Patent Application
20180155312
The present invention relates to a novel compound and an organic electronic device using the same, more particularly to a novel compound as electron-transporters and an organic electronic device using the same.
With the advance of technology, various organic electronic devices that make use of organic materials have been energetically developed. Examples of organic electronic devices include organic light emitting devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors.
OLED was initially invented and proposed by Eastman Kodak Company through a vacuum evaporation method. Dr. Ching Tang and Steven VanSlyke of Kodak Company deposited an electron transport material such as tris(8-hydroxyquinoline)aluminum(III) (abbreviated as Alq3) on a transparent indium tin oxide glass (abbreviated as ITO glass) formed with a hole transport layer of organic aromatic diamine thereon, and subsequently deposited a metal electrode onto an electron transport layer to complete the fabrication of the OLED. OLEDs have attracted lots of attention due to their numerous advantages, such as fast response speed, light weight, compactness, wide viewing angle, high brightness, higher contrast ratio, no need of backlight, and low power consumption. However, the OLEDs still have the problems such as low efficiency and short lifetime.
To overcome the problem of low efficiency, one of the approaches is to interpose some interlayers between the cathode and the anode. With reference to
Another approach is to modify the materials of ETL for OLEDs to render the electron transport materials to exhibit hole-blocking ability. Examples of conventional electron transport materials include 3,3′-[5′-[3-(3-Pyridinyl)phenyl][1,1′:3′,1″-terphenyl]-3,3″-diyl]bispyridine (TmPyPb), 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene(TPBi), tris(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane(3TPYMB), 1,3-bis(3,5-dipyrid-3-yl-phenyl)benzene(BmPyPb), and 9,10-bis(3-(pyridin-3-yl)phenyl)anthracene(DPyPA).
However, even using the foresaid electron transport materials, the current efficiency of OLEDs still needs to be improved. Therefore, the present invention provides a novel compound to mitigate or obviate the problems in the prior art.
An objective of the present invention is to provide a novel compound useful for an organic electronic device.
Another objective of the present invention is to provide an organic electronic device using the novel compound, so as to improve the efficiency of the organic electronic device.
To achieve the foresaid objectives, the present invention provides a novel compound represented by the following Formula (I):
In formula (I), Y is an oxygen atom, a sulfur atom, or a sulfur dioxide group.
In formula (I), X1 and X2 are each independently C(Ra), the two (Ra)s are the same or different, and the two (Ra)s are joined together to form a first aryl ring.
In formula (I), X3 and X4 are each independently C(Rb), the two (Rb)s are the same or different, and the two (Rb)s are joined together to form a second aryl ring or a heteroaryl ring.
In formula (I), Z1 to Z12 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a trifluoromethyl group, a halogen group, a cyano group, a nitro group, an alkyl group having 1 to 40 carbon atoms, an alkenyl group having 2 to 40 carbon atoms, an alkynyl group having 2 to 40 carbon atoms, a cycloalkyl group having 3 to 60 ring carbon atoms, a heterocycloalkyl group having 3 to 60 ring carbon atoms, an aryl group having 6 to 60 ring carbon atoms, a heteroaryl group having 3 to 60 ring carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an aryloxy group having 6 to 60 ring carbon atom, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 60 ring carbon atoms, an alkylboron group having 1 to 40 carbon atoms, an arylboron group having 6 to 60 ring carbon atom, a phosphine group having 1 to 40 carbon atoms, and a phosphine oxide group having 1 to 40 carbon atoms.
In accordance with the present invention, the double bond between X1 and X2 in Formula (I) and the bonds between the two joined (Ra)s are conjugated and commonly construct the first aryl ring. Likely, the double bond between X3 and X4 in Formula (I) and the bonds between the two joined (Rb)s are conjugated and commonly construct the second aryl ring or the heteroaryl ring.
Preferably, the first aryl ring extended from X1 and X2 in Formula (I) and the second aryl ring extended from X3 and X4 in Formula (I) are each independently a substituted or unsubstituted 6 to 60-membered carbon ring, more preferably a substituted or unsubstituted 6 to 20-membered carbon ring. For example, the substituted or unsubstituted 6 to 60-membered carbon ring may be selected from the group consisting of: a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted pyrene ring, a substituted or unsubstituted fluoranthene ring, a substituted or unsubstituted benzofluoranthene ring, and a substituted or unsubstituted fluorene ring, but is not limited thereto. More preferably, the substituted or unsubstituted 6 to 60-membered carbon ring is a substituted or unsubstituted benzene structure, a substituted or unsubstituted naphthalene ring or a substituted or unsubstituted fluorene ring. The substitution group on the 6 to 20-membered carbon ring may be, but not limited to, a halogen group, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms.
Preferably, the heteroaryl ring extended from X3 and X4 in Formula (I) may contain at least one furan group or at least one thiophene group. For example, the heteroaryl ring may be, but not limited to, a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted dibenzothiophene ring, a substituted or unsubstituted dibenzothiophene sulfone ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted isobenzofuran ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted isobenzothiophene ring.
Preferably, Z1 to Z12 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 30 ring carbon atoms, a heterocycloalkyl group having 3 to 30 ring carbon atoms, an aryl group having 6 to 30 ring carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 30 ring carbon atoms, an alkylsilyl group having 1 to 12 carbon atoms, an arylsilyl group having 6 to 30 ring carbon atoms, an alkylboron group having 1 to 12 carbon atoms, an arylboron group having 6 to 30 ring carbon atoms, a phosphine group having 1 to 12 carbon atoms, and a phosphine oxide group having 1 to 12 carbon atoms.
In a case that Y is an oxygen atom, the compound may be, for example, represented by any one of the following Formulae:
In a case that Y is a sulfur atom, the compound may be, for example, represented by any one of the following Formulae:
In a case that Y is a sulfur dioxide group, the compound is represented by any one of the following Formulae:
In accordance with the present invention, the foresaid A1 and A2 are each independently C(Rc), the two (Rc)s are the same or different. The two (Rc)s are joined together to form an aromatic structure contained in the second aryl ring or the heteroaryl ring.
In accordance with the present invention, each of the foresaid Z13 is selected from the group consisting of: a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a phenyl group.
Preferably, the aromatic structure formed by the two (Rc)s may be a substituted or unsubstituted 6 to 20-membered carbon aromatic cyclic structure, for example, but not limited to, a substituted or unsubstituted benzene structure, a substituted or unsubstituted naphthalene structure, a substituted or unsubstituted anthracene structure, a substituted or unsubstituted phenanthrene structure, a substituted or unsubstituted pyrene structure, a substituted or unsubstituted fluoranthene structure, a substituted or unsubstituted benzofluoranthene structure, or a substituted or unsubstituted fluorene structure. The substitution group on the 6 to 20-membered carbon aromatic cyclic structure may be, but not limited to, a halogen group, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
Preferably, at least one of Z1 to Z8 in any one of formulae may be selected from the group consisting of: an alkyl group having 1 to 40 carbon atoms and substituted with at least one functional group, an alkenyl group having 2 to 40 carbon atoms and substituted with at least one functional group, an alkynyl group having 2 to 40 carbon atoms and substituted with at least one functional group, a cycloalkyl group having 3 to 60 ring carbon atoms and substituted with at least one functional group, a heterocycloalkyl group having 3 to 60 ring carbon atoms and substituted with at least one functional group, an aryl group having 6 to 60 ring carbon atoms and substituted with at least one functional group, a heteroaryl group having 3 to 60 ring carbon atoms containing at least one nitrogen atom, an alkoxy group having 1 to 40 carbon atoms and substituted with at least one functional group, an aryloxy group having 6 to 60 ring carbon atoms and substituted with at least one functional group, an alkylsilyl group having 1 to 40 carbon atoms and substituted with at least one functional group, an arylsilyl group having 6 to 60 ring carbon atoms and substituted with at least one functional group, an alkylboron group having 1 to 40 carbon atoms and substituted with at least one functional group, an arylboron group having 6 to 60 ring carbon atoms, a phosphine group having 1 to 40 carbon atoms and substituted with at least one functional group, and a phosphine oxide group having 1 to 40 carbon atoms and substituted with at least one functional group; and the other of Z1 to Z8 in any one of foresaid formulae may be a hydrogen atom, a deuterium atom, or any other substitution groups as mentioned in the specification. Said functional group is selected from the group consisting of: a cyano group, a nitro group, a fluoro group, and a chloro group.
More specifically, at least one of Z1 to Z8 in any one of foresaid formulae may be a specific aromatic substitution. The specific aromatic substitution may be selected from the group consisting of:
wherein R1 to R7 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 30 ring carbon atoms, a heterocycloalkyl group having 3 to 30 ring carbon atoms, an aryl group having 6 to 30 ring carbon atoms, a heteroaryl group having 3 to 20 ring carbon atoms, an alkoxy group having 1 to 40 carbon atoms, an aryloxy group having 6 to 30 ring carbon atoms, an alkylsilyl group having 1 to 40 carbon atoms, an arylsilyl group having 6 to 30 ring carbon atoms, an alkylboron group having 1 to 40 carbon atoms, an arylboron group having 6 to 30 ring carbon atoms, a phosphine group having 1 to 30 carbon atoms, and a phosphine oxide group having 1 to 30 carbon atoms;
wherein n is a positive integral from 0 to 4, m is a positive integral from 0 to 3, o is a positive integral from 0 to 3, and the total of m and o is not more than 5.
Preferably, R1 to R3 each may independently be, for example, but not limited to, phenyl group, pyridine group, pyrimidine group, pyrazine group, pyridazine group, phenylpyridine group, phenylpyrimidine group, phenylpyrazine group, or phenylpyridazine group.
In an embodiment, at least one of Z1 to Z8 in any one of foresaid formulae may preferably be
wherein R1 may be pyridinyl group or cyanophenyl group, and R2 and R3 may be any substitution group as stated above.
In another embodiment, at least one of Z1 to Z8 in any one of foresaid formulae may preferably be
wherein R2 may be pyridinyl group or cyanophenyl group, and R1 and R3 may be any substitution group as stated above.
In further another embodiment, at least one of Z1, Z2, Z3, Z6, Z7, and Z8 in any one of foresaid formulae may be a substituted triazine group with two phenyl groups, two pyridine groups, two pyrimidine groups, two pyrazine groups, two pyridazine groups, two phenylpyridine groups, two phenylpyrimidine groups, two phenylpyrazine groups, or two phenylpyridazine groups.
Preferably, at least one of Z1, Z2, Z3, Z6, Z7, and Z8 in any one of foresaid formulae may be the specific aromatic substitution as stated above, and Z4 and Z5 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an alkynyl group having 2 to 12 carbon atoms. Or, at least one of Z2, Z3, Z6, and Z7 in any one of foresaid formulae may be the specific aromatic substitution as stated above, and Z1, Z4, Z5, Z8 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an alkynyl group having 2 to 12 carbon atoms.
Preferably, at least one of Z2, Z3, Z6, and Z7 in any one of foresaid formulae is selected from the group consisting of:
Preferably, at least one of Z1, Z2, Z3, Z6, Z7, and Z8 in any one of foresaid formulae may be the specific aromatic substitution as stated above, and Z4 and Z5 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an alkynyl group having 2 to 12 carbon atoms.
Preferably, Z9 to Z12 in Formula (I) are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an alkynyl group having 2 to 12 carbon atoms.
In accordance with the present invention, Z1 and Z8 may be the same or different. In accordance with the present invention, Z2 and Z7 may be the same or different. In accordance with the present invention, Z3 and Z6 may be the same or different. In one embodiment, any two of Z1, Z2, Z3, Z6, Z7, and Z8 may be the same substitution as stated above, and the others of Z1, Z2, Z3, Z6, Z7, and Z8 may be a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms.
For example, Z1, Z4 to Z8 are each independently a hydrogen atom or a deuterium atom, and Z2 and/or Z3 may be a specific aromatic substitution. Or, Z1, Z2, Z4, Z5, Z7, and Z8 are each independently a hydrogen atom or a deuterium atom, and Z3 and Z6 are both the above specific aromatic substitutions.
For example, the compound may be selected from the group consisting of:
The present invention also provides an organic electronic device, comprising a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode. The organic layer comprises the novel compound as described above.
Preferably, the organic electronic device is an organic light emitting device (OLED). More preferably, the novel compound of the present invention may be used as an electron transport material or a hole blocking layer.
Specifically, the organic light emitting device may comprise:
a hole injection layer formed on the first electrode;
a hole transport layer formed on the hole injection layer;
an emission layer formed on the hole transport layer;
an electron transport layer formed on the emission layer;
an electron injection layer formed between the electron transport layer and the second electrode.
In one embodiment, the organic layer may be the electron transport layer, i.e., the electron transport layer comprises the novel compound as stated above.
Preferably, the hole injection layer may be a two-layered structure, i.e., the OLED comprises a first hole injection layer and a second hole injection layer disposed between the first electrode and the hole transport layer.
Preferably, the hole transport layer may be a two-layered structure, i.e., the OLED comprises a first hole transport layer and a second hole transport layer disposed between the two-layered hole injection layer and the emission layer.
Preferably, the electron transport layer is made of the novel compound such as Compounds I to CCCIV. The OLEDs using the novel compound as the electron transport material can have an improved efficiency compared to commercial OLEDs using known electron transport material, such as 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole; bis(2-methyl-8quinolinolato)(p-phenylphenolato) aluminum; and 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD), as the electron transport material.
Preferably, the OLED comprises a hole blocking layer formed between the electron transport layer and the emission layer, to block holes overflow from the emission layer to the electron transport layer. Said hole blocking layer may be made of the foresaid novel compound, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) or 2,3,5,6-tetramethyl-phenyl-1,4-(bis-phthalimide) (TMPP), but not limited thereto. In another embodiment, the organic layer may be the hole blocking layer, i.e., the hole blocking layer comprises the novel compound as stated above.
Preferably, the OLED comprises an electron blocking layer formed between the hole transport layer and the emission layer, to block electrons overflow from the emission layer to the hole transport layer. Said electron blocking layer may be made of 9,9′-[1,1′-biphenyl]-4,4′-diylbis-9H-carbazole (CBP) or 4,4′,4″-tri(N-carbazolyl)-triphenylamine (TCTA), but not limited thereto.
In the presence of such a hole blocking layer and/or an electron blocking layer in an OLED, the OLED has a higher luminous efficiency compared to a typical OLED.
Said first and second hole transport layers may be made of, for example, but not limited to: N1,N1′-(biphenyl-4,4′-diyl)bis(N1-(naphthalen-1-yl)-N4,N4′-diphenylbenzene-1,4-diamine); or N4,N4′-di(naphthalen-1-yl)-N4,N4′-diphenylbiphenyl-4,4′-diamine (NPB).
Said first and second hole injection layers may be made of, for example, but not limited to, polyaniline or polyethylenedioxythiophene.
Said emission layer can be made of an emission material including a host and a dopant. The host of the emission material is, for example, but not limited to, 9-(4-(naphthalen-1-yl)phenyl)-10-(naphthalen-2-yl) anthracene.
For red OLEDs, the dopant of the emission material is, for example, but not limited to: organometallic compounds of iridium (II) having perylene ligands, fluoranthene ligands or periflanthene ligands. For green OLEDs, the dopant of the emission material is, for example, but not limited to: diaminofluorenes; diaminoanthracenes; or organometallic compounds of iridium (II) having phenylpyridine ligands. For blue OLEDs, the dopant of the emission material is, for example, but not limited to: diaminofluorenes; diaminoanthracenes; diaminopyrenes; or organicmetallic compounds of iridium (II) having phenylpyridine ligands. With various host materials of the emission layer, the OLED can emit lights in red, green or blue.
Said electron injection layer may be made of an electron injection material, for example, but not limited to (8-oxidonaphthalen-1-yl)lithium(II).
Said first electrode is, for example, but not limited to, an indium-doped tin oxide electrode.
Said second electrode has a work function lower than that of the first electrode. The second electrode is, for example, but not limited to, an aluminum electrode, an indium electrode, or a magnesium electrode.
Other objectives, advantages and novel features of the invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.
Hereinafter, one skilled in the arts can easily realize the advantages and effects of a novel compound and an organic light emitting device using the same in accordance with the present invention from the following examples. It should be understood that the descriptions proposed herein are just preferable examples only for the purpose of illustrations, not intended to limit the scope of the invention. Various modifications and variations could be made in order to practice or apply the present invention without departing from the spirit and scope of the invention.
Synthesis of Intermediate A1
Intermediate A1 used for preparing a novel compound was synthesized by the following steps. The synthesis pathway of the Intermediate A1 was summarized in Scheme A1.
Step 1: Synthesis of Intermediate A1-1
A mixture of 3-bromodibenzo[a,d]cyclohepten-5-one (86 g, 1.0 eq), N-bromosuccinimide (NBS) (106 g, 2 eq), benzyl peroxide (0.7 g, 0.01 eq) in carbon tetrachloride (CCl4) (5 times of starting material) was heated to 85° C. The reaction progress was monitored by high performance liquid chromatography (HPLC). After completion of the reaction, the precipitate was separated by filtration and washed with CH3OH, which was then purified by recrystallization. The purified product was concentrated to dryness, whereby white solid products were obtained in an amount of 123 g and a yield of 92.3%.
The solid product was identified as Intermediate A1-1 by a field desorption mass spectroscopy (FD-MS) analysis. FD-MS analysis: C15H9Br3O: theoretical value of 444.94 and observed value of 444.94.
Step 2: Synthesis of Intermediate A1-2
The obtained Intermediate A1-1 (116.0 g, 1.0 eq) was dissolved in 960 ml of THF (1.0 M), and the reaction was cooled to 0° C. and then treated with potassium tert-butoxide (K-OtBu) (87.8 g, 3.0 eq). The reaction was allowed to stir at 0° C. for 1 hour, and then stirred at room temperature for additional 12 hours. After completion of the reaction, the reaction was quenched by DI water and the organic layer was recovered by solvent extraction operation and dried over sodium sulfate. The solvent was removed from the organic layer by distillation under reduced pressure, and the resulting residue was purified by silica gel column chromatography. The purified product was concentrated to dryness, whereby a light yellow solid product was obtained in a yield of 60.3%.
The solid product was identified as Intermediate A1-2 by FD-MS analysis. FD-MS analysis C19H11BrO2: theoretical value of 351.19 and observed value of 351.19.
Step 3: Synthesis of Intermediate A1-3
A suspension of Intermediate A1-2 (1.0 eq) and 5% Pd/C (0.025 eq) in ethyl acetate (EA, 2.0 M) was stirred for 3 hours to 6 hours under a hydrogen atmosphere (H2) provided by a balloon of hydrogen. The resulting mixture was filtered through a pad of celite and washed with EA, and the filtrate was concentrated under reduced pressure to obtain 100 g (100%) of a yellow solid product.
The solid product was identified as Intermediate A1-3 by FD-MS analysis. FD-MS analysis C19H13BrO2: theoretical value of 353.21 and observed value of 353.21. The intermediate A1-3 can be directly used in the following step without further purification.
Step 4: Synthesis of Intermediate A1-4
Intermediate A1-3 (53 g, 1.0 eq) and p-toluenesulfonic acid (PTSA) (2.0 eq) in 530 ml of toluene was heated to reflux for 12 hours. The reaction mixture was cooled to room temperature and then quenched with a saturated aqueous solution of NaHCO3 and extracted with CH2Cl2. The organic layer was washed with water, brine and dried with anhydrous Na2SO4 subsequently. Then the resulting solution was concentrated under reduced pressure and purified by column chromatography on silica gel with CH2Cl2/hexane 1/1 (v/v) as eluent, whereby a light yellow solid product was obtained in an amount of 46.0 g and a yield of 91.5%.
The solid product was identified as Intermediate A1 by FD-MS analysis. FD-MS analysis C19H11BrO: theoretical value of 335.19 and observed value of 335.19.
Synthesis of Intermediate A2
Intermediate A2 used for preparing a novel compound was synthesized in a similar manner as Intermediate A1 through steps 1 to 4, except that the starting material 3-bromodibenzo[a,d]cyclohepten-5-one was replaced by 2-bromodibenzo[a,d]cyclohepten-5-one (CAS No. 198707-82-3). The synthesis pathway of Intermediate A2 was summarized in Scheme A2. All intermediates were analyzed according to the methods as described above, and the results were listed in Table 1.
Synthesis of Intermediate A3
Intermediate A3 used for preparing a novel compound was synthesized in a similar manner as Intermediate A1 through steps 1 to 4, except that the starting material 3-bromodibenzo[a,d]cyclohepten-5-one was replaced by 3,7-dibromodibenzo[a, d]cyclohepten-5-one (CAS No. 226946-20-9). The synthesis pathway of Intermediate A3 was summarized in Scheme A3. All intermediates were analyzed as described above, and the results were listed in Table 1.
Modifications of Intermediates A1 to A3
In addition to the Intermediates A1 to A3, one person skilled in the art can adopt other starting materials and successfully synthesize other desired intermediates through a reaction mechanism similar to Schemes A1 to A3. Applicable modifications of Intermediates A1 to A3 may be, for example, but not limited to, Intermediates A4 to A15 as follows.
Synthesis of Intermediates B1 to B4
Intermediates B1 to B4 were synthesized by reacting 1-fluoro-2-nitrobenzene and phenol derivative. A general synthesis pathway for Intermediate Bn was summarized in Scheme B-1. In the following Scheme B-1, “Reactant An” may be any one of Reactants A1 to A4 as listed in Table 2-1, and “Intermediate Bn” may be any one of Intermediates B1 to B4.
According to the Scheme B-1, each of Intermediates B1 to B4 was synthesized by the steps 1 to 3 as follows.
Step 1: Synthesis of Intermediate Bn-1
The mixture of Ar1—OH (referred Reactant An, 1 eq.), 1-fluoro-2-nitrobenzene (50 g, 1 eq.), and Cs2CO3 (230.9 g, 2 eq.) in DMF (2080 ml, 0.17M) was stirred at 90° C. under an argon atmosphere. After the completion of the reaction, DMF was distilled out. The residue was quenched with water, extracted with EA and dried over magnesium sulfate, followed by concentration under reduced pressure after filtration. The crude mixture was purified by silica-gel column chromatography, and then identified as Intermediate Bn-1 by FD-MS analysis. Take Intermediate B1-1 as an example, FD-MS analysis: C12H9NO3: theoretical value of 215.2 and observed value of 215.2.
Step 2: Synthesis of Intermediate Bn-2
The mixture of intermediate Bn-1 (1 eq.), 5% Pd/C(10 g, 0.015 eq) in EtOH (680 ml, 0.5M) was stirred at 70° C. Hydrazine monohydrate (31.6 g, 2 eq.) was then slowly added to the mixture. After the completion of the reaction, the solution was filtered through a pad of Celite, followed by concentration under reduced pressure to obtain intermediate Bn-2. The product was identified as intermediate B1-2 by FD-MS analysis. Take Intermediate B1-2 as an example, FD-MS analysis: C12H11NO: theoretical value of 185.22 and observed value of 185.22.
Step 3: Synthesis of Intermediate Bn
The mixture of intermediate Bn-2 (1 eq.), PTSA*H2O (172.5 g, 3 eq) in Acetonitrile (224 ml, 1.3 M) was cooled to 5° C. using a ice bath. NaNO2 (41.7 g, 2 eq.) in 240 ml water was added dropwise. After the addition was finished, the mixture was kept at 5° C. for 1 hr. The resulting diazonium salt was treated slowly with KI (100 g, 2 eq.) in 300 ml water. After the completion of the reaction, the residue was extracted with EtOAc and the combined organic layer was washed with a 10% Na2SO3(aq) and then dried over Na2SO4. The organic layer was concentrated under reduced pressure after filtration. The crude mixture was purified by silica-gel column chromatography to obtain intermediate Bn.
The chemical structure of Ar1—OH used for synthesizing Intermediate B1 n, i.e., Intermediates B1 to B4, the yield, and the chemical structures of the products obtained in steps 1 to 3 were listed in Table 2-1. All Intermediate Bn, including Intermediates B1 to B4, were analyzed by FD-MS, and the results were listed in Table 2-1.
Reactant A1
Intermediate B1-1
Intermediate B1-2
Intermediate B1
Reactant A2
Intermediate B2-1
Intermediate B2-2
Intermediate B2
Reactant A3
Intermediate B3-1
Intermediate B3-2
Intermediate B3
Reactant A4
Intermediate B4-1
Intermediate B4-2
Intermediate B4
Synthesis of Intermediate B5 and B6
Unlike Intermediates B1 to B4, Intermediates B5 and B6 were synthesized by reacting 2-bromobenzenethiol and aryl iodide. Another general synthesis pathway for Intermediate Bn was summarized in Scheme B-2. In the following Scheme B-2, “Reactant An” may be any one of Reactants A5 and A6 as listed in Table 2-2 or the like, and “Intermediate Bn” may be any one of Intermediates B5 and B6.
According to the Scheme B-2, a mixture of Pd2(dba)3(0.5% eq), DPEphos (0.01 eq), and NaOt-Bu (1.5 eq) were added to a screw-cap vial followed by toluene and a stir bar. Iodobenzene (1.0 eq) and 2-bromobenzenethiol (1.05 eq) were added. The vial was sealed and the mixture stirred at 100° C. for 1 h. The crude mixture was filtered through a pad of Celite and the filtrate was concentrated. The residue was purified by filtration through a short column of silica gel and eluted with heptane to give Intermediate Bn.
The chemical structure of I—Ar1 used for synthesizing Intermediate Bn, i.e., Intermediates B5 to B6, the chemical structures of the Intermediate Bn, and the yield were listed in Table 2-2. All Intermediate Bn, including Intermediates B5 to B6, were analyzed by FD-MS, and the results were listed in Table 2-2.
Reactant A5
Intermediate B5
Reactant A6
Intermediate B6
Modifications of Intermediates B1 to B4
In addition to the Intermediates B1 to B4, one person skilled in the art can adopt any halonitrobenzenes other than 1-fluoro-2-nitrobenzene and any phenol derivative other than Reactants A1 to A4 to successfully synthesize other desired Intermediate Bn through a reaction mechanism similar to Scheme B-1. Applicable modifications of Intermediates B1 to B4 may be, for example, but not limited to, Intermediates B7 to B18 as follows.
Modifications of Intermediates B5 and B6
In addition to the Intermediates B5 and B6, one person skilled in the art can adopt any halobenzenethiol other than 2-bromonzenethiol and any aryl iodide other than Reactants A5 and A6 to successfully synthesize other desired Intermediate Bn through a reaction mechanism similar to Scheme B-2. Applicable modifications of Intermediates B5 and B6 may be, for example, but not limited to, Intermediates B19 to B34 as follows.
Synthesis of Intermediate Cn
The foresaid Intermediates B1 to B34, especially Intermediates B1 to B6, could be further adopted to synthesize Intermediate Cn. A general synthesis pathway for Intermediate Cn was summarized in Scheme C-1. In the following Scheme C-1, “Intermediate An” may be any one of foresaid Intermediates A1 to A15 or the like, “Intermediate Bn” may be any one of foresaid Intermediates B1 to B34 or the like, and “Intermediate Cn” may be any one of Intermediates C1 to C12 as listed in Table 3-1 or the like. Intermediates C1 to C12 were each synthesized by the following steps.
Step 1: Synthesis of Alcohol Intermediate
Intermediate Bn (1.0 eq) was dissolved in 120 mL of anhydrous THF (0.4M), and cooled to −78° C. n-Butyllithium (n-BuLi)(2.5 M, 1.0 eq) was slowly added to the above cooled solution, and the reaction mass was stirred for 1 h. After 1 h of stirring, Intermediate An (0.7 eq) was added to the reaction solution and stirred for additional 3 h at normal temperature. After the completion of the reaction, it was quenched by saturated solution of ammonium chloride, and extracted with organic solvent. The organic layer was separated, concentrated, and recrystallized with petroleum ether to obtain a white solid product.
The white solid product was analyzed by FD-MS, and the result was listed in Table 3-1. The chemical structures of Intermediates Cn-1 were listed in Table 3-1.
Step 2: Synthesis of Intermediate Cn
The foresaid Intermediate Cn-1 (1.0 eq), acetic acid (w/v=1/3 to the reactant) and H2SO4 (5 drops) were mixed, and then stirred at 110° C. for 6 h. The solvent was then removed under reduced pressure, and the residue was purified with column chromatography. The residual mass was recrystallized with toluene to obtain a white solid product.
The solid product was identified by FD-MS analysis. The chemical structures, yields, formulae, and mass analyzed by FD-MS of Intermediates C1 to C12 were listed in Table 3-1.
Intermediate C1-1/ C31H21BrO2/ 505.40
Intermediate C1/ C31H19BrO/ 487.39
Intermediate C2-1
Intermediate C2
Intermediate C3-1
Intermediate C3/ C31H18Br2O/ 566.28
Intermediate C4-1
Intermediate C4
Intermediate C5-1
Intermediate C5/ C35H20Br2O/ 616.34
Intermediate C6-1
Intermediate C6
Intermediate C7-1
Intermediate C7 C40H27BrO/ 603.55
Intermediate C8-1
Intermediate C8 C40H26Br2O/ 682.44
Intermediate C9-1
Intermediate C9/ C31H19BrS/ 503.45
Intermediate C10-1
Intermediate C10
Intermediate C11-1
Intermediate C11
Intermediate C12-1
Intermediate C12/ C35H20Br2S/ 632.41
Synthesis of Intermediate C13
The foresaid Intermediates C9 to C12 could be further oxidized to synthesize other Intermediate Cn. Take Intermediate C9 as an example, the Intermediate C9 could be oxidized into Intermediate C13 by a method of Scheme C-2.
A mixture of Intermediate C9 (20 g, 1.0 eq) and 30% aqueous hydrogen peroxide (7.0 eq) in HOAc (250 ml) was heated at 100° C. for 8 h under nitrogen atmosphere. After the completion of the reaction, the reaction mixture was washed with water, followed by filtered to get solid crude mixture. The crude mixture was purified by silica-gel column chromatography to obtain Intermediate C13 in a yield of 85.3%.
The solid product was identified as intermediate C13 by FD-MS analysis. FD-MS analysis: C31H19BrO2S: theoretical value of 535.45 and observed value of 535.45
Synthesis of Intermediate C14
Intermediates C14 was synthesized in a similar manner as Intermediate C13, except that the Intermediate C9 was replaced by Intermediate C10.
Modifications of Intermediates C1 to C12
In addition to the Intermediates C1 to C12, one person skilled in the art can adopt any intermediate An other than Intermediates A1 to A3 and any Intermediate Bn other than Intermediates B1 to B6 to successfully synthesize other desired Intermediate Cn through a reaction mechanism similar to Scheme C-1. Applicable modifications of Intermediates C1 to C12 may be, for example, but not limited to, Intermediates C15 to C46 as follows.
Modifications of Intermediates C13 and C14
In addition to the Intermediates C13 and C14, one person skilled in the art can adopt other Intermediate Cn, such as Intermediates C9 to C12, C31 to C46 to synthesize other desired Intermediate Cn through a reaction mechanism similar to Scheme C-2 or Scheme C-3. Applicable modifications of Intermediates C13 and C14 may be, for example, but not limited to, Intermediates C47 to C58 as follows.
Synthesis of Intermediate Cn-B
The foresaid Intermediate Cn could be further modified into an Intermediate Cn-B through Miyaura borylation reaction. “Intermediate Cn-B” was directed to a compound derived from Intermediate Cn whose bromo group was replaced by (pinacolato)boron group. A synthesis pathway of Intermediate Cn-B was summarized in Scheme C1-B. Intermediate Cn-B was synthesized by the following steps.
A mixture of bis(pinacolato)diboron (1.2 eq), Intermediate Cn (1.0 eq), 1,1-bis(diphenylphosphino)-ferrocene dichloropalladium (II) (PdCl2(dppf)) (0.015 eq), and potassium acetate (KOAc) (3.0 eq) in 1,4-dioxane (0.3 M) was stirred at 110° C. for 8 hours under nitrogen atmosphere. After cooling to room temperature, the solvent was then removed under reduced pressure, and the residue was purified via column chromatography to obtain a pale yellow solid product.
The pale yellow solid product was identified by FD-MS analysis. The chemical structures, yields, formulae, and mass analyzed by FD-MS of Intermediates Cn-B were listed in Table 3-2.
Intermediate C1
Intermediate C1-B
Intermediate C2
Intermediate C2-B
Intermediate C4
Intermediate C4-B
Intermediate C6
Intermediate C6-B
Intermediate C9
Intermediate C9-B
Intermediate C10
Intermediate C10-B
Intermediate C11
Intermediate C11-B
Intermediate C13
Intermediate C13-B
Intermediate C14
Intermediate C14-B
Modifications of Intermediate Cn-B
In addition to the Intermediate Cn-B, one person skilled in the art can adopt any one of foresaid Intermediates Cn to undergo a Miyaura borylation reaction to successfully synthesize other desired Intermediate Cn-B.
Synthesis of Novel Compounds
Each of the foresaid Intermediates Cn and Cn-B could be reacted with various reactants to synthesis various claimed novel compounds. The general synthesis pathway of the claimed novel compound was summarized in Scheme I. In the following Scheme I, “Reactant B” may be any one of Reactants B1 to B11 as listed in Table 4, and “Intermediate C” may be any one of the foresaid Intermediates Cn and Cn-B or the like. The compounds were each synthesized by the following steps.
A mixture of Intermediate Cn or CnB (1.0 eq), Pd(OAc)2(0.01 eq), P(Cy)2(2-biphenyl) 0.04 eq), toluene/ethanol (0.5M, v/v=10/1), 3.0 M potassium carbonate solution, and Reactant B (2.1 eq) was stirred at 100° C. for 12 h under nitrogen atmosphere. After the completion of the reaction, water and toluene were added to the reaction mass. Subsequently, the organic layer was recovered by solvent extraction operation and dried over sodium sulfate. The solvent was then removed from the organic layer under reduced pressure, and the resulting residue was purified by silica gel column chromatography. The obtained residue was recrystallized with toluene to obtain white solid as claimed novel compound.
Reactant B and Intermediate Cn or CnB adopted to synthesize Compounds I to XXVI were listed in Table 5. Compounds I to XXVI were identified by H1-NMR and FD-MS, and the chemical structure, yield, formula and mass of each of Compounds I to XXVI were also listed in Table 5. According to
Compound I
Compound II
Compound III
Compound IV
Compound V
Compound VI
Compound VII
Compound VIII
Compound IX
Compound X
Compound XI
Compound XII
Compound XIII
Compound XIV
Compound XV
Compound XVI
Compound XVII
Compound XVIII
Compound XIX
Compound XX
Compound XXI
Compound XXII
Compound XXIII
Compound XXIV
Compound XXV
Compound XXVI
Modifications of Compounds I to XXVI
In addition to the Compounds I to XXVI, one person skilled in the art can react any Intermediate C, i.e., the foresaid Intermediate Cn or Cn-B, with any Reactant B through a reaction mechanism similar to Scheme I to synthesize other desired claimed novel compounds.
Preparation of OLED Devices
A glass substrate coated with an ITO layer (abbreviated as ITO substrate) in a thickness of 1500 Å was placed in distilled water containing a detergent dissolved therein, and was ultrasonically washed. The detergent was a product manufactured by Fischer Co., and the distilled water was distilled water filtered twice through a filter (Millipore Co.). After the ITO layer had been washed for 30 minutes, it was ultrasonically washed twice with distilled water for 10 minutes. After the completion of washing, the glass substrate was ultrasonically washed with isopropyl alcohol, acetone and methanol solvents and then dried, after which it was transported to a plasma cleaner. Then the substrate was cleaned with oxygen plasma for 5 minutes, and then transferred to a vacuum evaporator.
After that, various organic materials and metal materials were sequentially deposited on the ITO substrate to obtain the OLED device of Examples 1 to 33. The vacuum degree during the deposition was maintained at 1×10−6 to 3×10−7 torr. Herein, the ITO substrate was deposited with a first hole injection layer (HIL-1), a second hole injection layer (HIL-2), a first hole transporting layer (HTL-1), a second hole transporting layer (HTL-2), a blue/green/red emission layer (BEL/GEL/REL), an electron transporting layer (ETL), an electron injection layer (EIL), and a cathode (Cthd).
Herein, HAT was a material for forming HIL-1 and was a dopant for forming HIL-2; HI-2 was a material for forming HIL-2; HT-1 and HT-2 were materials for forming HTL-1 and HTL-2; conventional ET and novel compounds of the present invention were materials for forming ETL; Liq was a dopant for forming ETL and a material for forming EIL. RH/GH/BH were host material for forming REL/GEL/BEL, and RD/GD/BD were dopants for forming REL/GEL/BEL. The main difference of the OLEDs between Example and Comparative Example was that the ETL of OLED in following comparative examples was made of BCP but the ETL of OLED in following examples was made of the novel compounds of the present invention were listed in Table 5. The detailed chemical structures of foresaid commercial materials were listed in Table 6.
Preparation of Red OLED Devices
To prepare the red OLED device, multiple organic layers were respectively deposited on the ITO substrate according to the sequence as listed in Table 7, and the materials and the thicknesses of the organic layers in red OLED devices were also listed in Table 7.
Preparation of Green OLED Devices
To prepare the green OLED device, multiple organic layers were respectively deposited on the ITO substrate according to the sequence as listed in Table 8, and the materials and the thicknesses of the organic layers in green OLED devices were also listed in Table 8.
Preparation of Blue OLED Devices
To prepare the blue OLED device, multiple organic layers were respectively deposited on the ITO substrate according to the sequence as listed in Table 9, and the materials and the thicknesses of the organic layers in blue OLED devices were also listed in Table 9.
Performance of OLED Device
To evaluate the performance of OLED devices, red, green, and blue OLED devices were measured by PR650 as photometer and Keithley 2400 as power supply. Color coordinates (x,y) were determined according to the CIE chromaticity scale (Commission Internationale de L'Eclairage, 1931). The results were shown in Table 10. For the blue and red OLED devices, the data were collected at 1000 nits. For the green OLED devices, the data were collected at 3000 nits.
The materials of ETL, color and data of CIE, driving voltage, current efficiency, and external quantum efficiency (EQE) of Examples 1 to 33 and Comparative Examples 1 to 3 were listed in Table 10.
Based on the results, in comparison with the commercial electron transport material, adopting Compounds I to XXVI as the electron transport material can reduce the driving voltage and improve the current efficiency and the external quantum efficiency of the red, green, or blue OLEDs. It demonstrated that the novel compound of the present invention is suitable as an electron transport material for any color OLEDs, and allows the OLEDs using the same to have low driving voltage and improved current efficiency as well as improved external quantum efficiency.
Even though numerous characteristics and advantages of the present invention have been set forth in the foregoing description, together with details of the structure and features of the invention, the disclosure is illustrative only. Changes may be made in the details, especially in matters of shape, size, and arrangement of parts within the principles of the invention to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed.
Pursuant to 35 U.S.C. § 119(e), this application claims the benefits of the priority to U.S. Provisional Patent Application No. 62/430,982, filed Dec. 7, 2016 and of the priority to U.S. Provisional Patent Application No. 62/433,371, filed Dec. 13, 2016. The contents of the prior applications are incorporated herein by their entirety.
| Number | Date | Country | |
|---|---|---|---|
| 62430982 | Dec 2016 | US | |
| 62433371 | Dec 2016 | US |
