Patent Application
20200274070
The present invention relates to a novel compound and an organic electronic device using the same, more particularly to a novel compound as an electron transport material or a hole blocking material 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 the 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 W. 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 short lifetime.
To overcome the problem of short lifetime, 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 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 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 lifespan 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 prolong the lifespan 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), *a1, a2*, *b, and *c represent bonding sites, *b is bonded to one of *a1 and a2*, and *c is bonded to the other of *a1 and a2*.
In Formula (I), G1-*b is represented by
In Formula (I), G2 is selected from the group consisting of:
wherein Z1 and Z2 are each independently selected from the group consisting of: a substituted aryl group having 6 to 60 ring carbon atoms, an unsubstituted aryl group having 6 to 60 ring carbon atoms, a substituted heteroaryl group having 3 to 60 ring carbon atoms, and an unsubstituted heteroaryl group having 3 to 60 ring carbon atoms.
m1 to m4 are each independently an integer 0 or 1, and m1 to m4 are the same or different.
L1 to L4 are each independently an arylene group having 6 to 60 ring carbon atoms, and L1 to L4 are the same or different.
Y1 to Y3 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 30 ring carbon atoms, and Y1 to Y3 are the same or different.
Preferably, the compound may be represented by any one of the following Formulae (I-I) to (I-XVI):
Preferably, said Z1 and Z2 are each independently 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, a trifluoromethyl group, an unsubstituted alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with a substituent, an unsubstituted alkenyl group having 2 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms substituted with a substituent, an unsubstituted alkynyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms substituted with a substituent, an unsubstituted aryl group having 6 to 30 ring carbon atoms, an aryl group having 6 to 30 ring carbon atoms substituted with a substituent, an unsubstituted heteroaryl group having 3 to 30 ring carbon atoms, and a heteroaryl group having 3 to 30 ring carbon atoms substituted with a substituent, wherein the substituent is selected from the group consisting of: a deuterium atom, a halogen group, a cyano group, a nitro group, and a trifluoromethyl group.
m is an integer from 1 to 4, n is an integer from 1 to 3, and o is an integer 1 or 2.
Preferably, said Z1 is selected from the group consisting of:
said Z2 is 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, a trifluoromethyl group, an unsubstituted alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with a substituent, an unsubstituted alkenyl group having 2 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms substituted with a substituent, an unsubstituted alkynyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms substituted with a substituent, an unsubstituted aryl group having 6 to 30 ring carbon atoms, an aryl group having 6 to 30 ring carbon atoms substituted with a substituent, an unsubstituted heteroaryl group having 3 to 30 ring carbon atoms, and a heteroaryl group having 3 to 30 ring carbon atoms substituted with a substituent, wherein the substituent is selected from the group consisting of: a deuterium atom, a halogen group, a cyano group, a nitro group, and a trifluoromethyl group.
m is an integer from 1 to 4, n is an integer from 1 to 3, and o is an integer 1 or 2.
More preferably, said R1 to R7 of said Z1 and Z2 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halogen group, a cyano group, a nitro group, a trifluoromethyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a phenyl group, a napthyl group, a biphenyl group, a triphenyl group, and a trifluoromethylphenyl group.
More specifically, said Z1 and Z2 are each independently selected from the group consisting of:
More specifically, said G2 of Formula (I) is selected from the group consisting of:
Preferably, G2 of Formula (I) is selected from the group consisting of:
Preferably, the arylene groups having 6 to 60 ring carbon atoms represented by said L1 to L4 are each independently selected from the group consisting of:
wherein m is an integer from 1 to 4, n is an integer from 1 to 3, and o is an integer 1 or 2.
X1 to X2 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a halo 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, an alkoxy group having 1 to 12 carbon atoms, an aryl group having 6 to 30 ring carbon atoms, a heteroaryl group having 3 to 30 ring carbon atoms, and an aryloxy group having 6 to 30 ring carbon atoms.
More preferably, said Y1 to Y3 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a phenyl group, a biphenyl group, and a napthyl group.
In this specification, said “arylene group having 6 to 60 ring carbon atoms” denoted by L1, L2, L3, or L4 may be an unsubstituted arylene group having 6 to 60 ring carbon atoms or an arylene group having 6 to 60 ring carbon atoms substituted with a substituent. The substituent on the arylene group may be any one of X1 to X2 as stated above.
In this specification, said “alkyl group” may be an unsubstituted alkyl group or an alkyl group substituted with a substituent, said “alkenyl group” may be an unsubstituted alkenyl group or an alkenyl group substituted with a substituent, and said “alkynyl group” may be an unsubstituted alkynyl group or an alkynyl group substituted with a substituent. The substituent on the alkyl group, alkenyl group, or alkynyl group may be, for example, but not limited to a deuterium atom.
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. The novel compound may be, but is not limited to, any one of Compounds 1 to 1826.
Preferably, the organic electronic device is an organic light emitting device (OLED).
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 an electron transport material which is the novel compound as stated above.
For example, the electron transport layer may be a single-layered configuration or a multi-layered configuration disposed between the emission layer and the electron injection layer. When the electron transport layer is the multi-layered configuration, e.g., the electron transport layer comprises a first electron transport layer and a second electron transport layer, the first electron transport material of the first electron transport layer may be made of a single novel compound and the second electron transport material of the second electron transport layer may be made of another single novel compound or any single conventional compound. Or, the first electron transport material of the first electron transport layer may be made of a novel compound in combination with another single novel compound or any single conventional compound, and so as the second electron transport material.
Said first and/or second electron transport layer comprises the novel compound such as Compounds 1 to 1826. The OLEDs using the novel compound as the electron transport material can have a prolonged lifespan compared to the commercial OLEDs using known electron transport materials of ETL, such as BCP, TmPyPb, TPBi, 3TPYMB, BmPyPb, and DPyPA.
Preferably, the OLED further comprises a hole blocking layer (HBL), formed between the electron transport layer and the emission layer, to block holes overflow from the emission layer to the electron transport layer.
In another embodiment, the organic layer may be the hole blocking layer, i.e., the hole blocking layer comprises a hole blocking material which is the novel compound as stated above. More specifically, said hole blocking layer comprises the novel compound such as Compounds 1 to 1826. The OLEDs using the novel compound as the hole blocking material can have a prolonged lifespan compared to commercial OLEDs using known hole blocking materials of HBL, such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) and 2,3,5,6-tetramethyl-phenyl-1,4-(bis-phthalimide) (TMPP).
Preferably, the hole injection layer may be a single-layered configuration or a multi-layered configuration, 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.
The aforesaid hole injection layer(s) may be made of, for example, but not limited to: polyaniline, polyethylenedioxythiophene, 4,4′,4″-Tris[(3-methylphenyl)phenylamino]triphenylamine (m-MTDATA), or N1,N1′-(biphenyl-4,4′-diyl)bis(N1-(naphthalen-1-yl)-N4,N4′-diphenylbenzene-1,4-diamine).
Preferably, the hole transport layer may be a two-layered configuration, 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.
Said first and second hole transport layers may be made of, for example, but not limited to: 1,1-bis[(di-4-tolylamino)phenylcyclohexane](TAPC), a carbazole derivative such as N-phenyl carbazole, and N4,N4′-di(naphthalen-1-yl)-N4,N4′-diphenylbiphenyl-4,4′-diamine (NPB).
Preferably, the 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 quinoline derivative ligands or isoquinoline derivative ligands; an osmium complex; or a platinum complex. 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: an aminoperylene derivative; a diaminochrysene; diaminopyrenes; or organicmetallic compounds of iridium (II) having pyridinato picolinate ligands. With various host materials of the emission layer, the OLED can emit lights in red, green or blue.
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 it is not limited thereto.
In the presence of such a hole blocking layer and/or an electron blocking layer in an OLED, the OLED has an improved efficiency compared to a conventional OLED.
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.
Intermediate An used for preparing a novel compound was synthesized by the following steps.
In step 1, the general synthesis pathway of Intermediate An-1 was summarized in Scheme A1, which can be used to prepare Intermediates A1 to A8.
In Scheme A1, A is oxygen or sulfur; Y1 to Y3 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 30 ring carbon atoms, and Y1 to Y3 are the same or different.
Taking Intermediate A1-1 as an example of Intermediate An-1, the synthesis pathway of Intermediate A1-1 was summarized in Scheme A1-1.
A mixture of 1-bromo-4-iododibenzofuran (1.0 eq), 1-dibenzofuranboronic acid (1.0 eq), tris(dibenzylideneacetone)dipalladium[Pd2(dba)3] (0.005 eq), and triphenylphosphine (PPh3) (0.02 eq) was in a mixed solution of methoxymethane (DME) (0.5 M) and Na2CO3 aqueous solution (2.0 M). The reaction mixture was heated to about 85° C. and stirred for 12 to 16 hours under nitrogen atmosphere. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated crude product was then separated by filtration to obtain a crude product. After the filtration, the crude product was purified by recrystallization method using toluene to obtain a white solid product in 77.4% yield.
The white solid product was identified as Intermediate A1-1 by a field desorption mass spectroscopy (FD-MS) analysis. FD-MS analysis: C24H13BrO2; theoretical value: 412.01; observed value: 412.01.
Intermediates A2-1 to A8-1, which also can be used for preparing a novel compound, were respectively synthesized in a similar manner as Intermediate A1-1 through step 1, except that the starting material Reactant A1 was replaced by Reactants A2 to A8, respectively. All intermediates were analyzed as described above, and the results were listed in Table 1.
Modifications of Intermediates A1-1 to A8-1
In addition to Intermediates A1-1 to A8-1, one person skilled in the art can adopt other applicable starting materials (e.g., the starting materials with different choices of Y1 to Y3 and the starting materials with different choices of L1 and L2) and successfully synthesize other desired intermediates through a reaction mechanism similar to Scheme A1-1.
For example, other applicable starting materials may be, but are not limited to, the following reactants.
In step 2, the general synthesis pathway of Intermediate An was summarized in Scheme A2.
In Scheme A2, A is oxygen or sulfur; Y1 to Y3 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 30 ring carbon atoms, and Y1 to Y3 are the same or different.
Taking Intermediate A1 as an example of Intermediate An, the synthesis pathway of Intermediate A1 was summarized in Scheme A2-1.
A mixture of Intermediate A1-1 (1.0 eq), bis(pinacolato)diboron (1.20 eq), 1,1′-bis(diphenylphosphino)-ferrocene dichloropalladium (II) [PdCl2(dppf)] (0.025 eq), and potassium acetate (KOAc) (3.0 eq) in 1,4-dioxane (0.5 M) was degassed with nitrogen and then heated at about 90° C. for 16 hours. After cooling to room temperature, the precipitated crude product was separated by filtration to obtain a crude product. Then, the crude product was purified by column chromatography on silica gel with CH2Cl2/hexane (1:1 v/v) as eluent, and the eluent was concentrated under reduced pressure and then recrystallized with hexane to obtain a white solid product in 89.0% yield.
The white solid product was identified as Intermediate A1 by a FD-MS analysis. FD-MS analysis: C3H25BO4; theoretical value: 460.18; observed value: 460.18.
Intermediates A2 to A8, which also can be used for preparing a novel compound, were respectively synthesized in a similar manner as Intermediate A1 through step 2, except that the starting material Intermediate A1-1 was replaced by Intermediates A2-1 to A8-1, respectively. All intermediates were analyzed as described above, and the results were listed in Table 2.
Intermediate An used for preparing a novel compound can also be synthesized by the following steps.
In step 1′, the general synthesis pathway of Intermediate An-1 was summarized in Scheme A3, which can be used to prepare Intermediates A9 to A16.
In Scheme A3, A is oxygen or sulfur; Y1 to Y3 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 30 ring carbon atoms, and Y1 to Y3 are the same or different.
Taking Intermediate A9-1 as an example of Intermediate An-1, the synthesis pathway of Intermediate A9-1 was summarized in Scheme A3-1.
A mixture of 1-bromo-4-aminodibenzofuran (1.0 eq), 1-dibenzofuranboronic acid (1.0 eq), tris(dibenzylideneacetone)dipalladium[Pd2(dba)3] (0.005 eq), and triphenylphosphine (PPh3) (0.02 eq) was placed in a mixed solution of methoxymethane (DME) (0.5 M) and Na2CO3 aqueous solution (2.0 M). Afterward, the following synthetic procedures were in a same manner as stated in Scheme A1-1. A white solid product was obtained in 69.2% yield.
The product was identified as Intermediate A9-1 by a FD-MS analysis. FD-MS analysis: C24H15NO2; theoretical value: 349.11; observed value: 349.11.
Intermediates A10-1 to A16-1, which also can be used for preparing a novel compound, were respectively synthesized in a similar manner as Intermediate A9-1 through step 1′, except that the starting material Reactant A1 was replaced by Reactants A2 to A8, respectively. All intermediates were analyzed as described above, and the results were listed in Table 3.
Modifications of Intermediates A9-1 to A16-1
In addition to Intermediates A9-1 to A16-1, one person skilled in the art can adopt other applicable starting materials (e.g., the starting materials with different choices of Y1 to Y3 and the starting materials with different choices of L1 and L2) and successfully synthesize other desired intermediates through a reaction mechanism similar to Scheme A3-1.
For example, other applicable starting materials may be, but are not limited to, the following reactants.
In step 2′-1 and step 2′-2, the general synthesis pathway of Intermediate An was summarized in Scheme A4.
In Scheme A4, A is oxygen or sulfur; Y1 to Y3 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 30 ring carbon atoms, and Y1 to Y3 are the same or different.
Taking Intermediate A9 as an example of Intermediate An, the synthesis pathway of Intermediate A9 was summarized in Scheme A4-1.
Intermediate A9-1 (1.0 eq) was added into a solution mixed with p-Toluenesulfonic acid⋅H2O (p-TsOH.H2O) (3.0 eq) and CH3CN (0.5 M). Afterward, the mixed solution resulting with suspension of amine salt was cooled to below 10° C., and then an aqueous solution of NaNO2 (2.0 eq) and KI (2.5 eq) was gradually added to the foresaid cooled solution, and the reaction mass was stirred for 1 hour, and then its temperature was raised to 20° C. and the reaction mass was stirred overnight. After that, the pH value of the solution was adjusted by saturated solution of NaHCO3 until the pH value of the solution was between 9 and 10. The precipitate was separated by filtration or extracted with CH2Cl2, and then purified by flash chromatography with eluent (hexane to CH2Cl2 is 3 to 1) to obtain a crude solid product.
A mixture of the crude solid product (1.0 eq), bis(pinacolato)diboron (1.20 eq), 1,1′-bis(diphenylphosphino)-ferrocene dichloropalladium (II) [PdCl2(dppf)] (0.025 eq), and potassium acetate (KOAc) (3.0 eq) in 1,4-dioxane (0.5 M) was degassed with nitrogen and then heated at about 90° C. for 16 hours. Afterward, the following synthetic procedures are in a same manner as stated in Scheme A2-1. A white solid product was obtained in 55.6% yield.
The white solid product was identified as Intermediate A9 by a FD-MS analysis. FD-MS analysis: C30H25BO4; theoretical value: 460.18; observed value: 460.18.
Intermediates A10 to A16, which also can be used for preparing a novel compound, were respectively synthesized in a similar manner as Intermediate A9 through step 2′-1 and step 2′-2, except that the starting material Intermediate A9-1 was replaced by Intermediates A10-1 to A16-1, respectively. All intermediates were analyzed as described above, and the results were listed in Table 4.
In Table 4, the yields of A9 to A16 were calculated by multiplying the yield of the step 2′-1 (65.6% to 71.4%) and the yield of the step 2′-2 (88.6% to 93.5%) in Scheme A4-1.
Modifications of Intermediates A1 to A16
In addition to the foresaid synthesis pathway, modification of Intermediates A1 to A16 also can be implemented by the following summarized synthesis pathway.
In Scheme A5, A is oxygen or sulfur; Y1 to Y3 are each independently selected from the group consisting of: a hydrogen atom, a deuterium atom, an alkyl group having 1 to 12 carbon atoms, and an aryl group having 6 to 30 ring carbon atoms, and Y1 to Y3 are the same or different.
For more detailed descriptions, an intermediate was prepared as follows.
A mixture of (1-(dibenzofuran-4-yl)-4-iododibenzofuran) (50.0 g 1.0 eq), 4-chlorophenylboronic acid (1.05 eq, CAS No. 1679-18-1), Pd(OAc)2 (0.01 eq), PCy2(2-biPh) (0.04 eq), and K2CO3 (2.0 eq) was placed in a mixed solution of toluene (340 mL), ethanol (34 mL) and H2O (72 mL). The reaction mixture was heated to about 80° C. under reflux and stirred for 16 hours under nitrogen atmosphere. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the crude product was extracted and collected by the organic layer. The organic layer was dried over MgSO4, separated by filtration and concentrated to dryness. A resulting residue was purified by silica gel column chromatography to obtain 43 g of white solid product in an yield of 89%.
The white solid product was identified by a FD-MS analysis. FD-MS analysis: C30H17ClO2; theoretical value: 444.91; observed value: 444.91.
Each of the foresaid Intermediates, e.g., Intermediates An could be reacted with various reactants to synthesize various claimed novel compounds. The general synthesis pathway of the claimed novel compound was summarized in Scheme I. In the following Scheme I, “Reactant Bn” may be any one of Reactants B1 to B9 and B9′ as listed in Table 5, and “Intermediate A” may be any one of the foresaid Intermediates An or the like. The compounds were each synthesized by the following steps.
Scheme I
In Scheme I, a mixture of Intermediate A (1.0 eq), Reactant Bn (1.0 eq), Pd2(dba)3 (0.01 eq), PCy3*HBF4 (0.02 eq), sodium carbonate solution (2.0 M) in 1,4-dioxane/toluene (2:1 v/v) as solvent was refluxed for about 12 to 16 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated crude product was then separated by filtration to obtain a crude product. After the filtration, the crude product was purified by recrystallization method using otho-dichlorobenzene to obtain a white solid product as the claimed novel compounds.
Another synthesis pathway of the claimed novel compound was summarized in Scheme II. In the following Scheme II, “Reactant Bn” may be any one of Reactants B10 to B11 as listed in Table 6, and “Intermediate A” may be any one of the foresaid Intermediates An or the like. The compounds were each synthesized by the following steps.
Scheme II
In Scheme II, a mixture of Intermediate A (1.0 eq), Reactant Bn (1.0 eq), Pd(OAc)2 (0.01 eq), PCy2(2-bi-phenyl) (0.02 eq), sodiumcarbonate solution (2.0 M) in toluene/EtOH (1:0.1 v/v) as solvent was refluxed for about 8 to 12 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated crude product was then separated by filtration to obtain a crude product. After the filtration, the crude product was purified by recrystallization method using otho-dichlorobenzene to obtain a white solid product as the claimed novel compounds.
Intermediate A and Reactant Bn adopted to synthesize the claimed novel compounds were listed in Table 7.
Compounds 1 to 20 were identified by 1H-NMR and FD-MS, and the chemical structure, yield, formula, mass of each of Compounds 1 to 20 were also listed in Table 7. Also, the 1H-NMR result of each of Compounds 1 to 5 and 7 to 20 were listed in Table 8.
1H-NMR results of Compounds 1 to 5 and 7 to 20.
1H-NMR
1H NMR (500 MHz, CDCl3): δ 9.04(dd, 2H), 8.85(dd, 2H), 8.73(d, 1H), 8.58(d, 1H), 8.15~8.00(m, 5H), 7.78(dd, 4H), 7.65~7.38(m, 16H) ppm.
1H NMR (500 MHz, CDCl3): δ 9.00(s, 2H), 8.80(d, 2H), 8.70(d, 1H), 8.48(d, 1H), 8.22(s, 1H), 8.10(d, 1H), 8.06(s,1H), 8.00(d, 1H), 7.92(d, 1H), 7.82(d, 1H), 7.75(d, 4H), 7.57-7.68(m, 5H), 7.48-7.51(m, 6H), 7.38-7.43(m, 3H), 7.23(m, 1H) ppm.
1H NMR (500 MHz, CDCl3): δ 9.02(dd, 2H), 8.83(dd, 2H), 8.73(d, 1H), 8.53(d, 2H), 8.12~8.03(m, 3H), 7.86-7.55(m, 12H), 7.53~7.36(m, 9H) ppm.
1H NMR (500 MHz, CDCl3): δ 8.97(dd, 4H), 8.79(dd, 2H), 8.04(d, 2H), 7.79(dd, 8H), 7.62~7.41(m, 15H) ppm.
1H NMR (500 MHz, CDCl3): δ 9.08(dd, 2H), 8.81(dd, 2H), 8.75(d, 1H), 8.58(d, 1H), 8.13(d, 1H), 8.07~8.00(m, 3H), 7.88(dd, 2H), 7.74(dd, 4H), 7.66(dd, 2H), 7.59~7.46(m, 9H), 7.40(m, 3H), 7.24(dd, 1H) ppm.
1H NMR (500 MHz, CDCl3): δ 9.13(dd, 2H), 8.87(dd, 2H), 8.23(d, 1H), 8.06(d, 1H), 7.97(dd, 1H), 7.85(dd, 4H), 7.80~7.35(m, 19H), 7.11(dd, 1H) ppm.
1H NMR (500 MHz, CDCl3): δ 9.01(d, 2H), 8.98(d, 2H), 8.83(dd, 2H), 8.20(d, 2H), 8.12(d, 1H), 8.07~8.02(m, 2H), 7.87~7.39(m, 23H), 7.12(dd, 1H) ppm.
1H NMR (500 MHz, CDCl3): δ 8.95(d, 1H), 8.80(dd, 2H), 8.63(d, 1H), 8.51(d, 2H), 8.44(d, 2H), 8.26(dd, 2H), 8.14(s, 1H), 7.95~7.89(m, 4H), 7.84~7.76(m, 4H), 7.72(d, 1H), 7.67(t, 1H), 7.60~7.52(m, 4H), 7.48~7.39(m, 5H), 7.17(t, 1H) ppm.
1H NMR (500 MHz, CDCl3): δ 8.58-8.53(m, 4H), 8.44(d, 1H), 8.39~8.36(m, 2H), 8.30(s, 1H), 8.11~8.00(m, 6H), 7.75~7.73(m, 5H), 7.60~7.36(m, 12H), 7.16(dd, 1H) ppm.
1H NMR (500 MHz, CDCl3): δ 8.79~8.77(m, 2H), 8.52(d, 2H), 8.22(s, 1H), 8.17~7.99(m, 6H), 7.87(d, 1H), 7.78(dd, 4H), 7.60~7.38(m, 15H), 7.20(dd, 1H) ppm.
1H NMR (500 MHz, CDCl3): δ 8.99(d, 2H), 8.37(dd, 2H), 8.22(d, 1H), 8.16(s, 1H), 8.10~7.99(m, 5H), 7.87(d, 1H), 7.76(dd, 4H), 7.61~7.56(m, 6H), 7.49~7.44(m, 6H), 7.40~7.38(m, 3H), 7.22(dd, 1H) ppm.
1H NMR (500 MHz, CDCl3): δ 9.02(s, 1H), 8.83(t, 4H), 8.10(d, 1H), 8.06(t, 2H), 7.94(d, 1H), 7.76(d, 1H), 7.70(d, 1H), 7.65(d, 1H), 7.61(d, 4H), 7.50(d, 1H), 7.47(t, 1H), 7.43(m, 4H), 7.38(t, 1H), 7.04(d, 1H), 6.97(t, 1H) ppm.
1H NMR (500 MHz, CDCl3): δ 9.0(s, 1H), 8.85-8.80(m, 3H), 8.57(d, 2H), 8.12(d, 1H), 8.04(d, 1H), 8.01(s, 1H), 7.82(d, 4H), 7.71(t, 2H), 7.63(d, 1H), 7.58~7.53(m, 9H), 7.46~7.39(m, 5H), 7.07~7.01(dd, 2H) ppm.
1H NMR (500 MHz, CDCl3): δ 8.97(s, 1H), 8.78(t, 3H), 8.56(d, 2H), 8.23(s, 1H), 7.9(d, 2H), 7.80(d, 4H), 7.75(s, 2H), 7.64(dd, 2H), 7.58~7.51(m, 9H), 7.49-7.42(q, 4H), 7.37(t, 1H), 7.12(t, 1H) ppm.
1H NMR (500 MHz, CDCl3): δ 8.95(d, 1H), 8.80(dd, 2H), 8.64(dd, 1H), 8.50(d, 2H), 8.43(d, 2H), 8.16(s, 1H), 8.05-8.00(m, 4H), 7.94(dt, 1H), 7.90(d, 2H), 7.79(d, 2H), 7.69(d, 1H), 7.58~7.52(m, 5H), 7.48(t, 2H), 7.41~7.39(m, 4H), 7.17(t, 1H) ppm.
1H NMR (500 MHz, CDCl3): δ 9.04(d, 2H), 8.8(d, 1H), 8.71(d, 1H), 8.55(d, 1H), 8.28(d, 1H), 8.23(d, 1H), 8.08(d, 1H), 8.00(d, 1H), 7.84~7.83(m, 2H), 7.80~7.77(m, 4H), 7.70~7.57(m, 6H), 7.52~7.43(, 8H), 7.43(dd, 2H) ppm.
1H NMR (500 MHz, CDCl3): δ 8.80(s, 2H), 8.74(s, 1H), 8.55(s, 2H), 8.34~8.29(m, 1H), 8.23~8.16(m, 2H), 8.08(s, 2H), 8.02(s, 1H), 7.96~7.91(m, 1H), 7.87(s,2H), 7.80(d, 4H), 7.70(dd, 1H), 7.60~7.50(m, 9H), 7.50~7.44(m, 2H), 7.29~7.21(m, 2H) ppm.
1H NMR (500 MHz, CDCl3): δ 8.97(d, 1H), 8.91(dd, 1H), 8.31(q, 1H), 8.25(d, 1H), 8.18(dd, 1H), 8.0(d, 1H), 7.73-7.77(m, 3H), 7.66-7.69(m, 3H), 7.49-7.57(m, 3H), 7.38-7.43(m, 3H), 6.99-7.02(m, 2H) ppm.
1H NMR (500 MHz, CDCl3): δ 9.09(d, 2H), 8.84(dd, 3H), 8.42(s, 1H), 8.16(d, 1H), 7.99-8.03(m, 2H), 7.93(d, 1H), 7.83(d, 4H), 7.71(d, 1H), 7.67(d, 1H), 7.42-7.60(m, 14H), 7.08(t, 1H) ppm.
Modifications of the Claimed Novel Compounds
In addition to Compounds 1 to 20, one person skilled in the art can react any Intermediate A, i.e., the foresaid Intermediate An, or the like, with any Reactant Bn or the like through a reaction mechanism similar to Scheme I or Scheme II to synthesize other desired claimed novel compounds.
Preparation of OLED Devices
A glass substrate coated with an ITO layer (hereinafter referred to 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 51 and Comparative Examples 1 to 12. 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 hole injection layer (HIL), 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, HI-D was a dopant with HI for forming HIL; HT1 was a material for forming HTL-1, and B-HT2/G-HT2/R-HT2 were respectively materials for forming blue, green and red HTL-2; conventional ET and novel compounds of the present invention were materials for forming ETL; Liq was a dopant for forming ETL and was a material for forming EIL. RH/GH/BH were host materials for forming REL/GEL/BEL, and RD/GD/BD were dopants for forming REL/GEL/BEL. The main difference of the OLEDs between Examples and Comparative Examples was that the ETL of the OLED in the following comparative examples was made of ET1 or ET2 but the ETL of OLED in the following examples was made of the novel compounds of the present invention listed in Table 7. The detailed chemical structures of foresaid commercial materials were listed in Table 9.
OLEDs with a Single Electron Transport Layer
In OLEDs with a single electron transport layer, various organic materials and metal materials were sequentially deposited on the ITO substrate to obtain the OLED device of Examples 1 to 32 and Comparative Examples 1 to 6. Herein, as shown in
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 10, and the materials and the thicknesses of the organic layers in blue OLED devices were also listed in Table 10.
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 11, and the materials and the thicknesses of the organic layers in green OLED devices were also listed in Table 11.
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 12, and the materials and the thicknesses of the organic layers in red OLED devices were also listed in Table 12.
Performance of OLED Devices
To evaluate the performance of OLED devices, the 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).
Measurement of Lifespan
The evaluation of lifespan was measured by OLED life time test system (Chroma model 58131). Measurements of lifespan for blue, green, and red OLEDs were respectively performed according to the following circumstances.
For blue OLEDs, the evaluation of lifespan (T85) was defined as a period taken for luminance reduction to 85% of the initial luminance at 2000 nits. The results of blue OLEDs were shown in Table 13.
For green OLEDs, the evaluation of lifespan (T95) was defined as a period taken for luminance reduction to 95% of the initial luminance at 7000 nits. The results of green OLEDs were shown in Table 14.
For red OLEDs, the evaluation of lifespan (T90) was defined as a period taken for luminance reduction to 90% of the initial luminance at 6000 nits. The results of red OLEDs were shown in Table 15.
The materials of ETL, datas of CIE and lifespan of Examples 1 to 32 and Comparative Examples 1 to 6 were listed in Table 13, Table 14 and Table 15.
As shown in Tables 13 to 15, in comparison with the conventional ET materials (i.e., ET1 and ET2), adopting the novel compounds of the present invention as the electron transport material can effectively prolong lifespan of the blue, green, or red OLEDs with a single electron transport layer.
OLEDs with Double Electron Transport Layer
Like OLEDs with a single electron transport layer, various organic materials and metal materials were sequentially deposited on the ITO substrate to obtain the OLED device of Examples 33 to 51 and Comparative Examples 7 to 12. Herein, as shown in
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 16, and the materials and the thicknesses of the organic layers in blue OLED devices were also listed in Table 16.
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 17, and the materials and the thicknesses of the organic layers in green OLED devices were also listed in Table 17.
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 18, and the materials and the thicknesses of the organic layers in red OLED devices were also listed in Table 18.
Performance of OLED Devices
The evaluation of the performance of OLED devices with double electron transport layers was performed in a same manner with OLEDs devices with a single electron transport layer.
Measurement of Lifespan
The evaluation of lifespan OLED devices with double electron transport layers was also measured. The materials of ETL-2, data of CIE and lifespan of Examples 33 to 51 and Comparative Examples 7 to 12 were listed in Table 19, Table 20 and Table 21.
As shown in Tables 19 to 21, in comparison with the conventional ET materials (i.e., ET1 and ET2), adopting the novel compounds of the present invention as the electron transport material of the second electron transport layer also can effectively prolong lifespan of the blue, green, or red OLEDs with double electron transport layers.
Measurement of Driving Voltage
In addition to lifespan of OLEDs, the evaluation of driving voltage of OLED devices with double electron transport layers was also performed. The materials of ETL-2, data of CIE and driving voltage of Examples 33, 36, 40 to 42, 45 to 47 and 51, and Comparative Examples 7 to 12 were listed in Table 22.
As shown in Table 22, in comparison with the conventional ET materials (i.e., ET1 and ET2), adopting the novel compounds of the present invention as the electron transport material of the second electron transport layer can additionally reduce driving voltage of the blue, green, or red OLEDs with double electron transport layers.
In brief, regardless of in OLED devices with single or double electron transport layers, in comparison with the conventional ET materials, adopting the novel compounds of the present invention as the electron transport material can effectively prolong lifespan of the blue, green, or red OLEDs. Moreover, in OLED devices with double electron transport layers, adopting the novel compounds of the present invention as the electron transport material can further reduce the driving voltage of the blue, green, or red OLEDs.
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. 62/811,241, filed Feb. 27, 2019. The contents of the prior application are incorporated herein by its entirety.
| Number | Date | Country | |
|---|---|---|---|
| 62811241 | Feb 2019 | US |
