl include: a 6-membered monocyclic ring, such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl, a polycyclic ring, such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl, 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, and 2-pyrimidinyl, but are not limited thereto.
The term “alkylpoxy group”, as used herein, means a monovalent substituent represented by R′O—, in which R′ is an alkyl group of 1 to 40 carbon atoms and may include a linear, branched, or cyclic structure. Examples of the alkylpoxy group include methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, and pentoxy, but are not limited thereto.
The term “aryloxy”, as used herein, means a monovalent substituent represented by RO—, in which R is an aryl group of 6 to 40 carbon atoms. Examples of the aryloxy include phenyloxy, naphthyloxy, and diphenyloxy, but are not limited thereto.
As used herein, the term “alkylsilyl” refers to a silyl substituted with an alkyl group of 1 to 40 carbon atoms and is intended to encompass mono-, di-, and trialkylsilyl. The term “arylsilyl” refers to a silyl substituted with an aryl group of 5 to 60 carbon atoms and is intended to encompass mono-, di, and triarylsilyl.
As used herein, the term “alkylboron” refers to a boron group substituted with an alkyl group of 1 to 40 carbon atoms, and the term “arylboron: refers to a boron group substituted with an aryl group of 6 to 60 carbon atoms.
As used herein, the term “alkyl groupphosphinyl” refers to a phosphine group substituted with an alkyl group of 1 to 40 carbon atoms and is indented to encompass mono- and dialkyl groupphosphinyl. Also, the term “arylphosphinyl” refers to a phosphine group substituted with a mono- or diaryl of 6 to 60 carbon atoms and is intended to encompass mono- and diarylphosphinyl.
As used herein, the term “arylamine” refers to an amine substituted with an aryl group of 6 to 60 carbon atoms and is intended to encompass mono- and diarylamine.
The term “heteroarylamine”, as used herein, means an amine substituted with a heteroaryl group having 5 to 60 nuclear atoms and is intended to encompass mono- and diheteroarylamines.
The term “(aryl)(heteroaryl)amine”, as used herein, means an amine substituted with an aryl group of 6 to 60 carbon atoms and a heteroaryl group having 5 to 60 nuclear atoms.
The “fused ring”, as used herein, means a fused aliphatic ring of 3 to 40 carbon atoms, a fused aromatic ring of 6 to 60 carbon atoms, a fused heteroaliphatic ring of 3 to 60 nuclear atoms, a fused heteroaromatic ring of 5 to 60 nuclear atoms, or a combined form thereof.
The present disclosure also provides an organic electroluminescent device (hereinafter referred to as “organic EL device”) including the compound represented by Chemical Formula 1.
Below, the organic EL devices according to the first to the third embodiments of the present disclosure will be described in detail in conjunction with
As shown in
The at least one organic layer (300) may include at least one of a hole injection layer (310), a hole transport layer (320), a light-emitting layer (330), an electron transport auxiliary layer (360), an electron transport layer (340), and an electron injection layer (350), wherein the organic layer (300) contains the compound represented by Chemical Formula 1. Specifically, the organic layer containing the compound of Chemical Formula 1 may be an electron transport layer (340). That is, the compound represented by Chemical Formula 1 is used as an electron transport layer material in an organic EL device. In such an organic EL device, electrons can be easily injected from the cathode or the electron injection layer to the electron transport layer with the aid of the compound of Chemical Formula 1 and then move toward the light-emitting layer, so that holes and electrons highly combine with each other. Thus, the organic EL device of the present disclosure is excellent in luminous efficiency, power efficiency, and luminance. Moreover, the compound of Chemical Formula 1 is superb in terms of thermal stability and electrochemical stability and as such, can enhance the performance of the organic EL device.
The compound of Chemical Formula 1 may be used alone or in combination with an electron transport layer material known in the art.
The electron transport layer material that may be used in combination with the compound of Chemical Formula 1 includes an electron transport material commonly known in the art. Non-limiting examples of available electron transport materials may include oxazole-based compounds, isoxazole-based compounds, triazole-based compounds, isothiazole-based compounds, oxadiazole-based compounds, thiadiazole-based compounds, perylene-based compounds, aluminum complexes (e.g., Alq3, tris(8-quinolinolato)-aluminum), and gallium complexes (e.g., Gaq′2OPiv, Gag′2OAc, and 2(Gaq′2)). These may be used solely or two or more types thereof may be used in combination.
In the present disclosure, when the compound of Chemical Formula 1 and the material for the electron transport layer are used in combination, a mixing ratio thereof is not particularly limited, and may be appropriately adjusted within a range known in the art.
No particular limitations are imparted to the structure of the organic EL device of the present disclosure, but, for example, an anode (100), at least one organic layer (300), and a cathode (200) may be sequentially deposited on a substrate (see
According to an embodiment, the organic EL device, as shown in
The organic EL device of the present disclosure may be fabricated by forming organic layers and electrodes with materials and methods known in the art, except that at least one organic layer (300) [e.g., electron transport layer (340)] contains the compound represented by Chemical Formula 1.
The organic layer may be formed using a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, and thermal transfer.
No particular limitations are imparted to a substrate available in the present disclosure. Non-limiting examples of the substrate available in the present disclosure include silicon wafers, quartz, glass plates, metal plates, plastic films, and sheets.
In addition, examples of an anode material include, but are not limited to: metals such as vanadium, chromium, copper, zinc, and gold or an alloy thereof; 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 SnO2:Sb; conductive polymers such as polythiophene, poly(3-methylthiophene), poly [3,4-(ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole, or polyaniline; and carbon black.
Furthermore, examples of cathode materials available in the present disclosure include, but are not limited to, a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead, or an alloy thereof; a multi-layered material such as LiF/Al or LiO2/Al.
Moreover, so long as it is known in the art, any material for the hole injection layer, the hole transport layer, the light-emitting layer, and the electron injection layer may be used without particular limitations.
Referring to
As shown in
Such a tandem organic EL device includes at least two light-emitting units, with a charge generation layer interposed between adjacent light-emitting units and as such, can be configured to increase the number of light-emitting units.
According to an embodiment, the plurality of light-emitting units may include a 1st light-emitting unit (400), a 2nd light-emitting unit (500), . . . , and an m−1th light-emitting unit (m=an integer of 3 or greater, specifically 3-4). In this regard, a charge generation layer (600) including an N-type charge generation layer (610) and a P-type charge generation layer (620) is disposed between the adjacent light-emitting units, wherein the N-type charge generation layer (610) contains the compound represented by Chemical Formula 1.
Specifically, the organic EL device according to the present disclosure includes: an anode (100) and a cathode (200), which face each other; a first light-emitting unit (400) disposed on the anode (100); a second light-emitting unit (500) disposed on the first light-emitting unit (400); a charge generation layer (600), disposed between the first and the second light-emitting unit (400, 500), including an N-type charge generation layer (610) and a P-type charge generation layer (620). The N-type charge generation layer (610) contains the compound represented by Chemical Formula 1.
The light-emitting units (400, 500) each include a hole transport layer (410, 510), a light-emitting layer (420, 520), and an electron transport layer (430, 530). Specifically, the first light-emitting unit (400) may include a first hole transport layer (410), a first light-emitting layer (420), and a first electron transport layer (430) while a second light-emitting unit (500) may include a hole transport layer (510), a light-emitting layer (520), and an electron transport layer (530). Optionally, the first light-emitting unit (400) may further include a hole injection layer (440).
So long as it is known in the art, any material may be employed for the hole transport layer (410, 510), the light-emitting layer (420, 520), the electron transport layer (430, 530), and the hole injection layer (440).
Being disposed between adjacent light-emitting units (400, 500), the charge generation layer (CGL) (600) can control the charges between the light-emitting units (400, 500) to make a charge balance.
The charge generation layer (600) includes an N-type charge generation layer (610), positioned adjacent to the first light-emitting unit (400), for supplying electrons to the first light-emitting unit (400); and a P-type charge generation layer (620), positioned adjacent to a second light-emitting unit (500), for supplying holes to the second light-emitting unit (500).
The N-type charge generation layer (610) includes the compound represented by Chemical Formula 1. With excellent electron mobility, the compound of Chemical Formula 1 exhibits excellent electron injection and transport potentials. Hence, when applied as an N-type charge generation layer material to an organic EL device, the compound of Chemical Formula 1 can prevent the device from increasing in progressive driving voltage and decreasing in lifespan.
According to an embodiment, the N-type charge generation layer (610) contains one host having an electron transport property, and the host is the compound represented by Chemical Formula 1. In contrast to an N-type charge generation layer containing two hosts, the N-type charge generation layer (610) of the present disclosure can be prepared through co-deposition, which may lead to an improvement in process efficiency.
The N-type charge generation layer (610) may further include an N-type dopant.
So long as it is commonly used for an N-type charge generation layer in the art, any material may be available in the present disclosure without particular limitations. Examples of the material include: alkali metals, such as Li, Na, K, Rb, Cs, Fr, and so on; alkaline earth metals, such as Be, Mg, Ca, Sr, Ba, Ra, and so on; metals in Group 15, such as Bi (bismuth), Sb (antimony), and so on; lanthanide metals, such as La (lanthanum), Ce (cerium), Pr (preseodyminum), Nd (neodymium), Pm (promethium), Sm (samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Yb (ytterbium), and Lu (lutetium); and compounds of at least one of the metals. In addition, the N-type charge generation layer may be an organic N-type dopant that has an electron donor property and can donor at least a part of electric charges to an organic host (e.g., the compound of Chemical Formula 1) to form a charge-transfer complex with the organic host, and may be exemplified by bis(ethylenedithio)tetrathiafulvalene (BEDT-TTF) and tetrathiafulvalene (TTF).
The thickness of the N-type charge generation layer (610) is not particularly limited and may range, for example, from about 5 to 30 nm.
The P-type charge generation layer (620) may be composed of a metal or a P-type doped organic material. Here, the metal may be exemplified by Al, Cu, Fe, Pb, Zn, Au, Pt, W, In, Mo, Ni, and Ti and may be used alone or in the form of an alloy of two or more metals. In addition, no particular limitations are imparted to any P-type dopant and host that are commonly used for the P-type doped organic material. Examples of the P-type dopant include F4-TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane), iodide, FeCl3, FeF3, and SbCl5. These dopants may be used solely or in combination. Non-limiting examples of the host include NPB (N,N′-bis(naphthaen-1-yl)-N,N′-bis(phenyl)-benzidine), TPD (N,N′-bis(3-methylphenyl)N,N′-bis(phenyl)-benzidine), and TNB (N,N,N′,N′-tetra-naphthalenyl-benzidine). These hosts may be used solely or in combination.
Because the anode (100) and the cathode (200) are the same as in the first to the third embodiment, a description thereof is omitted.
A better understanding of the present disclosure may be obtained through the following examples which are set forth to illustrate, but are not to be construed as limiting the present disclosure.
4-Chloro-2,9-dimethyl-1,10-phenanthroline (5 g, 20.6 mmol), 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine (9.6 g, 20.6 mmol), Pd(OAc)2 (0.2 g, 1.0 mmol), Xphos (1.0 g, 2.1 mmol), and Cs2CO3 (13.5 g, 41.3 mmol) were added to a mixture of toluene (50 ml), EtOH (10 ml), and H2O (10 ml) and heated for 12 hours under reflux. After completion of the reaction, extraction was conducted with methylene chloride. The extract was added with MgSO4 and then filtered. The solvent was removed from the filtered organic layer which was then purified by column chromatography to afford the target compound (9.0 g, yield: 80%).
[LCMS]: 545
The same procedure as in Synthesis Example 1, with the exception of using 2-phenyl-4-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.9 g, yield: 79%).
[LCMS]: 545
The same procedure as in Synthesis Example 1, with the exception of using 2-phenyl-4-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzofuro[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.2 g, yield: 75%).
[LCMS]: 529
The same procedure as in Synthesis Example 1, with the exception of using 4-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.5 g, yield: 76%).
[LCMS]: 545
The same procedure as in Synthesis Example 1, with the exception of using XXX instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, 4-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine was carried out to afford the target compound (8.5 g, yield: 76%).
[LCMS]: 545
The same procedure as in Synthesis Example 1, with the exception of using 6,8-diphenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.0 g, yield: 70%).
[LCMS]: 554
The same procedure as in Synthesis Example 1, with the exception of using 6,8-diphenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.0 g, yield: 70%).
[LCMS]: 554
The same procedure as in Synthesis Example 1, with the exception of using 6-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.1 g, yield: 72%).
[LCMS]: 478
The same procedure as in Synthesis Example 1, with the exception of using 8-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.1 g, yield: 72%).
[LCMS]: 478
The same procedure as in Synthesis Example 1, with the exception of using 2,3,5-triphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (9.2 g, yield: 76%).
[LCMS]: 591
The same procedure as in Synthesis Example 1, with the exception of using 2,3,5-triphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (9.2 g, yield: 76%).
[LCMS]: 591
The same procedure as in Synthesis Example 1, with the exception of using 4-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)quinazoline instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.1 g, yield: 71%).
[LCMS]: 489
The same procedure as in Synthesis Example 1, with the exception of using 1-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole was instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, carried out to afford the target compound (7.0 g, yield: 71%).
[LCMS]: 477
4-Chloro-2,9-diethyl-1,10-phenanthroline (5.6 g, 20.6 mmol), 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine (9.6 g, 20.6 mmol), Pd(OAc)2 (0.2 g, 1.0 mmol), Xphos (1.0 g, 2.1 mmol), and Cs2CO3 (13.5 g, 41.3 mmol) were added to a mixture of toluene (50 ml), EtOH (10 ml), and H2O (10 ml) and heated for 12 hours under reflux. After completion of the reaction, extraction was conducted with methylene chloride. The extract was added with MgSO4 and then filtered. The solvent was removed from the filtered organic layer which was then purified by column chromatography to afford the target compound (9.0 g, yield: 75%).
[LCMS]: 573
The same procedure as in Synthesis Example 14, with the exception of using 2-phenyl-4-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine was carried out to afford the target compound (9.0 g, yield: 75%).
[LCMS]: 573
The same procedure as in Synthesis Example 14, with the exception of using 2-phenyl-4-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzofuro[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.6 g, yield: 75%).
[LCMS]: 557
The same procedure as in Synthesis Example 14, with the exception of using 4-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.5 g, yield: 72%).
[LCMS]: 573
The same procedure as in Synthesis Example 14, with the exception of using 4-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.5 g, yield: 72%).
[LCMS]: 573
The same procedure as in Synthesis Example 14, with the exception of using 6,8-diphenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.6 g, yield: 72%).
[LCMS]: 582
The same procedure as in Synthesis Example 14, with the exception of using 6,8-diphenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.6 g, yield: 72%).
[LCMS]: 582
The same procedure as in Synthesis Example 14, with the exception of using 6-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.5 g, yield: 71%).
[LCMS]: 506
The same procedure as in Synthesis Example 14, with the exception of using 8-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.5 g, yield: 71%).
[LCMS]: 506
The same procedure as in Synthesis Example 14, with the exception of using 2,3,5-triphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (9.2 g, yield: 72%).
[LCMS]: 619
The same procedure as in Synthesis Example 14, with the exception of using 2,3,5-triphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (9.2 g, yield: 72%).
[LCMS]: 619
The same procedure as in Synthesis Example 14, with the exception of using 4-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)quinazoline instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.5 g, yield: 70%).
[LCMS]: 517
The same procedure as in Synthesis Example 14, with the exception of using 1-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.7 g, yield: 74%).
[LCMS]: 505
4-Chloro-2,9-diisopropyl-1,10-phenanthroline (6.15 g, 20.6 mmol), 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine (9.6 g, 20.6 mmol), Pd(OAc)2 (0.2 g, 1.0 mmol), Xphos (1.0 g, 2.1 mmol), and Cs2CO3 (13.5 g, 41.3 mmol) were added to a mixture of toluene (50 ml), EtOH (10 ml), and H2O (10 ml) and heated for 12 hours under reflux. After completion of the reaction, extraction was conducted with methylene chloride. The extract was added with MgSO4 and then filtered. The solvent was removed from the filtered organic layer which was then purified by column chromatography to afford the target compound (9.7 g, yield: 78%).
[LCMS]: 601
The same procedure as in Synthesis Example 27, with the exception of using 2-phenyl-4-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidin, was carried out to afford the target compound (9.7 g, yield: 78%).
[LCMS]: 601
The same procedure as in Synthesis Example 27, with the exception of using 2-phenyl-4-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzofuro[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidin, was carried out to afford the target compound (9.0 g, yield: 75%).
[LCMS]: 585
The same procedure as in Synthesis Example 27, with the exception of using 4-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidin, was carried out to afford the target compound (9.7 g, yield: 78%).
[LCMS]: 601
The same procedure as in Synthesis Example 27, with the exception of using 4-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidin, was carried out to afford the target compound (9.7 g, yield: 78%).
[LCMS]: 601
The same procedure as in Synthesis Example 27, with the exception of using 6,8-diphenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidin, was carried out to afford the target compound (8.8 g, yield: 70%).
[LCMS]: 610
The same procedure as in Synthesis Example 27, with the exception of using 6,8-diphenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidin, was carried out to afford the target compound (8.8 g, yield: 70%).
[LCMS]: 610
The same procedure as in Synthesis Example 27, with the exception of using 6-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidin, was carried out to afford the target compound (7.4 g, yield: 67%).
[LCMS]: 534
The same procedure as in Synthesis Example 27, with the exception of using 8-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidin, was carried out to afford the target compound (7.4 g, yield: 67).
[LCMS]: 534
The same procedure as in Synthesis Example 27, with the exception of using 2,3,5-triphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidin, was carried out to afford the target compound (8.6 g, yield: 65%).
[LCMS]: 647
The same procedure as in Synthesis Example 27, with the exception of using 2,3,5-triphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidin, was carried out to afford the target compound (8.6 g, yield: 65%).
[LCMS]: 647
The same procedure as in Synthesis Example 27, with the exception of using 4-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)quinazoline instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidin, was carried out to afford the target compound (7.1 g, yield: 63%).
[LCMS]: 545
The same procedure as in Synthesis Example 27, with the exception of using 1-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidin, was carried out to afford the target compound (7.1 g, yield: 65%).
[LCMS]: 533
2,9-Di-tert-butyl-4-chloro-1,10-phenanthroline (6.75 g, 20.6 mmol), 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine (9.6 g, 20.6 mmol), Pd(OAc)2 (0.2 g, 1.0 mmol), Xphos (1.0 g, 2.1 mmol), and Cs2CO3 (13.5 g, 41.3 mmol) were added to a mixture of toluene (50 ml), EtOH (10 ml), and H2O (10 ml) and heated for 12 hours under reflux. After completion of the reaction, extraction was conducted with methylene chloride. The extract was added with MgSO4 and then filtered. The solvent was removed from the filtered organic layer which was then purified by column chromatography to afford the target compound (8.3 g, yield: 64%).
[LCMS]: 629
The same procedure as in Synthesis Example 40, with the exception of using 2-phenyl-4-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidin instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.3 g, yield: 64%).
[LCMS]: 629
The same procedure as in Synthesis Example 40, with the exception of using XXX instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine 2-phenyl-4-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzofuro[3,2-d]pyrimidine was carried out to afford the target compound (8.1 g, yield: 64%).
[LCMS]: 613
The same procedure as in Synthesis Example 40, with the exception of using 4-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.3 g, yield: 64).
[LCMS]: 629
The same procedure as in Synthesis Example 40, with the exception of using 4-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.3 g, yield: 64%).
[LCMS]: 629
The same procedure as in Synthesis Example 40, with the exception of using 6,8-diphenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.0 g, yield: 61%).
[LCMS]: 638
The same procedure as in Synthesis Example 40, with the exception of using 6,8-diphenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.0 g, yield: 61%).
[LCMS]: 638
The same procedure as in Synthesis Example 40, with the exception of using 6-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.2 g, yield: 62%).
[LCMS]: 562
The same procedure as in Synthesis Example 40, with the exception of using 8-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.2 g, yield: 62%).
[LCMS]: 562
The same procedure as in Synthesis Example 40, with the exception of using 2,3,5-triphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.7 g, yield: 63%).
[LCMS]: 675
The same procedure as in Synthesis Example 40, with the exception of using 2,3,5-triphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (8.7 g, yield: 63%).
[LCMS]: 675
The same procedure as in Synthesis Example 40, with the exception of using 4-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)quinazoline instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.1 g, yield: 60%).
[LCMS]: 573
The same procedure as in Synthesis Example 40, with the exception of using 1-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.0 g, yield: 60%).
[LCMS]: 561
4-Chloro-2-ethyl-9-methyl-1,10-phenanthroline (5.3 g, 20.6 mmol), 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine (9.6 g, 20.6 mmol), Pd(OAc)2 (0.2 g, 1.0 mmol), Xphos (1.0 g, 2.1 mmol), and Cs2CO3 (13.5 g, 41.3 mmol) were added to a mixture of toluene (50 ml), EtOH (10 ml), and H2O (10 ml) and heated for 12 hours under reflux. After completion of the reaction, extraction was conducted with methylene chloride. The extract was added with MgSO4 and then filtered. The solvent was removed from the filtered organic layer which was then purified by column chromatography to afford the target compound (7.6 g, yield: 66%).
[LCMS]: 559
The same procedure as in Synthesis Example 53, with the exception of using 2-phenyl-4-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.6 g, yield: 66%).
[LCMS]: 559
The same procedure as in Synthesis Example 53, with the exception of using 2-phenyl-4-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzofuro[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.4 g, yield: 66%).
[LCMS]: 543
The same procedure as in Synthesis Example 53, with the exception of using 4-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.6 g, yield: 66%).
[LCMS]: 559
The same procedure as in Synthesis Example 53, with the exception of using 4-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.6 g, yield: 66%).
[LCMS]: 559
The same procedure as in Synthesis Example 53, with the exception of using 6,8-diphenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.5 g, yield: 64%).
[LCMS]: 568
The same procedure as in Synthesis Example 53, with the exception of using 6,8-diphenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.5 g, yield: 64%).
[LCMS]: 568
The same procedure as in Synthesis Example 53, with the exception of using 6-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (6.1 g, yield: 61%).
[LCMS]: 492
The same procedure as in Synthesis Example 53, with the exception of using 8-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (6.1 g, yield: 61%).
[LCMS]: 492
The same procedure as in Synthesis Example 53, with the exception of using 2,3,5-triphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.5 g, yield: 60%).
[LCMS]: 605
The same procedure as in Synthesis Example 53, with the exception of using 2,3,5-triphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.5 g, yield: 60%).
[LCMS]: 605
The same procedure as in Synthesis Example 53, with the exception of using 4-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)quinazoline instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (6.3 g, yield: 61%).
[LCMS]: 503
The same procedure as in Synthesis Example 53, with the exception of using 1-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (6.3 g, yield: 62%).
[LCMS]: 491
4-chloro-2-isopropyl-9-methyl-1,10-phenanthroline (5.6 g, 20.6 mmol), 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine (9.6 g, 20.6 mmol), Pd(OAc)2 (0.2 g, 1.0 mmol), Xphos (1.0 g, 2.1 mmol), Cs2CO3 (13.5 g, 41.3 mmol)
were added to a mixture of toluene (50 ml), EtOH (10 ml), and H2O (10 ml) and heated for 12 hours under reflux. After completion of the reaction, extraction was conducted with methylene chloride. The extract was added with MgSO4 and then filtered. The solvent was removed from the filtered organic layer which was then purified by column chromatography to afford the target compound (7.1 g, yield: 60%).
[LCMS]: 573
The same procedure as in Synthesis Example 66, with the exception of using 2-phenyl-4-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.1 g, yield: 60%).
[LCMS]: 573
The same procedure as in Synthesis Example 66, with the exception of using 2-phenyl-4-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzofuro[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (6.9 g, yield: 60%).
[LCMS]: 529
The same procedure as in Synthesis Example 66, with the exception of using 4-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.1 g, yield: 60%).
[LCMS]: 573
The same procedure as in Synthesis Example 66, with the exception of using 4-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.1 g, yield: 60%).
[LCMS]: 573
The same procedure as in Synthesis Example 66, with the exception of using 6,8-diphenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.1 g, yield: 59%).
[LCMS]: 582
The same procedure as in Synthesis Example 66, with the exception of using 6,8-diphenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.1 g, yield: 59%).
[LCMS]: 582
The same procedure as in Synthesis Example 66, with the exception of using 6-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (6.1 g, yield: 59%).
[LCMS]: 506
The same procedure as in Synthesis Example 66, with the exception of using 8-phenyl-2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,2,4]triazolo[1,5-a]pyridine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (6.1 g, yield: 59).
[LCMS]: 506
The same procedure as in Synthesis Example 66, with the exception of using 2,3,5-triphenyl-6-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.7 g, yield: 60%).
[LCMS]: 619
The same procedure as in Synthesis Example 66, with the exception of using 2,3,5-triphenyl-6-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyrazine instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (7.7 g, yield: 60%).
[LCMS]: 619
The same procedure as in Synthesis Example 66, with the exception of using 4-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)quinazoline instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (6.2 g, yield: 58%).
[LCMS]: 517
The same procedure as in Synthesis Example 66, with the exception of using 1-phenyl-2-(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1H-benzo[d]imidazole instead of 2-phenyl-4-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)benzo[4,5]thieno[3,2-d]pyrimidine, was carried out to afford the target compound (6.0 g, yield: 58%).
[LCMS]: 505
The compound synthesized in Synthesis Example 1 was subjected to highly pure sublimation purification by a typically known method, and then a blue organic EL device was fabricated as follows.
A glass substrate having a thin coat of indium tin oxide (ITO) 1,500 A thick was ultrasonically washed with distilled water. After completion of the washing with distilled water, the substrate was again washed a solvent such as isopropyl alcohol, acetone, methanol, etc., under ultrasonication, and dried. The substrate was cleansed with UV for 5 minutes in a UV ozone cleaner (Power sonic 405, Hwashin Tech) and then transferred to a vacuum evaporator.
DS-205 (Doosan Corporation Electronics, 80 nm)/NPB (15 nm)/ADN+5% DS-405 (Doosan Corporation Electronics, 30 nm)/Compound A-1 (30 nm)/LiF (1 nm)/Al (200 nm) were laminated in that order on the ITO transparent electrode prepared above, to fabricate an organic EL device. The structures of NPB and ADN are as follows.
Blue organic EL devices were fabricated in the same manner as in Example 1, with the exception that the compounds listed in Table 1, instead of Compound a-1, were used as respective electron transport layer materials.
Blue organic EL devices were fabricated in the same manner as in Example 1, with the exception that the following Compounds A to H, instead of Compound A-1, were used as respective electron transport layer materials.
The blue organic EL devices fabricated in Examples 1 to 78 and Comparative Examples 1 to 8 were measured for driving voltage, current efficiency, and light-emitting wavelength at a current density of 10 mA/cm2 and the measurements are summarized in Table 1, below.
As can be seen in Table 1, the blue EL devices (Examples 1 to 78) which employed the electron transport layers containing the compounds of the present disclosure in which the phenanthroline moiety has alkyl group substituents at positions 2 and 9 therein were improved in driving voltage and current efficiency, compared to those that employed the electron transport layers containing unsubstituted phenanthroline moieties (Comparative Examples 1-2) and phenanthroline moieties substituted with aryls (Comparative Examples 3-4). In addition, the compounds of the present disclosure used in Examples 1-78 are lower in sublimation temperature than the compounds bearing the phenanthroline moiety substituted with aryl groups (Compounds C and D), and thus can prevent the devices from being deteriorated when applied to the fabrication of the devices.
Furthermore, a more improvement was brought about in device characteristics by the compounds of the present disclosure in which the phenanthroline moiety has alkyl group substituents at positions 2 and 9 than compounds in which the phenanthroline moiety has alkyl group substituents at other positions. Meanwhile, compared to the devices of Comparative Examples 1 to 4 employing the compounds in which the phenanthroline moiety is unsubstituted or substituted with aryl groups (i.e., Compounds A-D), the device of Comparative Example 5 employing the compound in which the phenanthroline moiety has alkyl group substituents at positions 2 and 8 (i.e., Compound E), and the device of Comparative Example 6 employing the compound in which the phenanthroline moiety has alkyl group substituents at positions 2 and 6 (i.e., Compound F) exhibited slightly improved current efficiency, but the characteristics of the device were not significantly improved because the active sites unique to phenanthroline was not blocked. The data indicate that even if the compound contains a phenanthroline derivative having an alkyl group introduced thereinto, the thermal stability of the material can be maintained only when the alkyl group is substituted at positions 2 and 9, which are the active sites of phenanthroline.
In addition, the devices of Examples 1-78 employing the compounds of the present disclosure in which the phenanthroline moiety has alkyl group substituents at position 2 and 9 and a heteroaryl substituent (e.g., EWG) at position 4 were lower in driving voltage and higher in luminous efficiency than those of Comparative Examples 7-8 employing the compounds in which the phenanthroline moiety has alkyl group substituents at positions 2 and 9 and a heteroaryl substituent at a different position from position 4 (e.g., position 3 or 5). From these data, it was understood that even if the compounds have the phenanthroline moiety in which alkyl groups are substituted at both positions 2 and 9, the position where the electron withdrawing group (EWG) is introduced also has a great effect on device characteristics.
Compound A-1 synthesized in Synthesis Example 1 was subjected to highly pure sublimation purification by a typically known method, and then a blue organic EL device was fabricated as follows.
A glass substrate having a thin coat of indium tin oxide (ITO) 1,500 A thick was ultrasonically washed with distilled water. After completion of the washing with distilled water, the substrate was again washed a solvent such as isopropyl alcohol, acetone, methanol, etc., under ultrasonication, and dried. The substrate was cleansed with UV for 5 minutes in a UV ozone cleaner (Power sonic 405, Hwashin Tech) and then transferred to a vacuum evaporator.
DS-205 (Doosan Corporation Electronics, 80 nm)/NPB (15 nm)/ADN+5% DS-405 (Doosan Corporation Electronics, 30 nm)/Alq3 (30 nm)/Compound 1 (30 nm)/DS-505 (Doosan Corporation Electronics, 15 nm/NPB (15 nm)/CBP+10% (piq)2Ir(acac)(40 nm)/Alq3 (30 nm)/LiF (1 nm)/Al (200 nm) were laminated in that order on the ITO transparent electrode prepared above, to fabricate an organic EL device. The structures of NPB and ADN are as shown above, and the structures of Alq3, CBP, and (piq)2Ir(acac) are as follows.
Blue organic EL devices were fabricated in the same manner as in Example 79, with the exception that the compounds listed in Table 2, instead of Compound A-1, were used as respective N-type charge generation layer materials.
Blue organic EL devices were fabricated in the same manner as in Example 79, with the exception that the following Compounds A to H, instead of Compound 1, were used as respective N-type charge generation layer materials. Structures of Compounds A to H are as shown in Comparative Examples 1 to 8.
The blue organic EL devices fabricated in Examples 79 to 156 and Comparative Examples 9 to 16 were measured for driving voltage and current efficiency at a current density of 10 mA/cm2 and the measurements are summarized in Table 2, below.
As can be seen in Table 2, the blue EL devices (Examples 79-156) which employed N-type charge generation layers containing the compounds in which the phenanthroline moiety has alkyl groups as substituents at positions 2 and 9 were improved in driving voltage and current efficiency, compared to those that employed electron transport layers containing unsubstituted phenanthroline moieties (Comparative Examples 9-10) and phenanthroline moieties substituted with aryls (Comparative Examples 11-12). In addition. the compounds of the present disclosure used in Examples 79-156 are lower in sublimation temperature than the compounds bearing the phenanthroline moiety substituted with aryl groups (Compounds C and D), and thus can prevent the devices from being deteriorated when applied to the fabrication of the devices.
Furthermore, the devices of Examples 83-164 containing as N-type charge generation materials the compounds of the present disclosure in which the phenanthroline moiety has alkyl group substituents at positions 2 and 9 were observed to exhibit higher performance in terms of driving voltage and current efficiency, compared to those of Comparative Examples 13-14 using the compounds in which the phenanthroline moiety has alkyl group substituents at different positions. Meanwhile, compared to the devices of Comparative Examples 9 to 14 employing the compounds in which the phenanthroline moiety is unsubstituted or substituted with aryl groups, the device of Comparative Example 13 employing the compound in which the phenanthroline moiety has alkyl group substituents at positions 2 and 8 (i.e., Compound E), and the device of Comparative Example 14 employing the compound in which the phenanthroline moiety has alkyl group substituents at positions 2 and 6 (i.e., Compound F) exhibited slightly improved current efficiency, but the characteristics of the device were not significantly improved because the active sites unique to phenanthroline was not blocked. The data imply that even if the compound contains a phenanthroline derivative having an alkyl group introduced thereinto, the thermal stability of the material can be maintained only when the alkyl group is substituted at positions 2 and 9, which are the active sites.
In addition, the devices of Examples 79-156 employing the compounds of the present disclosure in which the phenanthroline moiety has alkyl group substituents at position 2 and 9 and an aryl substituent at position 4 were lower in driving voltage and higher in luminous efficiency than those of Comparative Examples 15-16 employing the compounds in which the phenanthroline moiety has alkyl group substituents at positions 2 and 9 and an aryl substituent at a different position from position 4 (e.g., position 3 or 5).
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2020-0081616 | Jul 2020 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2021/008425 | 7/2/2021 | WO |
