Patent Application
20230371373
The present invention relates to an organic electroluminescence device, a compound, an organic-electroluminescence-device material, and an electronic device.
When a voltage is applied to an organic electroluminescence device (hereinafter, occasionally referred to as “organic EL device”), holes are injected from an anode and electrons are injected from a cathode into an emitting layer. The injected electrons and holes are recombined in the emitting layer to form excitons. Specifically, according to the electron spin statistics theory, singlet excitons and triplet excitons are generated at a ratio of 25%:75%.
A fluorescent organic EL device using light emission from singlet excitons has been applied to a full-color display such as a mobile phone and a television set, but an internal quantum efficiency is said to be at a limit of 25%. Studies have thus been made to improve performance of the organic EL device.
For instance, the organic EL device is expected to emit light more efficiently using triplet excitons in addition to singlet excitons. In view of the above, a highly-efficient fluorescent organic EL device using thermally activated delayed fluorescence (hereinafter simply referred to as “delayed fluorescence” in some cases) has been proposed and studied.
A thermally activated delayed fluorescence (TADF) mechanism uses such a phenomenon in which inverse intersystem crossing from triplet excitons to singlet excitons thermally occurs when a material having a small energy difference (ΔST) between singlet energy level and triplet energy level is used. Thermally activated delayed fluorescence is explained in “Yuki Hando-tai no Debaisu Bussei (Device Physics of Organic Semiconductors)” (edited by ADACHI Chihaya, published by Kodansha, issued on Apr. 1, 2012, on pages 261-268).
Patent Literature 1 discloses an organic EL device containing a delayed fluorescent compound and a biscarbazole compound substituted by an aryl group in an emitting layer.
Patent Literature 2 discloses an organic EL device containing a delayed fluorescent compound, a compound having a carbazole group and a dibenzothiophene group or a dibenzofuran group in an emitting layer.
Patent Literature 1: WO2019/013063
Patent Literature 2: WO2020/122118
A further improvement in performance of the organic EL device has been demanded for an improvement in performance of an electronic device such as a display.
An object of the invention is to provide an organic electroluminescence device excellent in performance, particularly, having an improved luminous efficiency, and an electronic device including the organic electroluminescence device.
Another object of the invention is to provide a compound capable of achieving an organic electroluminescence device excellent in performance, particularly, having an improved luminous efficiency, and an organic-electroluminescence-device material containing the compound.
According to an aspect of the invention, there is provided an organic electroluminescence device including: an anode; a cathode; an emitting layer provided between the anode and the cathode, in which the emitting layer contains a compound M3 represented by a formula (11), a formula (12) or a formula (13) below and a delayed fluorescent compound M2, the compound M3 and the compound M2 are different in structure, and a singlet energy S1(M3) of the compound M3 and a singlet energy S1(M2) of the compound M2 satisfy a relationship of a numerical formula (Numerical Formula 1) below.
In the formulae (11) to (13):
According to another aspect of the invention, there is provided an electronic device including the organic electroluminescence device according to the aspect of the invention.
According to still another aspect of the invention, there is provided a compound represented by a formula (121) or (122) below.
In the formulae (121) and (122):
According to a further aspect of the invention, there is provided a compound represented by one of formulae (131) to (134) below.
In the formulae (131) to (134):
According to a still further aspect of the invention, there is provided a compound represented by a formula (141), (142) or (143) below
In the formulae (141) to (143):
According to a still further aspect of the invention, there is provided an organic-electroluminescence-device material containing the compound according to the aspect of the invention.
According to the above aspect of the invention, there can be provided an organic electroluminescence device excellent in performance, particularly, having an improved luminous efficiency, and an electronic device including the organic electroluminescence device.
According to the above aspect of the invention, there can be provided a compound capable of achieving an organic electroluminescence device excellent in performance, particularly, having an improved luminous efficiency, and an organic-electroluminescence-device material containing the compound.
An arrangement of an organic EL device according to a first exemplary embodiment of the invention will be described below.
The organic EL device includes an anode, a cathode, and an organic layer between the anode and the cathode. The organic layer includes at least one layer formed from an organic compound(s). Alternatively, the organic layer includes a plurality of layers formed from an organic compound(s). The organic layer may further contain an inorganic compound(s). In the organic EL device of the exemplary embodiment, at least one layer of the organic layer is an emitting layer. For instance, the organic layer may be one emitting layer, or may further include a layer(s) usable in the organic EL device. Examples of the layer usable in the organic EL device, which are not particularly limited, include at least one selected from the group consisting of a hole injecting layer, a hole transporting layer, an electron injecting layer, an electron transporting layer, and a blocking layer.
The organic EL device of the exemplary embodiment includes the emitting layer between the anode and the cathode.
An organic EL device 1 includes a light-transmissive substrate 2, an anode 3, a cathode 4, and an organic layer 10 provided between the anode 3 and the cathode 4. The organic layer 10 includes a hole injecting layer 6, a hole transporting layer 7, an emitting layer 5, an electron transporting layer 8, and an electron injecting layer 9 that are layered on the anode 3 in this order.
In an exemplary arrangement of the exemplary embodiment, the emitting layer may contain a metal complex.
In an exemplary arrangement of the exemplary embodiment, the emitting layer preferably does not contain a phosphorescent material (dopant material).
In an exemplary arrangement of the exemplary embodiment, the emitting layer preferably does not contain a heavy-metal complex and a phosphorescent rare earth metal complex. Examples of the heavy-metal complex herein include iridium complex, osmium complex, and platinum complex.
In an exemplary arrangement of the exemplary embodiment, the emitting layer also preferably does not contain a metal complex.
In the organic EL device of the exemplary embodiment, the emitting layer contains a compound M3 represented by a formula (11), (12) or (13) below and a delayed fluorescent compound M2.
In this arrangement, the compound M2 is preferably a dopant material (also referred to as a guest material, emitter or luminescent material), and the compound M3 is preferably a host material (also referred to as a matrix material).
The inventors have found that a high-performance organic EL device is achievable by using the compound M3 represented by the formula (11), (12) or (13) with the delayed fluorescent compound M2.
In general, a moiety having a large absolute value of an energy level of LUMO (lowest unoccupied molecular orbital) is often introduced into a molecule of a delayed fluorescent compound to reduce ΔST, which would also often increase an absolute value of an energy level of HOMO (highest occupied molecular orbital) of the entire molecule thereof. However, having a large absolute value of an energy level of HOMO may hinder hole injection into the emitting layer from the hole transporting layer, decreasing the luminous efficiency.
The compound M3 has a “biscarbazole structure excellent in hole injectability and hole transportability” and a “three-fused ring structure containing a hetero atom” (specifically, dibenzofuran, dibenzothiophen or carbazole) exhibiting a high heat stability contributing to a stable formation of an amorphous thin film.
In the exemplary embodiment, the emitting layer is made to contain the delayed fluorescent compound M2 and the compound M3 having the two structures (“biscarbazole structure” and “three-fused ring structure containing a hetero atom”), whereby the emitting layer can reduce hindrance to hole injection from the hole transporting layer to the emitting layer and can be obtained in a form of an amorphous thin film that is unlikely to be crystallized. As a result, luminous efficiency is considered to be improved.
Therefore, according to the exemplary embodiment, the organic EL device having a high performance, particularly, an improved luminous efficiency is achievable.
The wording “a high performance” in the exemplary embodiment means at least one of improving the luminous efficiency, emitting light for a long life, or decreasing drive voltage.
Patent Literature 2 discloses a biscarbazole structure in which a position 3 of one carbazole is bonded to the other carbazole. However, the luminous efficiency is decreased in the organic EL device in which the compound having the biscarbazole structure of Patent Literature 2 (e.g., a compound Ref-1 in Table 1 below) and the delayed fluorescent compound M2 are contained in the emitting layer. This is considered to be because an absolute value of an HOMO energy level is too small.
For instance, if the compound M3 having too small absolute value of the HOMO energy level and the delayed fluorescent compound M2 are contained in the emitting layer, hindrance to hole injection from the compound M3 to the compound M2, and exciplex formation of the compound M3 and the compound M2 are likely to occur, thereby causing decrease in efficiency.
Table 1 shows absolute values of HOMO energy level obtained by molecular orbital calculation for a compound M3-1 and a compound M3-5 as the compound M3 and a compound Ref-1 as the compound M3.
The molecular orbital calculation was performed using Gaussian98 at the B3LYP/6-31G* level.
In Table 1, the compound M3-1 and the compound M3-5 are compounds used in Examples 1 and 2 described later. The compound Ref-1 is a compound used in Comparative 1 described later and the compound having the biscarbazole structure in Patent Literature 2.
The emitting layer of the exemplary embodiment contains the compound M3 represented by the formula (11), (12) or (13) below.
The compound M3 of the exemplary embodiment may be a thermally activated delayed fluorescent compound or a compound exhibiting no thermally activated delayed fluorescence. However, the compound M3 is preferably a compound exhibiting no thermally activated delayed fluorescence.
In the formulae (11) to (13):
In the formulae (11) to (13): when a carbon atom bonded to R31 is bonded to *, a hydrogen atom represented by R31, a substituent represented by R31, and a ring formed by involving R31 are not present.
In the formulae (11) to (13), when a carbon atom bonded to R32 is bonded to *, a hydrogen atom represented by R32, a substituent represented by R32, and a ring formed by involving R32 are not present.
In the formulae (11) to (13), when a carbon atom bonded to R33 is bonded to *, a hydrogen atom represented by R33, a substituent represented by R33, and a ring formed by involving R33 are not present.
In the formulae (11) to (13), when a carbon atom bonded to R34 is bonded to *, a hydrogen atom represented by R34, a substituent represented by R34, and a ring formed by involving R34 are not present.
In the formulae (11) to (13), when a carbon atom bonded to R35 is bonded to *, a hydrogen atom represented by R35, a substituent represented by R35, and a ring formed by involving R35 are not present.
In the formulae (11) to (13), when a carbon atom bonded to R36 is bonded to *, a hydrogen atom represented by R36, a substituent represented by R36, and a ring formed by involving R36 are not present.
In the formulae (11) to (13), when a carbon atom bonded to R37 is bonded to *, a hydrogen atom represented by R37, a substituent represented by R37, and a ring formed by involving R37 are not present.
In the formulae (11) to (13), when a carbon atom bonded to R38 is bonded to *, a hydrogen atom represented by R38, a substituent represented by R38, and a ring formed by involving R38 are not present.
In the formulae (11) to (13), when a nitrogen atom bonded to R39 is bonded to *, a substituent represented by R39 is not present.
In the formulae (11) to (13), when a carbon atom bonded to R25 is bonded to *1, a hydrogen atom represented by R25, a substituent represented by R25, and a ring formed by involving R25 are not present.
In the formulae (11) to (13), when a carbon atom bonded to R27 is bonded to *1, a hydrogen atom represented by R27, a substituent represented by R27, and a ring formed by involving R27 are not present.
In the formulae (11) to (13): when a carbon atom bonded to R28 is bonded to *1, a hydrogen atom represented by R28, a substituent represented by R28, and a ring formed by involving R28 are not present.
In the compound M3, it is preferable that a combination of R11 and R12, a combination of R12 and R13, a combination of R13 and R14, a combination of R15 and R11, a combination of R16 and R17, and a combination of R17 and R18 are not mutually bonded. In other words, it is preferable that R11 to R18 in the compound M3 are each independently a hydrogen atom or a substituent.
In the compound M3, it is also preferable that at least one combination of a combination of R11 and R12, a combination of R12 and R13, a combination of R13 and R14, a combination of R15 and R16, a combination of R16 and R17, or a combination of R17 and R18 are mutually bonded to form a ring.
In the compound M3, it is preferable that a combination of R21 and R22, a combination of R22 and R23, a combination of R23 and R24, a combination of R25 and R26, a combination of R26 and R27, and a combination of R27 and R26 are not mutually bonded. In other words, it is preferable that R21 to R28 in the compound M3 are each independently a hydrogen atom or a substituent.
In the compound M3, it is also preferable that at least one combination of a combination of R21 and R22, a combination of R22 and R23, a combination of R23 and R24, a combination of R25 and R26, a combination of R26 and R27, or a combination of R27 and R28 are mutually bonded to form a ring.
In the compound M3, it is preferable that a combination of R31 and R32, a combination of R32 and R33, a combination of R33 and R34, a combination of R35 and R36, a combination of R36 and R37, and a combination of R37 and R38 are not mutually bonded. In other words, it is preferable that R31 to R38 in the compound M3 are each independently a hydrogen atom or a substituent.
In the compound M3, it is also preferable that at least one combination of a combination of R31 and R32, a combination of R32 and R33, a combination of R33 and R34, a combination of R35 and R36, a combination of R36 and R37, or a combination of R37 and R38 are mutually bonded to form a ring.
The compound M3 is preferably a compound represented by one of formulae (111) to (114) below.
In the formulae (111) to (114), A2, L1, L2, X1, R11 to R18, R21 to R28 and R31 to R39 each independently represent the same as A2, L1, L2, X1, R11 to R18, R21 to R28 and R31 to R39 in the formulae (11) to (13) and one selected from carbon atoms bonded to R31 to R38 and a nitrogen atom bonded to R39 is bonded to *.
The compound M3 is also preferably a compound represented by one of formulae (115) to (119) below.
In the formulae (115) to (119), A2, L1, L2, X1, R11 to R18, R21 to R28 and R31 to R39 each independently represent the same as A2, L1, L2, X1, R11 to R18, R21 to R28 and R31 to R39 in the formulae (11) to (13) and one selected from carbon atoms bonded to R31 to R38 and a nitrogen atom bonded to R39 is bonded to *.
The compound M3 is also preferably a compound represented by one of the formulae (115), (117) and (119).
The compound M3 is also preferably a compound represented by one of the formulae (111) to (113) and (115) to (119).
The compound M3 is also preferably a compound represented by one of the formulae (111), (115) to (116) and (119).
In the compound M3, A2 is preferably a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 18 ring atoms.
In the compound M3, A2 is more preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted fluorenyl group, or a group represented by a formula (14) below.
In the compound M3, it is preferable that L2 is a single bond and A2 is a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 18 ring atoms.
In the compound M3, it is more preferable that L2 is a single bond and A2 is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted fluorenyl group, or a group represented by the formula (14).
In the compound M3, it is still more preferable that L2 is a single bond and A2 is an unsubstituted phenyl group.
In the formula (14): X4 is an oxygen atom, a sulfur atom, or NR319;
R311 to R318 each independently represent the same as R31 to R38 in the formulae (11) to (13); R319 each independently represents the same as R39 in the formulae (11) to (13); and one selected from carbon atoms bonded to R311 to R318 and a nitrogen atom bonded to R319 is bonded to L2.
In the formula (14), X4 is preferably an oxygen atom or a sulfur atom.
In the formula (14), it is preferable that R311 to R318 are each independently a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; and R319 is a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
In the formula (14), it is more preferable that R311 to R318 are each independently a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and R319 is a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms.
In the formula (14), it is still more preferable that R311 to R318 are each a hydrogen atom and R319 is a substituted or unsubstituted phenyl group.
In the compound M3, it is preferable that R1 to R18, R21 to R28 and R31 to R38 are each independently a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; and R39 is a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
In the compound M3, it is more preferable that R1 to R18, R21 to R28 and R31 to R38 are each independently a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms; and R39 is a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms.
In the formula (14), it is still more preferable that R11 to R18, R21 to R28 and R31 to R38 are each a hydrogen atom and R39 is a substituted or unsubstituted phenyl group.
In the compound M3, it is preferable that L1 and L2 are each independently a single bond or a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms.
In the compound M3, it is more preferable that L1 and L2 are each independently a substituted or unsubstituted phenylene group, a substituted or unsubstituted parabiphenylene group, or a substituted or unsubstituted paraterphenylene group.
In the compound M3, it is still more preferable that L1 and L2 are each independently a substituted or unsubstituted parabiphenylene group, or a substituted or unsubstituted paraterphenylene group.
In the compound M3, it is also preferable that L1 and L2 are each independently a single bond or at least one group selected from the group consisting of groups represented by formulae (L1) to (L7) below.
In the compound M3, it is also preferable that L2 is a single bond or a group represented by one of the formulae (L3), (L4) and (L6).
In the formulae (L1) to (L7): Ra is a hydrogen atom or a substituent; a plurality of Ra are mutually the same or different; Rb and Rc are each independently a hydrogen atom or a substituent, or a combination of Rb and Rc are mutually bonded to form a ring; and Ra, Rb and Rc as a substituent each independently represent the same as R11 to R18 as a substituent in the formulae (11) to (13).
In the formulae (L1) to (L7), Ra is each independently preferably a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, more preferably a hydrogen atom.
In the formula (L7), it is preferable that Rb and Rc are each independently a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a combination of Rb and Rc are mutually bonded to form a ring.
In the compound M3, it is preferable that X1 is an oxygen atom or a sulfur atom, or X1 is NR39 and a nitrogen atom bonded to NR39 is bonded to * in the formulae (11) to (13).
In the compound M3, it is more preferable that X1 is an oxygen atom or a sulfur atom.
In the compound M3, it is still more preferable that X1 is an oxygen atom.
In the compound M3, it is also preferable that X1 is an oxygen atom or a sulfur atom, and a carbon atom bonded to R31 is bonded to * in the formulae (11) to (13).
In the compound M3, it is also preferable that X1 is an oxygen atom or a sulfur atom, and a carbon atom bonded to R32 is bonded to * in the formulae (11) to (13).
In the compound M3, it is also preferable that X1 is an oxygen atom or a sulfur atom, and a carbon atom bonded to R33 is bonded to * in the formulae (11) to (13).
In the compound M3, it is also preferable that X1 is an oxygen atom or a sulfur atom, and a carbon atom bonded to R34 is bonded to * in the formulae (11) to (13).
In the compound M3, a substituent for “substituted or unsubstituted” group is each independently preferably a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 30 carbon, more preferably an unsubstituted aryl group having 6 to 30 ring carbon atoms, an unsubstituted heterocyclic group having 5 to 30 ring atoms, or an unsubstituted alkyl group having 1 to 30 carbon atoms.
A “hydrogen atom” used herein encompasses a protium atom, a deuterium atom, and a tritium atom. Accordingly, the compound M3 (compound represented by the formula (11), (12) or (13)) used in the organic EL device of the exemplary embodiment may contain a naturally occurring deuterium atom. Alternatively, a deuterium atom may be intentionally introduced into the compound M3 by using a starting compound in which a part or all of hydrogen atoms are deuterium atoms.
Accordingly, the compound M3 used in the organic EL device of the exemplary embodiment may contain at least one deuterium atom. Specifically, the compound M3 is a compound represented by the formula (11), (12) or (13) and at least one of hydrogen atom(s) contained in the compound M3 may be a deuterium atom.
When the compound M3 contains at least one deuterium atom, for instance, at least one hydrogen atom selected from hydrogen atoms below may be a deuterium atom:
The compound M3 of the exemplary embodiment can be manufactured, for instance, by a method described in Example described later. The compound M3 of the exemplary embodiment can be manufactured by application of known substitution reactions and materials depending on a target compound according to reactions described in Example described later.
Specific examples of the compound M3 in the exemplary embodiment include compounds below. However, the invention is by no means limited to the specifically listed compounds.
The emitting layer of the exemplary embodiment contains a delayed fluorescent compound M2.
Delayed fluorescence is explained in “Yuki Hando-tai no Debaisu Bussei (Device Physics of Organic Semiconductors)” (edited by ADACHI, Chihaya, published by Kodansha, on pages 261-268). This document describes that, if an energy difference ΔE13 of a fluorescent material between a singlet state and a triplet state is reducible, a reverse energy transfer from the triplet state to the singlet state, which usually occurs at a low transition probability, would occur at a high efficiency to express thermally activated delayed fluorescence (TADF). Further, a generation mechanism of delayed fluorescence is explained in
In general, emission of delayed fluorescence can be confirmed by measuring the transient PL (Photo Luminescence).
The behavior of delayed fluorescence can also be analyzed based on the decay curve obtained from the transient PL measurement. The transient PL measurement is a method of irradiating a sample with a pulse laser to excite the sample, and measuring the decay behavior (transient characteristics) of PL emission after the irradiation is stopped. PL emission in TADF materials is classified into a light emission component from a singlet exciton generated by the first PL excitation and a light emission component from a singlet exciton generated via a triplet exciton. The lifetime of the singlet exciton generated by the first PL excitation is on the order of nanoseconds and is very short. Therefore, light emission from the singlet exciton rapidly attenuates after irradiation with the pulse laser.
On the other hand, the delayed fluorescence is gradually attenuated due to light emission from a singlet exciton generated via a triplet exciton having a long lifetime. As described above, there is a large temporal difference between the light emission from the singlet exciton generated by the first PL excitation and the light emission from the singlet exciton generated via the triplet exciton. Therefore, the luminous intensity derived from delayed fluorescence can be determined.
An example of a method of measuring a transient PL using
A transient PL measuring device 100 in
The sample housed in the sample chamber 102 is obtained by forming a thin film, in which a matrix material is doped with a doping material at a concentration of 12 mass %, on the quartz substrate.
The thin film sample housed in the sample chamber 102 is irradiated with the pulse laser from the pulse laser 101 to excite the doping material. Emission is extracted in a direction of 90 degrees with respect to a radiation direction of the excited light. The extracted emission is divided by the spectrometer 103 to form a two-dimensional image in the streak camera 104. As a result, the two-dimensional image is obtainable in which the ordinate axis represents a time, the abscissa axis represents a wavelength, and a bright spot represents a luminous intensity. When this two-dimensional image is taken out at a predetermined time axis, an emission spectrum in which the ordinate axis represents the luminous intensity and the abscissa axis represents the wavelength is obtainable. Moreover, when this two-dimensional image is taken out at the wavelength axis, a decay curve (transient PL) in which the ordinate axis represents a logarithm of the luminous intensity and the abscissa axis represents the time is obtainable.
For instance, a thin film sample A was prepared as described above from a reference compound H1 as the matrix material and a reference compound D1 as the doping material and was measured in terms of the transient PL.
The decay curve was analyzed with respect to the above thin film sample A and a thin film sample B. The thin film sample B was produced in the same manner as described above from a reference compound H2 as the matrix material and the reference compound D1 as the doping material.
As described above, an emission decay curve in which the ordinate axis represents the luminous intensity and the abscissa axis represents the time can be obtained by the transient PL measurement. Based on the emission decay curve, a fluorescence intensity ratio between fluorescence emitted from a singlet state generated by photo-excitation and delayed fluorescence emitted from a singlet state generated by reverse energy transfer via a triplet state can be estimated. In a delayed fluorescent material, a ratio of the intensity of the slowly decaying delayed fluorescence to the intensity of the promptly decaying fluorescence is relatively large.
Specifically, Prompt emission and Delay emission are present as emission from the delayed fluorescent material. Prompt emission is observed promptly when the excited state is achieved by exciting the compound of the exemplary embodiment with a pulse beam (i.e., a beam emitted from a pulse laser) having a wavelength absorbable by the delayed fluorescent material. Delay emission is observed not promptly when the excited state is achieved but after the excited state is achieved.
An amount of Prompt emission, an amount of Delay emission and a ratio between the amounts thereof can be obtained according to the method as described in “Nature 492, 234-238, 2012” (Reference Document 1). The amount of Prompt emission and the amount of Delay emission may be calculated using a device different from one described in Reference Document 1 or one shown in
Herein, a sample produced by the following method is used for measuring delayed fluorescence of the compound M2. For instance, the compound M2 is dissolved in toluene to prepare a dilute solution with an absorbance of 0.05 or less at the excitation wavelength to eliminate the contribution of self-absorption. In order to prevent quenching due to oxygen, the sample solution is frozen and degassed and then sealed in a cell with a lid under an argon atmosphere to obtain an oxygen-free sample solution saturated with argon.
The fluorescence spectrum of the sample solution is measured with a spectrofluorometer FP-8600 (produced by JASCO Corporation), and the fluorescence spectrum of a 9,10-diphenylanthracene ethanol solution is measured under the same conditions. Using the fluorescence area intensities of both spectra, the total fluorescence quantum yield is calculated by an equation (1) in Morris et al. J. Phys. Chem. 80 (1976) 969. An amount of Prompt emission, an amount of Delay emission and a ratio between the amounts thereof can be obtained according to the method as described in “Nature 492, 234-238, 2012” (Reference Document 1). The amount of Prompt emission and the amount of Delay emission may be calculated using a device different from one described in Reference Document 1 or one shown in
In the exemplary embodiment, provided that an amount of Prompt emission of a measurement target compound (compound M2) is denoted by XP and an amount of Delay emission is denoted by XD, a value of XD/XP is preferably 0.05 or more.
The amounts of Prompt emission and Delay emission and a ratio of the amounts thereof in compounds other than the compound M2 herein are measured in the same manner as those of the compound M2.
The compound M2 is preferably a compound represented by a formula (2) or a formula (22) below, more preferably a compound represented by the formula (2).
In the formula (2):
In the formula (2a): R1 to R8 are each independently a hydrogen atom or a substituent, or at least one combination of a combination of R1 and R2, a combination of R2 and R3, a combination of R3 and R4, a combination of R5 and R6, a combination of R6 and R7, or a combination of R7 and R8 are mutually bonded to form a ring;
R1 to R8 as a substituent are each independently a halogen atom, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkyl halide group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 60 ring carbon atoms, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy halide group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 ring carbon atoms, a substituted or unsubstituted alkylamino group having 2 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 60 ring carbon atoms, a thiol group, a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylthio group having 6 to 30 ring carbon atoms; and
* represents a bonding position to a carbon atom in a six-membered ring in the formula (2).
In the formula (2b):
In the formula (2c):
In the formula (211), R2009 and R2010 are each independently a hydrogen atom or a substituent, or bonded to a part of an adjacent cyclic structure to form a ring, or a combination of R2009 and R2010 are mutually bonded to form a ring.
In the formula (212), X201 is CR2011R2012, NR2013, a sulfur atom, or an oxygen atom, and R2011, R2012 and R2013 are each independently a hydrogen atom or a substituent, or R2011 and R2012 are mutually bonded to form a ring.
R2009, R2010, R2011, R2012 and R2013 as a substituent each independently represent the same as R1 to R8 as a substituent in the formula (2a).
In the formula (211), R2009 and R2010 are each independently bonded to a part of an adjacent cyclic structure to form a ring, which specifically means any of (I) to (IV) below.
In the formula (211), a combination of R2009 and R2010 are mutually bonded to form a ring, which specifically means (V) below.
(I) When the cyclic structures represented by the formula (211) are adjacent to each other, between the two adjacent rings, at least one combination of the following are mutually bonded to form a ring: R2009 of one of the rings and R2009 of the other of the rings; R2009 of one of the rings and R2010 of the other of the rings; or R2010 of one of the rings and R2010 of the other of the rings.
(II) When the cyclic structure represented by the formula (211) and the benzene ring having R25 to R28 in the formula (2b) are adjacent to each other, between the two adjacent rings, at least one combination of the following are mutually bonded to form a ring: R2009 of one of the rings and R25 of the other of the rings; R2009 of one of the rings and R28 of the other of the rings; R2010 of one of the rings and R25 of the other of the rings; or R2010 of one of the rings and R28 of the other of the rings.
(III) When the cyclic structure represented by the formula (211) and the benzene ring having R2001 to R2004 in the formula (2c) are adjacent to each other, between the two adjacent rings, at least one combination of the following are mutually bonded to form a ring: R2009 of one of the rings and R2001 of the other of the rings; R2009 of one of the rings and R2004 of the other of the rings; R2010 of one of the rings and R2001 of the other of the rings; or R2010 of one of the rings and R2004 of the other of the rings.
(IV) When the cyclic structure represented by the formula (211) and the benzene ring having R2005 to R2008 in the formula (2c) are adjacent to each other, between the two adjacent rings, at least one combination of the following are mutually bonded to form a ring: R2009 of one of the rings and R2005 of the other of the rings; R2009 of one of the rings and R2008 of the other of the rings; R2010 of one of the rings and R2005 of the other of the rings; or R2010 of one of the rings and R2008 of the other of the rings.
(V) The combination of R2009 and R2010 of the cyclic structure represented by the formula (211) are mutually bonded to form a ring. In other words, (V) means that the combination of R2009 and R2010, which are bonded to the same ring, are mutually bonded to form a ring.
In the compound M2, it is preferable that Rx is each independently a hydrogen atom, an unsubstituted aryl group having 6 to 30 ring carbon atoms, an unsubstituted heterocyclic group having 5 to 30 ring atoms, or an unsubstituted alkyl group having 1 to 30 carbon atoms, and when Rx is an unsubstituted heterocyclic group having 5 to 30 ring atoms, Rx as an unsubstituted heterocyclic group having 5 to 30 ring atoms is a pyridyl group, pyrimidinyl group, triazinyl group, dibenzofuranyl group, or dibenzothienyl group.
Herein, the triazinyl group refers to a group obtained by excluding one hydrogen atom from 1,3,5-triazine, 1,2,4-triazine, or 1,2,3-triazine.
The triazinyl group is preferably a group obtained by excluding one hydrogen atom from 1,3,5-triazine.
In the compound M2, it is more preferable that Rx is each independently a hydrogen atom, an unsubstituted aryl group having 6 to 30 ring carbon atoms, an unsubstituted dibenzofuranyl group, or an unsubstituted dibenzothienyl group.
In the compound M2 of the exemplary embodiment, it is still more preferable that Rx is a hydrogen atom.
In the compound M2 of the exemplary embodiment, it is preferable that R1 to R8, R21 to R28, R2001 to R2008, R2009 to R2010, and R2011 to R2013 as a substituent are each independently an unsubstituted aryl group having 6 to 30 ring carbon atoms, an unsubstituted heterocyclic group having 5 to 30 ring atoms, or an unsubstituted alkyl group having 1 to 30 carbon atoms.
In the compound M2 of the exemplary embodiment, it is preferable that D1 is a group represented by one of formulae (D-21) to (D-27) below.
In the formula (D-21), R83 to R90 are each independently a hydrogen atom or a substituent.
In the formulae (D-21) to (D-27):
In the compound M2 of the exemplary embodiment, it is also more preferable that D1 is a group represented by the formula (D-21), (D-23), (D-24) or (D-25).
In the compound M2 of the exemplary embodiment, it is also still more preferable that D1 is a group represented by the formula (D-21), (D-23), or (D-25).
In the compound M2 of the exemplary embodiment, it is preferable that R83 to R90, R201 to R260, R151 and R152 are each independently a hydrogen atom, an unsubstituted aryl group having 6 to 14 ring carbon atoms, an unsubstituted heterocyclic group having 5 to 14 ring atoms, or an unsubstituted alkyl group having 1 to 6 carbon atoms.
In the compound M2 of the exemplary embodiment, it is preferable that R83 to R90 and R201 to R260 are each a hydrogen atom.
In the compound M2 of the exemplary embodiment, it is preferable that R151 and R152 are each independently an unsubstituted aryl group having 6 to 14 ring carbon atoms, an unsubstituted heterocyclic group having 5 to 14 ring atoms, or an unsubstituted alkyl group having 1 to 6 carbon atoms.
In the formula (22), Ar1 is a group selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted phosphoryl group, a substituted silyl group, a cyano group, a nitro group, a carboxy group, and groups represented by formulae (1a) to (1j) below.
In the formula (22), ArEWG is a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms that includes at least one nitrogen atom in a ring, or an aryl group having 6 to 30 ring carbon atoms that is substituted by at least one cyano group.
In the formula (22), ArX is each independently a hydrogen atom or a substituent, and ArX as a substituent is a group selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted phosphoryl group, a substituted silyl group, a cyano group, a nitro group, a carboxy group, and groups represented by the formulae (1a) to (1j).
In the formula (22), n is 0, 1, 2, 3, 4 or 5, and when n is 2, 3, 4 or 5, a plurality of ArX are mutually the same or different.
In the formula (22), a ring (A) is a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heterocycle, the ring (A) is a five-membered ring, a six-membered ring, or a seven-membered ring. The ring (A) may be an aromatic hydrocarbon ring or a heterocycle. Ar1 and ArX are bonded to respective ones of elements forming the ring (A).
In the formula (22), at least one of Ar or ArX is a group selected from the group consisting of groups represented by the formulae (1a) to (1j).
In the formulae (1a) to (1j), X1 to X20 are each independently a nitrogen atom (N) or a carbon atom bonded with RA1 (C—RA1).
In the formula (1b), one of X5 to X8 is a carbon atom bonded to one of X9 to X12, and one of X9 to X12 is a carbon atom bonded to one of X5 to X8.
In the formula (1c), one of X5 to X8 is a carbon atom bonded to a nitrogen atom in a ring including A2.
In the formula (1e), one of X5 to X8 and X18 is a carbon atom bonded to one of X9 to X12, and one of X9 to X12 is a carbon atom bonded to one of X5 to X8 and X18.
In the formula (1f), one of X5 to X8 and X18 is a carbon atom bonded to one of X9 to X12 and X19, and one of X9 to X12 and X19 is a carbon atom bonded to one of X5 to X8 and X18.
In the formula (1g), one of X5 to X8 is a carbon atom bonded to one of X9 to X12 and X19, and one of X9 to X12 and X19 is a carbon atom bonded to one of X5 to X8.
In the formula (1h), one of X5 to X8 and X18 is a carbon atom bonded to a nitrogen atom in a ring including A2.
In the formula (1i), one of X5 to X8 and X18 is a carbon atom bonded to a nitrogen atom that links a ring including X9 to X12 and X19 with a ring including X13 to X16 and X20.
In the formula (1j), one of X5 to X8 is a carbon atom bonded to a nitrogen atom that links a ring including X9 to X12 and X19 with a ring including X13 to X16 and X20.
RA1 is each independently a hydrogen atom or a substituent, or at least one combination of combinations of a plurality of RA1 are mutually directly bonded to form a ring or bonded via a hetero atom to form a ring.
RA1 as a substituent is a group selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted phosphoryl group, a substituted silyl group, a cyano group, a nitro group, and a carboxy group.
When a plurality of RA1 as a substituent are present, the plurality of RA1 are mutually the same or different.
In the formula (1a), when X1 to X8 are each a carbon atom bonded with RA1 (C—RA1), a plurality of RA1 preferably form no ring.
In the formulae (1a) to (1j), * represents a bonding position to the ring (A).
In the formulae (1a) to (1j), A1 and A2 are each independently a single bond, an oxygen atom (O), a sulfur atom (S), C(R2021)(R2022), Si(R2023)(R2024), C(═O), S(═O), SO2 or N(R2025). R2021 to R2025 are each independently a hydrogen atom or a substituent, and R2021 to R2025 as a substituent are each independently a group selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted phosphoryl group, a substituted silyl group, a cyano group, a nitro group, and a carboxy group.
In the formulae (1a) to (1j), Ara is a group selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted phosphoryl group, and a substituted silyl group. Ara is preferably a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms.
The formula (1a) is represented by a formula (1aa) below when A1 is a single bond, represented by a formula (1ab) below when A1 is O, represented by a formula (1ac) below when A1 is S, represented by a formula (1ad) below when A1 is C(R2021)(R2022), represented by a formula (1ae) below when A1 is Si(R2023)(R2024), represented by a formula (1af) below when A1 is C(═O), represented by a formula (1ag) below when A1 is S(═O), represented by a formula (1ah) below when A1 is SO2, and represented by a formula (1ai) below when A1 is N(R2025). In the formulae (1aa) to (1ai), X1 to X8 and R2021 to R2025 represent the same as described above. Linkages between rings via A1 and A2 in the formulae (1b), (1c), (1e) and (1g) to (1j) are the same as those in the formulae (1aa) to (1ai). In the formula (1aa), when X1 to X8 are each a carbon atom bonded with RA1 (C—RA1), a plurality of RA1 as a substituent preferably form no ring.
The compound M2 is preferably a compound represented by a formula (221) below.
Ar1, ArEWG, ArX, n and a ring (A) in the formula (221) respectively represent the same as Ar1, ArEWG, ArX, n and the ring (A) in the formula (22).
The compound M2 is also preferably a compound represented by a formula (222) below.
In the formula (222), Y1 to Y5 are each independently a nitrogen atom (N), a carbon atom bonded with a cyano group (C—CN), or a carbon atom bonded with RA2 (C—RA2), and at least one of Y1 to Y5 is N or C—CN. A plurality of RA2 are mutually the same or different. RA2 is each independently a hydrogen atom or a substituent, and RA2 as a substituent is a group selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted phosphoryl group, a substituted silyl group, a cyano group, a nitro group, and a carboxy group.
A plurality of RA2 are mutually the same or different.
In the formula (222), Ar1 represents the same as Ar1 in the formula (22).
In the formula (222), Ar2 to Ar5 are each independently a hydrogen atom or a substituent, and Ar2 to Ar5 as a substituent are each independently a group selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted phosphoryl group, a substituted silyl group, a cyano group, a nitro group, a carboxy group, and groups represented by the formulae (1a) to (1c).
In the formula (222), at least one of Ar1 to Ar5 is a group selected from the group consisting of groups represented by the formulae (1a) to (1c).
The compound M2 is also preferably a compound represented by a formula (11aa), (11bb) or (11cc) below.
In the formulae (11 aa), (11 bb) and (11 cc), Y1 to Y5, RA2, Ar2 to Ar5, X1 to X16, RA1 and Ara respectively represent the same as the above-described Y1 to Y5, RA2, Ar2 to Ar5, X1 to X16, RA1 and Ara.
The compound M2 is exemplified by a compound represented by a formula (23) below.
In the formula (23):
In the formula (23a):
In the formula (23), c is preferably 0 or 1.
Cz is also preferably represented by a formula (23b), (23c) or (23d) below.
In the formulae (23b), (23c) and (23d), Y21 to Y28 and Y51 to Y58 are each independently a nitrogen atom or CRA4.
In the formula (23b), at least one of Y25 to Y28 is a carbon atom bonded to one of Y51 to Y54, and at least one of Y51 to Y54 is a carbon atom bonded to one of Y25 to Y28.
In the formula (23c), at least one of Y25 to Y28 is a carbon atom bonded to a nitrogen atom in a five-membered ring of a nitrogen-containing fused ring including Y51 to Y58.
In the formula (23d), *a and *b each represent a bonding position to one of Y21 to Y28, at least one of Y25 to Y28 is the bonding position represented by *a, and at least one of Y25 to Y28 is the bonding position represented by *b.
n is 1, 2, 3 or 4;
RA4 is each independently a hydrogen atom or a substituent, or at least one combination of combinations of a plurality of RA4 are mutually bonded to form a ring; each RA4 as a substituent is independently a group selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted phosphoryl group, a substituted silyl group, a cyano group, a nitro group, and a carboxy group;
a plurality of RA4 are mutually the same or different;
Z21 and Z22 are each independently any one selected from the group consisting of an oxygen atom, a sulfur atom, NR45 and CR46R47;
R45 is a hydrogen atom or a substituent;
R46 and R47 are each independently a hydrogen atom or a substituent, or a combination of R46 and R47 are mutually bonded to form a ring;
R45, R46 and R47 as a substituent are each independently a substituent selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted fluoroalkyl group having 1 to 30 carbon atoms, <<nret>>
a substituted or unsubstituted cycloalkyl group having 3 to 30 ring carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted phosphoryl group, a substituted silyl group, a cyano group, a nitro group, and a carboxy group;
a plurality of R45 are mutually the same or different;
a plurality of R46 are mutually the same or different;
a plurality of R47 are mutually the same or different; and
* represents a bonding position to a carbon atom in a structure of a linking group represented by L23, or a bonding position to a carbon atom in a cyclic structure represented by Az.
Z21 is preferably NR45.
When Z21 is NR45, R45 is preferably a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms.
Z22 is preferably NR45.
When Z22 is NR45, R45 is preferably a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms.
Y51 to Y58 are preferably CRA4, provided that at least one of Y51 to Y58 is a carbon atom bonded to a cyclic structure represented by the formula (23a).
It is also preferable that Cz is represented by the formula (23d) and n is 1.
Az is preferably a cyclic structure selected from the group consisting of a substituted or unsubstituted pyrimidine group and a substituted or unsubstituted triazine group.
Az is a cyclic structure selected from the group consisting of a substituted pyrimidine ring and a substituted triazine ring, in which a substituent for each of the substituted pyrimidine ring and the substituted triazine ring is more preferably a group selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, still more preferably a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms.
When a pyrimidine ring and a triazine ring as Az have a substituted or unsubstituted aryl group as a substituent, the aryl group preferably has 6 to 20 ring carbon atoms, more preferably 6 to 14 ring carbon atoms, still more preferably 6 to 12 ring carbon atoms.
When Az has a substituted or unsubstituted aryl group as a substituent, the substituent is preferably a substituent selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted terphenyl group, and a substituted or unsubstituted fluorenyl group, more preferably a substituent selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, and a substituted or unsubstituted naphthyl group.
When Az has a substituted or unsubstituted heteroaryl group as a substituent, the substituent is preferably a substituent selected from the group consisting of a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted dibenzothiophenyl group.
It is preferable that RA4 is each independently a hydrogen atom or a substituent, and RA4 as a substituent is a substituent selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms and a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms.
When RA4 as a substituent is a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, RA4 as a substituent is preferably a substituent selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted terphenyl group, and a substituted or unsubstituted fluorenyl group, more preferably a substituent selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, and a substituted or unsubstituted naphthyl group.
When RA4 as a substituent is a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, RA4 as a substituent is preferably a substituent selected from the group consisting of a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted dibenzothiophenyl group.
R45, R46 and R47 as a substituent are preferably each independently a substituent selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, and a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
The compound M2 of the exemplary embodiment can be manufactured by a known method.
Specific examples of the compound M2 in the exemplary embodiment includes compounds below. However, the invention is by no means limited to the specifically listed compounds.
Relationship between Compound M3 and Compound M2 in Emitting Layer
In the organic EL device according to the exemplary embodiment, a singlet energy S1(M3) of the compound M3 and a singlet energy S1(M2) of the compound M2 satisfy a relationship of a numerical formula (Numerical Formula 1) below.
S
1(M3)>S1(M2) (Numerical Formula 1)
An energy gap T77K(M3) at 77K of the compound M3 is preferably larger than an energy gap T77K(M2) at 77K of the compound M2. In other words, a relationship of a numerical formula (Numerical Formula 11) below is preferably satisfied.
T
77K(M3)>T77K(M2) (Numerical Formula 11)
When the organic EL device according to the exemplary embodiment emits light, it is preferable that the compound M3 does not mainly emit light in the emitting layer.
Relationship between Triplet Energy and Energy Gap at 77K
Here, a relationship between a triplet energy and an energy gap at 77K will be described. In the exemplary embodiment, the energy gap at 77K is different from a typical triplet energy in some aspects.
The triplet energy is measured as follows. First, a solution in which a compound (measurement target) is dissolved in an appropriate solvent is encapsulated in a quartz glass tube to prepare a sample. A phosphorescence spectrum (ordinate axis: phosphorescent luminous intensity, abscissa axis: wavelength) of the sample is measured at a low temperature (77K). A tangent is drawn to the rise of the phosphorescence spectrum close to the short-wavelength region. The triplet energy is calculated by a predetermined conversion equation based on a wavelength value at an intersection of the tangent and the abscissa axis.
Herein, among the compounds of the exemplary embodiment, the thermally activated delayed fluorescent compound is preferably a compound having a small ΔST. When ΔST is small, intersystem crossing and inverse intersystem crossing are likely to occur even at a low temperature (77K), so that the singlet state and the triplet state coexist. As a result, the spectrum to be measured in the same manner as the above includes emission from both the singlet state and the triplet state. Although it is difficult to distinguish from which state, the singlet state or the triplet state, light is emitted, the value of the triplet energy is basically considered dominant.
Accordingly, in the exemplary embodiment, the triplet energy is measured by the same method as a typical triplet energy T, but a value measured in the following manner is referred to as an energy gap T77K in order to differentiate the measured energy from the typical triplet energy in a strict meaning. The measurement target compound is dissolved in EPA (diethylether:isopentane:ethanol=5:5:2 in volume ratio) at a concentration of 10 μmol/L, and the obtained solution is put in a quartz cell to provide a measurement sample. A phosphorescence spectrum (ordinate axis: phosphorescent luminous intensity, abscissa axis: wavelength) of the sample is measured at a low temperature (77K). A tangent is drawn to the rise of the phosphorescence spectrum close to the short-wavelength region. An energy amount is calculated by a conversion equation (F1) below based on a wavelength value λedge[nm] at an intersection of the tangent and the abscissa axis and is defined as an energy gap T77K at 77K.
T
77K [eV]=1239.85/λedge Conversion Equation (F1):
The tangent to the rise of the phosphorescence spectrum close to the short-wavelength region is drawn as follows. While moving on a curve of the phosphorescence spectrum from the short-wavelength region to the local maximum value closest to the short-wavelength region among the local maximum values of the phosphorescence spectrum, a tangent is checked at each point on the curve toward the long-wavelength of the phosphorescence spectrum. An inclination of the tangent is increased along the rise of the curve (i.e., a value of the ordinate axis is increased). A tangent drawn at a point of the local maximum inclination (i.e., a tangent at an inflection point) is defined as the tangent to the rise of the phosphorescence spectrum close to the short-wavelength region.
A local maximum point where a peak intensity is 15% or less of the maximum peak intensity of the spectrum is not counted as the above-mentioned local maximum peak intensity closest to the short-wavelength region. The tangent drawn at a point that is closest to the local maximum peak intensity closest to the short-wavelength region and where the inclination of the curve is the local maximum is defined as a tangent to the rise of the phosphorescence spectrum close to the short-wavelength region.
For phosphorescence measurement, a spectrophotofluorometer body F-4500 (manufactured by Hitachi High-Technologies Corporation) is usable. Any device for phosphorescence measurement is usable. A combination of a cooling unit, a low temperature container, an excitation light source and a light-receiving unit may be used for phosphorescence measurement.
A method of measuring a singlet energy S1 with use of a solution (occasionally referred to as a solution method) is exemplified by a method below.
A toluene solution of a measurement target compound at a concentration of 10 μmol/L is prepared and put in a quartz cell. An absorption spectrum (ordinate axis: absorption intensity, abscissa axis: wavelength) of the thus-obtained sample is measured at a normal temperature (300K). A tangent is drawn to the fall of the absorption spectrum close to the long-wavelength region, and a wavelength value λedge(nm) at an intersection of the tangent and the abscissa axis is assigned to a conversion equation (F2) below to calculate singlet energy.
S
1 [eV]=1239.85/λedge Conversion Equation (F2):
Any device for measuring absorption spectrum is usable. For instance, a spectrophotometer (U3310 manufactured by Hitachi, Ltd.) is usable.
The tangent to the fall of the absorption spectrum close to the long-wavelength region is drawn as follows. While moving on a curve of the absorption spectrum from the local maximum value closest to the long-wavelength region, among the local maximum values of the absorption spectrum, in a long-wavelength direction, a tangent at each point on the curve is checked. An inclination of the tangent is decreased and increased in a repeated manner as the curve falls (i.e., a value of the ordinate axis is decreased). A tangent drawn at a point where the inclination of the curve is the local minimum closest to the long-wavelength region (except when absorbance is 0.1 or less) is defined as the tangent to the fall of the absorption spectrum close to the long-wavelength region.
The local maximum absorbance of 0.2 or less is not counted as the above-mentioned local maximum absorbance closest to the long-wavelength region.
In the exemplary embodiment, a difference (S1−T77K) between the singlet energy S1 and the energy gap T77K at 77K is defined as ΔST.
In the exemplary embodiment, a difference ΔST(M2) between the singlet energy S1(M2) of the compound M2 and the energy gap T77K(M2) at 77K of the compound M2 is preferably less than 0.3 eV, more preferably less than 0.2 eV, still more preferably less than 0.1 eV, and still further more preferably less than 0.01 eV. In other words, ΔST(M2) preferably satisfies a relationship of one of numerical formulae (Numerical Formula 1A) to (Numerical Formula 1D) below.
ΔST(M2)=S1(M2)−T77K(M2)<0.3 eV (Numerical Formula 1A)
ΔST(M2)=S1(M2)−T77K(M2)<0.2 eV (Numerical Formula 1B)
ΔST(M2)=S1(M2)−T77K(M2)<0.1 eV (Numerical Formula 1C)
ΔST(M2)=S1(M2)−T77K(M2)<0.01 eV (Numerical Formula 1D)
The film thickness of the emitting layer of the organic EL device in the exemplary embodiment is preferably in a range from 5 nm to 50 nm, more preferably in a range from 7 nm to 50 nm, most preferably in a range from 10 nm to 50 nm. When the film thickness of the emitting layer is 5 nm or more, the formation of the emitting layer and the adjustment of the chromaticity are easy. When the film thickness of the emitting layer is 50 nm or less, an increase in the drive voltage is likely to be reduced.
For instance, content ratios of the compound M2 and the compound M3 in the emitting layer preferably fall within ranges shown below.
The content ratio of the compound M2 is preferably in a range from 10 mass % to 80 mass %, more preferably in a range from 10 mass % to 60 mass %, and still more preferably in a range from 20 mass % to 60 mass %.
The content ratio of the compound M3 is preferably in a range from 20 mass % to 90 mass %, more preferably in a range from 40 mass % to 90 mass %, and still more preferably in a range from 40 mass % to 80 mass %.
It should be noted that the emitting layer of the exemplary embodiment may contain a material other than the compound M2 and the compound M3.
The emitting layer may contain a single type of the compound M2 or may contain two or more types of the compound M2. The emitting layer may contain a single type of the compound M3 or may contain two or more types of the compound M3.
The inverse intersystem crossing caused in the compound M2 enables light emission from the lowest singlet state S1(M2) of the compound M2 to be observed when the emitting layer does not contain a fluorescent dopant with the lowest singlet state S1 smaller than the lowest singlet state S1(M2) of the compound M2. It is inferred that the internal quantum efficiency can be theoretically raised up to 100% also by using delayed fluorescence by the TADF mechanism.
In the organic EL device according to the exemplary embodiment, the emitting layer contains the delayed fluorescent compound M2 and the compound M3 having a larger singlet energy than the compound M2.
According to the exemplary embodiment, the organic EL device having a high performance, particularly, an improved luminous efficiency is achievable.
The organic EL device according to the exemplary embodiment is usable in an electronic device such as a display device and a light-emitting unit.
An arrangement of the organic EL device will be further described below.
The substrate is used as a support for the organic EL device. For instance, glass, quartz, plastics and the like are usable for the substrate. A flexible substrate is also usable. The flexible substrate is a bendable substrate, which is exemplified by a plastic substrate. Examples of the material for the plastic substrate include polycarbonate, polyarylate, polyethersulfone, polypropylene, polyester, polyvinyl fluoride, polyvinyl chloride, polyimide, and polyethylene naphthalate. Moreover, an inorganic vapor deposition film is also usable.
Metal, an alloy, an electrically conductive compound, a mixture thereof, or the like having a large work function (specifically, 4.0 eV or more) is preferably used as the anode formed on the substrate. Specific examples of the material include ITO (Indium Tin Oxide), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide, indium oxide containing tungsten oxide and zinc oxide, and graphene. In addition, gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chrome (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), titanium (Ti), and nitrides of a metal material (e.g., titanium nitride) are usable.
The material is typically formed into a film by a sputtering method. For instance, the indium oxide-zinc oxide can be formed into a film by the sputtering method using a target in which zinc oxide in a range from 1 mass % to 10 mass % is added to indium oxide. Moreover, for instance, the indium oxide containing tungsten oxide and zinc oxide can be formed by the sputtering method using a target in which tungsten oxide in a range from 0.5 mass % to 5 mass % and zinc oxide in a range from 0.1 mass % to 1 mass % are added to indium oxide. In addition, the anode may be formed by a vacuum deposition method, a coating method, an inkjet method, a spin coating method or the like.
Among the organic layers formed on the anode, since the hole injecting layer adjacent to the anode is formed of a composite material into which holes are easily injectable irrespective of the work function of the anode, a material usable as an electrode material (e.g., metal, an alloy, an electroconductive compound, a mixture thereof, and the elements belonging to the group 1 or 2 of the periodic table) is also usable for the anode.
The elements belonging to the group 1 or 2 of the periodic table, which are a material having a small work function, specifically, an alkali metal such as lithium (Li) and cesium (Cs), an alkaline earth metal such as magnesium (Mg), calcium (Ca) and strontium (Sr), an alloy containing the alkali metal and the alkaline earth metal (e.g., MgAg, AlLi), a rare earth metal such as europium (Eu) and ytterbium (Yb), and an alloy containing the rare earth metal are usable for the anode. It should be noted that the vacuum deposition method and the sputtering method are usable for forming the anode using the alkali metal, alkaline earth metal and the alloy thereof. Further, when a silver paste is used for the anode, the coating method and the inkjet method are usable.
It is preferable to use metal, an alloy, an electroconductive compound, a mixture thereof, or the like having a small work function (specifically, 3.8 eV or less) for the cathode. Examples of materials for the cathode include elements belonging to the group 1 or 2 of the periodic table, specifically, an alkali metal such as lithium (Li) and cesium (Cs), an alkaline earth metal such as magnesium (Mg), calcium (Ca) and strontium (Sr), an alloy containing the alkali metal and the alkaline earth metal (e.g., MgAg, AlLi), a rare earth metal such as europium (Eu) and ytterbium (Yb), and an alloy containing the rare earth metal.
It should be noted that the vacuum deposition method and the sputtering method are usable for forming the cathode using the alkali metal, alkaline earth metal and the alloy thereof. Further, when a silver paste is used for the cathode, the coating method and the inkjet method are usable.
By providing the electron injecting layer, various conductive materials such as Al, Ag, ITO, graphene, and indium oxide-tin oxide containing silicon or silicon oxide may be used for forming the cathode regardless of the work function. The conductive materials can be formed into a film using the sputtering method, inkjet method, spin coating method and the like.
The hole injecting layer is a layer containing a substance exhibiting a high hole injectability. Examples of the substance exhibiting a high hole injectability include molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chrome oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, tungsten oxide, and manganese oxide.
In addition, the examples of the highly hole-injectable substance include: an aromatic amine compound, which is a low-molecule organic compound, such that 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (abbreviation: TDATA), 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), 4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl(abbreviation: DPAB), 4,4′-bis(N-{4-[N′-(3-methylphenyl)-N′-phenylamino]phenyl}-N-phenylamino)biphenyl (abbreviation: DNTPD), 1,3,5-tris[N-(4-diphenylaminophenyl)-N-phenylamino]benzene (abbreviation: DPA3B), 3-[N-(9-phenylcarbazole-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA1), 3,6-bis[N-(9-phenylcarbazole-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA2), and 3-[N-(1-naphthyl)-N-(9-phenylcarbazole-3-yl)amino]-9-phenylcarbazole (abbreviation: PCzPCN1); and dipyrazino[2,3-f:20,30-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN).
In addition, a high polymer compound (e.g., oligomer, dendrimer and polymer) is usable as the substance exhibiting a high hole injectability. Examples of the high-molecule compound include poly(N-vinylcarbazole) (abbreviation: PVK), poly(4-vinyltiphenylamine) (abbreviation: PVTPA), poly[N-(4-{N′-[4-(4-diphenylamino)phenyl]phenyl-N′-phenylamino}phenyl)methacrylamide](abbreviation: PTPDMA), and poly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine] (abbreviation: Poly-TPD). Moreover, an acid-added high polymer compound such as poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonic acid) (PEDOT/PSS) and polyaniline/poly(styrene sulfonic acid) (PAni/PSS) are also usable.
The hole transporting layer is a layer containing a highly hole-transporting substance. An aromatic amine compound, carbazole derivative, anthracene derivative and the like are usable for the hole transporting layer. Specific examples of a material for the hole transporting layer include 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB), N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (abbreviation: TPD), 4-phenyl-4′-(9-phenylfluorene-9-yl)tiphenylamine (abbreviation: BAFLP), 4,4′-bis[N-(9,9-dimethylfluorene-2-yl)-N-phenylamino]biphenyl (abbreviation: DFLDPBi), 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (abbreviation: TDATA), 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), and 4,4′-bis[N-(spiro-9,9′-bifluorene-2-yl)-N-phenylamino]biphenyl (abbreviation: BSPB). The above-described substances mostly have a hole mobility of 10−6 cm2/(V·s) or more.
For the hole transporting layer, a carbazole derivative such as CBP, 9-[4-(N-carbazolyl)]phenyl-10-phenylanthracene (CzPA), and 9-phenyl-3-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (PCzPA) and an anthracene derivative such as t-BuDNA, DNA, and DPAnth may be used. A high polymer compound such as poly(N-vinylcarbazole) (abbreviation: PVK) and poly(4-vinyltriphenylamine) (abbreviation: PVTPA) is also usable.
However, in addition to the above substances, any substance exhibiting a higher hole transportability than an electron transportability may be used. It should be noted that the layer containing the substance exhibiting a high hole transportability may be not only a single layer but also a laminate of two or more layers formed of the above substance(s).
When the hole transporting layer includes two or more layers, one of the layers with a larger energy gap is preferably provided closer to the emitting layer. Such a material is exemplified by a compound EBL used in Examples described later.
The electron transporting layer is a layer containing a highly electron-transporting substance. For the electron transporting layer, 1) a metal complex such as an aluminum complex, beryllium complex, and zinc complex, 2) a hetero aromatic compound such as imidazole derivative, benzimidazole derivative, azine derivative, carbazole derivative, and phenanthroline derivative, and 3) a high polymer compound are usable. Specifically, as a low-molecule organic compound, a metal complex such as Alq, tris(4-methyl-8-quinolinato)aluminum (abbreviation: Almq3), bis(10-hydroxybenzo[h]quinolinato)beryllium (abbreviation: BeBq2), BAlq, Znq, ZnPBO and ZnBTZ is usable. In addition to the metal complex, a heteroaromatic compound such as 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis[5-(ptert-butylphenyl)-1,3,4-oxadiazole-2-yl]benzene (abbreviation: OXD-7), 3-(4-tert-butylphenyl)-4-phenyl-5-(4-biphenylyl)-1,2,4-triazole (abbreviation: TAZ), 3-(4-tert-butylphenyl)-4-(4-ethylphenyl)-5-(4-biphenylyl)-1,2,4-triazole (abbreviation: p-EtTAZ), bathophenanthroline (abbreviation: BPhen), bathocuproine (abbreviation: BCP), and 4,4′-bis(5-methylbenzoxazole-2-yl)stilbene (abbreviation: BzOs) is usable. In the exemplary embodiment, a benzimidazole compound is preferably usable. The above-described substances mostly have an electron mobility of 10−6 cm2/(V·s) or more. It should be noted that any substance other than the above substance may be used for the electron transporting layer as long as the substance exhibits a higher electron transportability than the hole transportability. The electron transporting layer may be provided in the form of a single layer or a laminate of two or more layers of the above substance(s).
Further, a high polymer compound is usable for the electron transporting layer. For instance, poly[(9,9-dihexylfluorene-2,7-diyl)-co-(pyridine-3,5-diyl)](abbreviation: PF-Py), poly[(9,9-dioctylfluorene-2,7-diyl)-co-(2,2′-bipyridine-6,6′-diyl)] (abbreviation: PF-BPy) and the like are usable.
The electron injecting layer is a layer containing a highly electron-injectable substance. Examples of a material for the electron injecting layer include an alkali metal, alkaline earth metal and a compound thereof, examples of which include lithium (Li), cesium (Cs), calcium (Ca), lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF2), and lithium oxide (LiOx). In addition, the alkali metal, alkaline earth metal or the compound thereof may be added to the substance exhibiting the electron transportability in use. Specifically, for instance, magnesium (Mg) added to Alq may be used. In this case, the electrons can be more efficiently injected from the cathode.
Alternatively, the electron injecting layer may be provided by a composite material in a form of a mixture of the organic compound and the electron donor. Such a composite material exhibits excellent electron injectability and electron transportability since electrons are generated in the organic compound by the electron donor. In this case, the organic compound is preferably a material excellent in transporting the generated electrons. Specifically, the above examples (e.g., the metal complex and the hetero aromatic compound) of the substance forming the electron transporting layer are usable. As the electron donor, any substance exhibiting electron donating property to the organic compound is usable. Specifically, the electron donor is preferably alkali metal, alkaline earth metal and rare earth metal such as lithium, cesium, magnesium, calcium, erbium and ytterbium. The electron donor is also preferably alkali metal oxide and alkaline earth metal oxide such as lithium oxide, calcium oxide, and barium oxide. Moreover, a Lewis base such as magnesium oxide is usable. Further, the organic compound such as tetrathiafulvalene (abbreviation: TTF) is usable.
A method for forming each layer of the organic EL device in the exemplary embodiment is subject to no limitation except for the above particular description. However, known methods of dry film-forming such as vacuum deposition, sputtering, plasma or ion plating and wet film-forming such as spin coating, dipping, flow coating or ink-jet are applicable.
A thickness of each of the organic layers in the organic EL device according to the exemplary embodiment is not limited except for the above particular description. In general, the thickness preferably ranges from several nanometers to 1 μm because excessively small film thickness is likely to cause defects (e.g. pin holes) and excessively large thickness leads to the necessity of applying high voltage and consequent reduction in efficiency.
An arrangement of an organic EL device according to a second exemplary embodiment of the invention will be described below. In the description of the second exemplary embodiment, the same components as those in the first exemplary embodiment are denoted by the same reference signs and names to simplify or omit an explanation of the components. In the second exemplary embodiment, the same materials and compounds as described in the first exemplary embodiment are usable, unless otherwise specified.
The organic EL device according to the second exemplary embodiment is different from the organic EL device according to the first exemplary embodiment in that the emitting layer further includes a fluorescent compound M1. The second exemplary embodiment is the same as the first exemplary embodiment in other respects.
Specifically, in the second exemplary embodiment, the emitting layer contains the compound M3 represented by the formula (11), (12) or (13) below, a delayed fluorescent compound M2, and a fluorescent compound M1.
In this arrangement, it is preferable that the compound M1 is a dopant material, the compound M2 is a host material, and the compound M3 is not a dopant material.
The emitting layer of the exemplary embodiment preferably contains the fluorescent compound M1.
The compound M1 of the exemplary embodiment is not a phosphorescent metal complex. The compound M1 is preferably not a heavy-metal complex. The compound M1 is also preferably not a metal complex.
The compound M1 of the exemplary embodiment is preferably a compound not exhibiting thermally activated delayed fluorescence.
A fluorescent material is usable as the compound M1 of the exemplary embodiment. Specific examples of the fluorescent material include a bisarylaminonaphthalene derivative, aryl-substituted naphthalene derivative, bisarylaminoanthracene derivative, aryl-substituted anthracene derivative, bisarylaminopyrene derivative, aryl-substituted pyrene derivative, bisarylamino chrysene derivative, aryl-substituted chrysene derivative, bisarylaminofluoranthene derivative, aryl-substituted fluoranthene derivative, indenoperylene derivative, acenaphthofluoranthene derivative, compound including a boron atom, pyromethene boron complex compound, compound having a pyromethene skeleton, metal complex of the compound having a pyrromethene skeleton, diketopyrrolopyrrole derivative, perylene derivative, and naphthacene derivative.
The compound M1 of the exemplary embodiment is preferably a compound represented by a formula (20) below.
In the formula (20):
When the compound M1 is a fluorescent compound, the compound M1 preferably emits light having a main peak wavelength in a range from 400 nm to 700 nm.
Herein, the main peak wavelength means a peak wavelength of a fluorescence spectrum exhibiting a maximum luminous intensity among fluorescence spectra measured in a toluene solution in which a measurement target compound is dissolved at a concentration ranging from 10−6 mol/l to 10−5 mol/l. A spectrophotofluorometer (F-7000 manufactured by Hitachi High-Tech Science Corporation) is used as a measurement device.
The compound M1 preferably exhibits red or green light emission.
Herein, the red light emission refers to light emission whose main peak wavelength of fluorescence spectrum is in a range from 600 nm to 660 nm.
When the compound M1 is a red fluorescent compound, the main peak wavelength of the compound M1 is preferably in a range from 600 nm to 660 nm, more preferably in a range from 600 nm to 640 nm, and still more preferably in a range from 610 nm to 630 nm.
Herein, the green light emission refers to light emission whose main peak wavelength of fluorescence spectrum is in a range from 500 nm to 560 nm.
When the compound M1 is a green fluorescent compound, the main peak wavelength of the compound M1 is preferably in a range from 500 nm to 560 nm, more preferably in a range from 500 nm to 540 nm, and still more preferably in a range from 510 nm to 540 nm.
Herein, the blue light emission refers to light emission whose main peak wavelength of fluorescence spectrum is in a range from 430 nm to 480 nm.
When the compound M1 is a blue fluorescent compound, the main peak wavelength of the compound M1 is preferably in a range from 430 nm to 480 nm, more preferably in a range from 440 nm to 480 nm.
A main peak wavelength of the light emitted from the organic EL device is measured as follows.
Voltage is applied on the organic EL devices such that a current density becomes 10 mA/cm2, where spectral radiance spectrum is measured by a spectroradiometer CS-2000 (manufactured by Konica Minolta, Inc.).
A peak wavelength of an emission spectrum, at which the luminous intensity of the resultant spectral radiance spectrum is at the maximum, is measured and defined as the main peak wavelength (unit: nm).
The compound M1 can be manufactured by a known method.
Specific examples of a compound represented by the formula (20) are shown below. However, the invention is by no means limited to the specifically listed compounds.
A coordinate bond between a boron atom and a nitrogen atom in a pyrromethene skeleton is shown by various means such as a solid line, a broken line, an arrow, and omission. Herein, the coordinate bond is shown by a solid line or a broken line, or the description of the coordinate bond is omitted.
Relationship between Compound M3, Compound M2 and Compound M1 in Emitting Layer
In the organic EL device according to the exemplary embodiment, a singlet energy S1(M1) of the compound M1 and a singlet energy S1(M2) of the compound M2 satisfy a relationship of a numerical formula (Numerical Formula 2) below.
S
1(M2)>S1(M1) (Numerical Formula 2)
Moreover, the singlet energy S1(M3) of the compound M3 is preferably larger than the singlet energy S1(M1) of the compound M1.
S
1(M3)>S1(M1) (Numerical Formula 2A)
The singlet energy S1(M3) of the compound M3, the singlet energy S1(M2) of the compound M2, and the singlet energy S1(M1) of the compound M1 preferably satisfy a relationship of a numerical formula (Numerical Formula 2B) below.
S
1(M3)>S1(M2)>S1(M1) (Numerical Formula 2B)
It is preferable that mainly the fluorescent compound M1 emits light in the emitting layer when the organic EL device of the exemplary embodiment emits light.
The organic EL device according to the exemplary embodiment preferably emits red light or green light.
Content ratios of the compound M3, the compound M2, and the compound M1 in the emitting layer preferably fall, for instance, within a range below.
The content ratio of the compound M3 is preferably in a range from 10 mass % to 80 mass %.
The content ratio of the compound M2 is preferably in a range from 10 mass % to 80 mass %, more preferably in a range from 10 mass % to 60 mass %, and still more preferably in a range from 20 mass % to 60 mass %.
The content ratio of the compound M1 is preferably in a range from 0.01 mass % to 10 mass %, more preferably in a range from 0.01 mass % to 5 mass %, and still more preferably in a range from 0.01 mass % to 1 mass %.
The upper limit of a total of the content ratios of the compound M3, the compound M2, and the compound M1 in the emitting layer is 100 mass %. It should be noted that the emitting layer of the exemplary embodiment may further contain material(s) other than the compounds M3, M2 and M1.
The emitting layer may contain a single type of the compound M3 or may contain two or more types of the compound M3. The emitting layer may contain a single type of the compound M2 or may contain two or more types of the compound M2. The emitting layer may contain a single type of the compound M1 or may contain two or more types of the compound M1.
As shown in
The organic EL device according to the second exemplary embodiment contains the delayed fluorescent compound M2, the compound M3 having the singlet energy larger than that of the compound M2, and the compound M1 having the singlet energy smaller than that of the delayed fluorescent compound M2 in the emitting layer.
According to the second exemplary embodiment, the organic EL device having a high performance, particularly, an improved luminous efficiency is achievable.
The organic EL device according to the second exemplary embodiment is usable in an electronic device such as a display device and a light-emitting unit.
A compound of a third exemplary embodiment is a compound represented by a formula (121) or (122) below. A compound falling under the formula (121) or (122) among the specific examples of the compound M3 of the first exemplary embodiment is also used as a specific example of the compound of the third exemplary embodiment.
In the formulae (121) and (122):
In the formulae (121) and (122): when a carbon atom bonded to R15 is bonded to *2, a hydrogen atom represented by R15, a substituent represented by R15, and a ring formed by involving R15 are not present.
In the formulae (121) and (122): when a carbon atom bonded to R17 is bonded to *2, a hydrogen atom represented by R17, a substituent represented by R17, and a ring formed by involving R17 are not present.
In the formulae (121) and (122): when a carbon atom bonded to R18 is bonded to *2, a hydrogen atom represented by R18, a substituent represented by R18, and a ring formed by involving R18 are not present.
In the formulae (121) and (122): when a carbon atom bonded to R25 is bonded to *1, a hydrogen atom represented by R25, a substituent represented by R25, and a ring formed by involving R25 are not present.
In the formulae (121) and (122): when a carbon atom bonded to R27 is bonded to *1, a hydrogen atom represented by R27, a substituent represented by R27, and a ring formed by involving R27 are not present.
In the formulae (121) and (122): when a carbon atom bonded to R28 is bonded to *1, a hydrogen atom represented by R28, a substituent represented by R28, and a ring formed by involving R28 are not present.
In the formulae (121) and (122): it is preferable that a combination of R11 and R12, a combination of R12 and R13, a combination of R13 and R14, a combination of R15 and R16, a combination of R16 and R17, and a combination of R17 and R18 are not mutually bonded.
In the formulae (121) and (122): it is preferable that a combination of R21 and R22, a combination of R22 and R23, a combination of R23 and R24, a combination of R15 and R16, a combination of R26 and R27, and a combination of R27 and R28 are not mutually bonded.
In the formulae (121) and (122): it is preferable that a combination of R31 and R32, a combination of R32 and R33, a combination of R33 and R34, a combination of R35 and R36, a combination of R3 and R37, and a combination of R37 and R38 are not mutually bonded.
The compound of the third exemplary embodiment is preferably a compound represented by the formula (121).
In the compound of the third exemplary embodiment, A2 is preferably a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 18 ring atoms.
In the compound of the third exemplary embodiment, A2 is more preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted fluorenyl group, or a group represented by the formula (14).
In the compound of the third exemplary embodiment, it is preferable that L2 is a single bond and A2 is a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 18 ring atoms.
In the compound of the third exemplary embodiment, it is more preferable that L2 is a single bond and A2 is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted fluorenyl group, or a group represented by the formula (14).
In the compound of the third exemplary embodiment, it is still more preferable that L2 is a single bond and A2 is an unsubstituted phenyl group.
In the compound of the third exemplary embodiment, it is preferable that R11 to R18, R21 to R28 and R31 to R38 are each independently a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and R39 is a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
In the compound of the third exemplary embodiment, it is more preferable that R11 to R18, R21 to R28 and R31 to R38 are each independently a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and R39 is a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms.
In the compound of the third exemplary embodiment, it is still more preferable that R11 to R18, R21 to R28 and R31 to R38 are each a hydrogen atom and R39 is a substituted or unsubstituted phenyl group.
In the compound of the third exemplary embodiment, it is preferable that L1 and L2 are each independently a single bond or a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms.
In the compound of the third exemplary embodiment, it is more preferable that L1 and L2 are each independently a substituted or unsubstituted phenylene group, a substituted or unsubstituted parabiphenylene group, or a substituted or unsubstituted paraterphenylene group.
In the compound of the third exemplary embodiment, it is still more preferable that L1 and L2 are each independently a substituted or unsubstituted parabiphenylene group or a substituted or unsubstituted paraterphenylene group.
In the compound of the third exemplary embodiment, it is also preferable that L1 and L2 are each independently a single bond or at least one group selected from the group consisting of groups represented by the formulae (L1) to (L7).
In the compound of the third exemplary embodiment, it is also more preferable that L2 is a single bond or a group represented by one of the formulae (L3), (L4) and (L6).
In the compound of the third exemplary embodiment, a substituent for “substituted or unsubstituted” group is each independently preferably a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 30 carbon, <<nret>>
more preferably an unsubstituted aryl group having 6 to 30 ring carbon atoms, an unsubstituted heterocyclic group having 5 to 30 ring atoms, or an unsubstituted alkyl group having 1 to 30 carbon atoms.
The compound of the third exemplary embodiment corresponds to a compound of an example of the compound M3 described in the first exemplary embodiment. Therefore, specific examples of the compound of the third exemplary embodiment are also shown in the examples of the compound M3 described in the first exemplary embodiment.
An organic EL device in an exemplary arrangement according to the third exemplary embodiment contains the compound of the third exemplary embodiment (compound represented by the formula (121) or (122)) in at least one of the organic layer(s). An organic EL device in another exemplary arrangement according to the third exemplary embodiment contains the compound of the third exemplary embodiment (compound represented by the formula (121) or (122)) in the emitting layer.
An organic EL device in still another exemplary arrangement according to the third exemplary embodiment is an organic EL device in which the compound M3 in the organic EL device according to the first exemplary embodiment is replaced by the compound of the third exemplary embodiment (compound represented by the formula (121) or (122)).
An organic EL device in a further exemplary arrangement according to the third exemplary embodiment is an organic EL device in which the compound M3 in the organic EL device according to the second exemplary embodiment is replaced by the compound of the third exemplary embodiment (compound represented by the formula (121) or (122)).
The compound according to the third exemplary embodiment enables a high performance, for instance, improvement in luminous efficiency of the organic EL device.
Accordingly, the organic EL device in the exemplary arrangement according to the third exemplary embodiment also has a high performance, for instance, a high luminous efficiency.
A compound of a fourth exemplary embodiment is a compound represented by one of formulae (131) to (134) below. A compound falling under one of the formulae (131) to (134) among the specific examples of the compound M3 of the first exemplary embodiment is used as a specific example of the compound of the fourth exemplary embodiment.
In the formulae (131) to (134):
In the formulae (131) to (134): when a carbon atom bonded to R31 is bonded to *, a hydrogen atom represented by R31, a substituent represented by R31, and a ring formed by involving R31 are not present.
In the formulae (131) to (134), when a carbon atom bonded to R32 is bonded to *, a hydrogen atom represented by R32, a substituent represented by R32, and a ring formed by involving R32 are not present.
In the formulae (131) to (134), when a carbon atom bonded to R33 is bonded to *, a hydrogen atom represented by R33, a substituent represented by R33, and a ring formed by involving R33 are not present.
In the formulae (131) to (134), when a carbon atom bonded to R34 is bonded to *, a hydrogen atom represented by R34, a substituent represented by R34, and a ring formed by involving R34 are not present.
In the formulae (131) to (134), when a carbon atom bonded to R35 is bonded to *, a hydrogen atom represented by R35, a substituent represented by R35, and a ring formed by involving R35 are not present.
In the formulae (131) to (134), when a carbon atom bonded to R36 is bonded to *, a hydrogen atom represented by R36, a substituent represented by R36, and a ring formed by involving R36 are not present.
In the formulae (131) to (134), when a carbon atom bonded to R37 is bonded to *, a hydrogen atom represented by R37, a substituent represented by R37, and a ring formed by involving R37 are not present.
In the formulae (131) to (134), when a carbon atom bonded to R38 is bonded to *, a hydrogen atom represented by R38, a substituent represented by R38, and a ring formed by involving R38 are not present.
In the formulae (131) to (134), when a nitrogen atom bonded to R39 is bonded to *, a substituent represented by R39 is not present.
In the formulae (131) to (134): it is preferable that a combination of R11 and R12, a combination of R12 and R13, a combination of R13 and R14, a combination of R15 and R16, a combination of R16 and R17, and a combination of R17 and R18 are not mutually bonded.
In the formulae (131) to (134): it is preferable that a combination of R21 and R22, a combination of R22 and R23, a combination of R23 and R24, a combination of R25 and R26, a combination of R26 and R27, and a combination of R27 and R28 are not mutually bonded.
In the formulae (131) to (134): it is preferable that a combination of R31 and R32, a combination of R32 and R33, a combination of R33 and R34, a combination of R35 and R36, a combination of R36 and R37, and a combination of R37 and R38 are not mutually bonded.
In the compound of the fourth exemplary embodiment, A2 is preferably a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 18 ring atoms. In the compound of the fourth exemplary embodiment, A2 is more preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted fluorenyl group, or a group represented by the formula (14).
In the compound of the fourth exemplary embodiment, it is preferable that L2 is a single bond and A2 is a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 18 ring atoms.
In the compound of the fourth exemplary embodiment, it is more preferable that L2 is a single bond and A2 is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted fluorenyl group, or a group represented by the formula (14).
In the compound of the fourth exemplary embodiment, it is still more preferable that L2 is a single bond and A2 is an unsubstituted phenyl group.
In the compound of the fourth exemplary embodiment, X1 is preferably NR39.
In the compound of the fourth exemplary embodiment, it is preferable that X1 is preferably NR39 and a nitrogen atom bonded to R39 is bonded to *.
In the compound of the fourth exemplary embodiment, it is preferable that R11 to R18, R21 to R28 and R31 to R38 are each independently a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and R39 is a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
In the compound of the fourth exemplary embodiment, it is more preferable that R11 to R18, R21 to R28 and R31 to R38 are each independently a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and R39 is a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms.
In the compound of the fourth exemplary embodiment, it is still more preferable that R11 to R18, R21 to R28 and R31 to R38 are each a hydrogen atom and R39 is a substituted or unsubstituted phenyl group.
In the compound of the fourth exemplary embodiment, it is preferable that Ar100 and L2 are each independently a single bond or a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms.
In the compound of the fourth exemplary embodiment, it is more preferable that Ar100 and L2 are each independently a substituted or unsubstituted phenylene group, a substituted or unsubstituted parabiphenylene group, or a substituted or unsubstituted paraterphenylene group.
In the compound of the fourth exemplary embodiment, it is still more preferable that Ar100 and L2 are each independently a substituted or unsubstituted parabiphenylene group or a substituted or unsubstituted paraterphenylene group.
In the compound of the fourth exemplary embodiment, it is also preferable that Ar100 and L2 are each independently a single bond or at least one group selected from the group consisting of groups represented by the formulae (L1) to (L7).
In the compound of the fourth exemplary embodiment, it is also more preferable that L2 is a single bond or a group represented by one of the formulae (L3), (L4) and (L6).
In the compound of the fourth exemplary embodiment, a substituent for “substituted or unsubstituted” group is each independently preferably a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 30 carbon, more preferably an unsubstituted aryl group having 6 to 30 ring carbon atoms, an unsubstituted heterocyclic group having 5 to 30 ring atoms, or an unsubstituted alkyl group having 1 to 30 carbon atoms.
The compound of the fourth exemplary embodiment corresponds to a compound of an example of the compound M3 described in the first exemplary embodiment. Therefore, specific examples of the compound of the fourth exemplary embodiment are also shown in the examples of the compound M3 described in the first exemplary embodiment.
An organic EL device in an exemplary arrangement according to the fourth exemplary embodiment contains the compound of the fourth exemplary embodiment (compound represented by one of the formulae (131) to (134)) in at least one of the organic layer(s). An organic EL device in another exemplary arrangement according to the fourth exemplary embodiment contains the compound of the fourth exemplary embodiment (compound represented by one of the formulae (131) to (134)) in the emitting layer.
An organic EL device in still another exemplary arrangement according to the fourth exemplary embodiment is an organic EL device in which the compound M3 in the organic EL device according to the first exemplary embodiment is replaced by the compound of the fourth exemplary embodiment (compound represented by one of the formulae (131) to (134)).
An organic EL device in a further exemplary arrangement according to the fourth exemplary embodiment is an organic EL device in which the compound M3 in the organic EL device according to the second exemplary embodiment is replaced by the compound of the fourth exemplary embodiment (compound represented by one of the formulae (131) to (134)).
The compound according to the fourth exemplary embodiment enables a high performance, for instance, improvement in luminous efficiency of the organic EL device.
Accordingly, the organic EL device in the exemplary arrangement according to the fourth exemplary embodiment also has a high performance, for instance, a high luminous efficiency.
A compound of a fifth exemplary embodiment is a compound represented by a formula (141), (142) or (143) below. A compound falling under the formula (141), (142) or (143) among the specific examples of the compound M3 of the first exemplary embodiment is used as a specific example of the compound of the fifth exemplary embodiment.
In the formulae (141) to (143):
In the formulae (141) to (143): when a carbon atom bonded to R31 is bonded to *, a hydrogen atom represented by R31, a substituent represented by R31, and a ring formed by involving R31 are not present.
In the formulae (141) to (143), when a carbon atom bonded to R32 is bonded to *, a hydrogen atom represented by R32, a substituent represented by R32, and a ring formed by involving R32 are not present.
In the formulae (141) to (143), when a carbon atom bonded to R33 is bonded to *, a hydrogen atom represented by R33, a substituent represented by R33, and a ring formed by involving R33 are not present.
In the formulae (141) to (143), when a carbon atom bonded to R4 is bonded to *, a hydrogen atom represented by R34, a substituent represented by R34, and a ring formed by involving R34 are not present.
In the formulae (141) to (143), when a carbon atom bonded to R35 is bonded to *, a hydrogen atom represented by R35, a substituent represented by R35, and a ring formed by involving R35 are not present.
In the formulae (141) to (143), when a carbon atom bonded to R36 is bonded to *, a hydrogen atom represented by R36, a substituent represented by R36, and a ring formed by involving R36 are not present.
In the formulae (141) to (143), when a carbon atom bonded to R37 is bonded to *, a hydrogen atom represented by R37, a substituent represented by R37, and a ring formed by involving R37 are not present.
In the formulae (141) to (143), when a carbon atom bonded to R38 is bonded to *, a hydrogen atom represented by R38, a substituent represented by R38, and a ring formed by involving R38 are not present.
In the formulae (141) to (143), when a nitrogen atom bonded to R39 is bonded to *, a substituent represented by R39 is not present.
In the formulae (141) to (143), when a carbon atom bonded to R25 is bonded to *1, a hydrogen atom represented by R25, a substituent represented by R25, and a ring formed by involving R25 are not present.
In the formulae (141) to (143), when a carbon atom bonded to R27 is bonded to *1, a hydrogen atom represented by R27, a substituent represented by R27, and a ring formed by involving R27 are not present.
In the formulae (141) to (143): when a carbon atom bonded to R28 is bonded to *1, a hydrogen atom represented by R28, a substituent represented by R28, and a ring formed by involving R28 are not present.
The compound of the fifth exemplary embodiment is preferably a compound represented by a formula (141A), (142A) or (143A) below.
In the formulae (141A), (142A) and (143A): A2, L2, X1, R11 to R18, R21 to R28, R31 to R39, R100 and n1 each independently represent the same as A2, L2, X1, R11 to R18, R21 to R28, R31 to R39, R100 and n1 in the formulae (141) to (143); four R100 are mutually the same or different; one of carbon atoms bonded to R25, R27 and R28 is bonded to *1, and one selected from carbon atoms bonded to R31 to R38 and a nitrogen atom bonded to R39 is bonded to *.
In the formulae (141A), (142A) and (143A): when a carbon atom bonded to R31 is bonded to *, a hydrogen atom represented by R31, a substituent represented by R31, and a ring formed by involving R31 are not present.
In the formulae (141A), (142A) and (143A): when a carbon atom bonded to R32 is bonded to *, a hydrogen atom represented by R32, a substituent represented by R32, and a ring formed by involving R32 are not present.
In the formulae (141A), (142A) and (143A): when a carbon atom bonded to R33 is bonded to *, a hydrogen atom represented by R33, a substituent represented by R33, and a ring formed by involving R33 are not present.
In the formulae (141A), (142A) and (143A): when a carbon atom bonded to R34 is bonded to *, a hydrogen atom represented by R34, a substituent represented by R34, and a ring formed by involving R34 are not present.
In the formulae (141A), (142A) and (143A): when a carbon atom bonded to R35 is bonded to *, a hydrogen atom represented by R35, a substituent represented by R35, and a ring formed by involving R35 are not present.
In the formulae (141A), (142A) and (143A): when a carbon atom bonded to R36 is bonded to *, a hydrogen atom represented by R36, a substituent represented by R36, and a ring formed by involving R36 are not present.
In the formulae (141A), (142A) and (143A): when a carbon atom bonded to R37 is bonded to *, a hydrogen atom represented by R37, a substituent represented by R37, and a ring formed by involving R37 are not present.
In the formulae (141A), (142A) and (143A): when a carbon atom bonded to R38 is bonded to *, a hydrogen atom represented by R38, a substituent represented by R38, and a ring formed by involving R38 are not present.
In the formulae (141A), (142A) and (143A), when a nitrogen atom bonded to R39 is bonded to *, a substituent represented by R39 is not present.
In the formulae (141A), (142A) and (143A): when a carbon atom bonded to R25 is bonded to *1, a hydrogen atom represented by R25, a substituent represented by R25, and a ring formed by involving R25 are not present.
In the formulae (141A), (142A) and (143A): when a carbon atom bonded to R27 is bonded to *1, a hydrogen atom represented by R27, a substituent represented by R27, and a ring formed by involving R27 are not present.
In the formulae (141A), (142A) and (143A): when a carbon atom bonded to R26 is bonded to *1, a hydrogen atom represented by R26, a substituent represented by R26, and a ring formed by involving R26 are not present.
In the formulae (141) to (143), (141A), (142A) and (143A): it is preferable that a combination of R11 and R12, a combination of R12 and R13, a combination of R13 and R14, a combination of R15 and R18, a combination of R16 and R17, and a combination of R17 and R18 are not mutually bonded.
In the formulae (141) to (143), (141A), (142A) and (143A): it is preferable that a combination of R21 and R22, a combination of R22 and R23, a combination of R23 and R24, a combination of R25 and R26, a combination of R26 and R27, and a combination of R27 and R28 are not mutually bonded.
In the formulae (141) to (143), (141A), (142A) and (143A): it is preferable that a combination of R31 and R32, a combination of R32 and R33, a combination of R33 and R34, a combination of R35 and R36, a combination of R36 and R37, and a combination of R37 and R38 are not mutually bonded.
In the formulae (141) to (143), (141A), (142A) and (143A), n1 is preferably 2 or 3.
In the compound of the fifth exemplary embodiment, A2 is preferably a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 18 ring atoms.
In the compound of the fifth exemplary embodiment, A2 is more preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted fluorenyl group, or a group represented by the formula (14).
In the compound of the fifth exemplary embodiment, it is preferable that L2 is a single bond and A2 is a substituted or unsubstituted aryl group having 6 to 18 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 18 ring atoms.
In the compound of the fifth exemplary embodiment, it is more preferable that L2 is a single bond and A2 is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted fluorenyl group, or a group represented by the formula (14).
In the compound of the fifth exemplary embodiment, it is still more preferable that L2 is a single bond and A2 is an unsubstituted phenyl group.
In the compound of the fifth exemplary embodiment, X1 is preferably NR39.
In the compound of the fifth exemplary embodiment, it is preferable that X1 is NR39 and a nitrogen atom bonded to R39 is bonded to *.
In the compound of the fifth exemplary embodiment, it is preferable that R1 to R18, R21 to R28 and R31 to R38 are each independently a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and R39 is a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
In the compound of the fifth exemplary embodiment, it is more preferable that R11 to R18, R21 to R28 and R31 to R38 are each independently a hydrogen atom or a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, and R39 is a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms.
In the compound of the fifth exemplary embodiment, it is still more preferable that R11 to R18, R21 to R28 and R31 to R38 are each a hydrogen atom and R39 is a substituted or unsubstituted phenyl group.
In the compound of the fifth exemplary embodiment, it is preferable that L2 is each independently a single bond or a substituted or unsubstituted arylene group having 6 to 30 ring carbon atoms.
In the compound of the fifth exemplary embodiment, it is more preferable that L2 is each independently a substituted or unsubstituted phenylene group, a substituted or unsubstituted parabiphenylene group, or a substituted or unsubstituted paraterphenylene group.
In the compound of the fifth exemplary embodiment, it is still more preferable that L2 is each independently a substituted or unsubstituted parabiphenylene group or a substituted or unsubstituted paraterphenylene group.
In the compound of the fifth exemplary embodiment, it is also preferable that L2 is each independently a single bond or at least one group selected from the group consisting of groups represented by the formulae (L1) to (L7).
In the compound of the fifth exemplary embodiment, it is also more preferable that L2 is a single bond or a group represented by one of the formulae (L3), (L4) and (L6).
In the compound of the fifth exemplary embodiment, a substituent for “substituted or unsubstituted” group is each independently preferably a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, or a substituted or unsubstituted alkyl group having 1 to 30 carbon, more preferably an unsubstituted aryl group having 6 to 30 ring carbon atoms, an unsubstituted heterocyclic group having 5 to 30 ring atoms, or an unsubstituted alkyl group having 1 to 30 carbon atoms.
The compound of the fifth exemplary embodiment also corresponds to a compound of an example of the compound M3 described in the first exemplary embodiment. Therefore, specific examples of the compound of the fifth exemplary embodiment are also shown in the examples of the compound M3 described in the first exemplary embodiment.
An organic EL device in an exemplary arrangement according to the fifth exemplary embodiment contains the compound of the fifth exemplary embodiment (compound represented by the formula (141), (142) or (143)) in at least one of the organic layer(s). An organic EL device in another exemplary arrangement according to the fifth exemplary embodiment contains the compound of the fifth exemplary embodiment (compound represented by the formula (141), (142) or (143)) in the emitting layer.
An organic EL device in still another exemplary arrangement according to the fifth exemplary embodiment is an organic EL device in which the compound M3 in the organic EL device according to the first exemplary embodiment is replaced by the compound of the fifth exemplary embodiment (compound represented by the formula (141), (142) or (143)).
An organic EL device in a further exemplary arrangement according to the fifth exemplary embodiment is an organic EL device in which the compound M3 in the organic EL device according to the second exemplary embodiment is replaced by the compound of the fifth exemplary embodiment (compound represented by the formula (141), (142) or (143)).
The compound according to the fifth exemplary embodiment enables a high performance, for instance, improvement in luminous efficiency of the organic EL device.
Accordingly, the organic EL device in the exemplary arrangement according to the fifth exemplary embodiment also has a high performance, for instance, a high luminous efficiency.
The compound of the third exemplary embodiment (compound represented by the formula (121) or (122)), the compound of the fourth exemplary embodiment (compound represented by one of the formulae (131) to (134)), and the compound of the fifth exemplary embodiment (compound represented by the formula (141), (142) or (143)), which are described above, may contain at least one deuterium atom.
An exemplary arrangement in which the compound of the third exemplary embodiment, the compound of the fourth exemplary embodiment, and the compound of the fifth exemplary embodiment contain at least one deuterium atom is exemplified by an exemplary arrangement in which the compound M3, in “the exemplary arrangement in which the compound M3 contains at least one deuterium atom” described in the first exemplary embodiment, is replaced by each of the compound of the third exemplary embodiment, the compound of the fourth exemplary embodiment, and the compound of the fifth exemplary embodiment.
An electronic device according to a sixth exemplary embodiment is installed with any one of the organic EL devices according to the above exemplary embodiments. Examples of the electronic device include a display device and a light-emitting unit. Examples of the display device include a display component (e.g., an organic EL panel module), TV, mobile phone, tablet and personal computer. Examples of the light-emitting unit include an illuminator and a vehicle light.
An organic-EL-device material of a seventh exemplary embodiment contains at least one of the compound of the third exemplary embodiment, the compound of the fourth exemplary embodiment, or the compound of the fifth exemplary embodiment.
The organic-EL-device material according to the seventh exemplary embodiment enables a high performance, for instance, improvement in luminous efficiency of the organic EL device.
The organic-EL-device material of the seventh exemplary embodiment may further contain an additional compound. When the organic-EL-device material of the seventh exemplary embodiment further contains an additional compound, the additional compound may be solid or liquid.
The scope of the invention is not limited by the above-described exemplary embodiments but includes any modification and improvement as long as such modification and improvement are compatible with the invention.
For instance, the emitting layer is not limited to a single layer, but may be provided by laminating a plurality of emitting layers. When the organic EL device has the plurality of emitting layers, it is only required that at least one of the emitting layers satisfies the conditions described in the above exemplary embodiments. For instance, the rest of the emitting layers may be a fluorescent emitting layer or a phosphorescent emitting layer with use of emission caused by electron transfer from the triplet excited state directly to the ground state.
When the organic EL device includes a plurality of emitting layers, these emitting layers may be mutually adjacently provided, or may form a so-called tandem organic EL device, in which a plurality of emitting units are layered via an intermediate layer.
For instance, a blocking layer may be provided adjacent to at least one of a side of the emitting layer close to the anode or a side of the emitting layer close to the cathode. The blocking layer is preferably provided in contact with the emitting layer to block at least any of holes, electrons, excitons or combinations thereof.
For instance, when the blocking layer is provided in contact with the side of the emitting layer close to the cathode, the blocking layer permits transport of electrons, and blocks holes from reaching a layer provided closer to the cathode (e.g., the electron transporting layer) beyond the blocking layer. When the organic EL device includes the electron transporting layer, the blocking layer is preferably interposed between the emitting layer and the electron transporting layer.
When the blocking layer is provided in contact with the side of the emitting layer close to the anode, the blocking layer permits transport of holes and blocks electrons from reaching a layer provided closer to the anode (e.g., the hole transporting layer) beyond the blocking layer. When the organic EL device includes the hole transporting layer, the blocking layer is preferably interposed between the emitting layer and the hole transporting layer.
Alternatively, the blocking layer may be provided adjacent to the emitting layer so that the excitation energy does not leak out from the emitting layer toward neighboring layer(s). The blocking layer blocks excitons generated in the emitting layer from being transferred to a layer(s) (e.g., the electron transporting layer and the hole transporting layer) closer to the electrode(s) beyond the blocking layer.
The emitting layer is preferably bonded with the blocking layer.
Specific structure, shape and the like of the components in the invention may be designed in any manner as long as an object of the invention can be achieved.
Herein, numerical ranges represented by “x to y” represents a range whose lower limit is the value (x) recited before “to” and whose upper limit is the value (y) recited after “to.”
Herein, the phrase “Rx and Ry are mutually bonded to form a ring” means, for instance, that Rx and Ry include a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a silicon atom, the atom(s) included in Rx (a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a silicon atom) and the atom(s) contained in Ry (a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a silicon atom) are bonded via a single bond(s), a double bond(s), a triple bond, and/or a divalent linking group(s) to form a ring having 5 or more ring atoms (specifically, a heterocycle or an aromatic hydrocarbon ring). x represents a number, a character or a combination of a number and a character. y represents a number, a character or a combination of a number and a character.
The divalent linking group is not limited. Examples of the divalent linking group include —O—, —CO—, —CO2—, —S—, —SO—, —SO2—, —NH—, —NRa-, and a group provided by a combination of two or more of these linking group.
Specific examples of the heterocyclic ring include a cyclic structure (heterocyclic ring) obtained by removing a bond from a “heteroaryl group Sub2” exemplarily shown in the later-described “Description of Each Substituent in Formula.” The heterocyclic ring may have a substituent.
Specific examples of the heterocyclic ring include a cyclic structure (heterocyclic ring) obtained by removing a bond from an “aryl group Sub1” exemplarily shown in the later-described “Description of Each Substituent in Formula.” The aromatic hydrocarbon ring may have a substituent.
Examples of Ra include a substituted or unsubstituted alkyl group Sub3 having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group Sub1 having 6 to 30 ring carbon atoms, and a substituted or unsubstituted heteroaryl group Sub2 having 5 to 30 ring atoms, which are exemplarily shown in the later-described “Description of Each Substituent in Formula.”
Rx and Ry are mutually bonded to form a ring, which means, for instance, that: an atom included in Rx1 and an atom included in Ry1 in a molecular structure represented by a formula (E1) below form a ring (cyclic structure) E represented by a formula (E2); an atom included in Rx1 and an atom included in Ry1 in a molecular structure represented by a formula (F1) below form a ring F represented by a formula (F2); an atom included in Rx1 and an atom included in Ry1 in a molecular structure represented by a formula (G1) below form a ring G represented by a formula (G2); an atom included in Rx1 and an atom included in Ry1 in a molecular structure represented by a formula (H1) below form a ring H represented by a formula (H2); and an atom included in Rx1 and an atom included in Ry1 in a molecular structure represented by a formula (I1) below form a ring I represented by a formula (I2).
In the formulae (E1) to (I1), * each independently represent a bonding position to another atom in a molecule. The two * in the formulae (E1), (F1), (G1), (H1) and (I1) correspond to two * in the formulae (E2), (F2), (G2), (H2) and (I2), respectively.
In the molecular structures represented by the formulae (E2) to (I2), E to I each represent a cyclic structure (the ring having 5 or more ring atoms). In the formulae (E2) to (I2), * each independently represent a bonding position to another atom in a molecule. The two * in the formula (E2) correspond to two * in the formula (E1). Similarly, two * in each of the formulae (F2) to (I2) correspond one-to-one to two *in each of the formulae (F1) to (I1).
For instance, in the formula (E1), Rx1 and Ry1 are mutually bonded to form a ring E in the formula (E2). When the ring E is an unsubstituted benzene ring, the molecular structure represented by the formula (E1) is the molecular structure represented by the formula (E3). Here, the two * in the formula (E3) each independently correspond to two *in each of the formulae (E1) and (E2).
For instance, in the formula (E1), Rx1 and Ry1 are mutually bonded to form a ring E in the formula (E2). When the ring E is an unsubstituted benzene ring, the molecular structure represented by the formula (E1) is the molecular structure represented by the formula (E4). Here, the two * in the formula (E4) each independently correspond to two * in each of the formulae (E1) and (E2). In the formulae (E3) to (E4), * each independently represent a bonding position to another atom in a molecule.
Herein, the ring carbon atoms refer to the number of carbon atoms among atoms forming a ring of a compound (e.g., a monocyclic compound, fused-ring compound, crosslinking compound, carbon ring compound, and heterocyclic compound) in which the atoms are bonded to each other to form the ring. When the ring is substituted by a substituent(s), carbon atom(s) included in the substituent(s) is not counted in the ring carbon atoms. Unless specifically described, the same applies to the “ring carbon atoms” described later. For instance, a benzene ring has 6 ring carbon atoms, a naphthalene ring has 10 ring carbon atoms, a pyridinyl group has 5 ring carbon atoms, and a furanyl group has 4 ring carbon atoms. When a benzene ring and/or a naphthalene ring is substituted by a substituent (e.g., an alkyl group), the number of carbon atoms of the alkyl group is not counted in the number of the ring carbon atoms. When a fluorene ring is substituted by a substituent (e.g., a fluorene ring) (i.e., a spirofluorene ring is included), the number of carbon atoms of the fluorene ring as a substituent is not counted in the number of the ring carbon atoms of the fluorene ring.
Herein, the ring atoms refer to the number of atoms forming a ring of a compound (e.g., a monocyclic compound, fused-ring compound, crosslinking compound, carbon ring compound, and heterocyclic compound) in which the atoms are bonded to each other to form the ring (e.g., monocyclic ring, fused ring, ring assembly). Atom(s) not forming a ring and atom(s) included in a substituent when the ring is substituted by the substituent are not counted in the number of the ring atoms. Unless specifically described, the same applies to the “ring atoms” described later. For instance, a pyridine ring has six ring atoms, a quinazoline ring has ten ring atoms, and a furan ring has five ring atoms. A hydrogen atom(s) and/or an atom(s) of a substituent which are bonded to carbon atoms of a pyridine ring and/or quinazoline ring are not counted in the ring atoms. When a fluorene ring is substituted by a substituent (e.g., a fluorene ring) (i.e., a spirofluorene ring is included), the number of atoms of the fluorene ring as a substituent is not counted in the number of the ring atoms of the fluorene ring.
The aryl group (occasionally referred to as an aromatic hydrocarbon group) herein is exemplified by an aryl group Sub1. The aryl group Sub1 preferably has 6 to 30 ring carbon atoms, more preferably 6 to 20 ring carbon atoms, still more preferably 6 to 14 ring carbon atoms, and still further more preferably 6 to 12 ring carbon atoms.
The aryl group Sub1 herein is at least one group selected from the group consisting of a phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, pyrenyl group, chrysenyl group, fluoranthenyl group, benz[a]anthryl group, benzo[c]phenanthryl group, triphenylenyl group, benzo[k]fluoranthenyl group, benzo[g]chrysenyl group, benzo[b]triphenylenyl group, picenyl group, and perylenyl group.
Among the aryl group Sub1, a phenyl group, biphenyl group, naphthyl group, phenanthryl group, terphenyl group and fluorenyl group are preferable. A carbon atom in a position 9 of each of 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group and 4-fluorenyl group is preferably substituted by a substituted or unsubstituted alkyl group Sub3 or a substituted or unsubstituted aryl group Sub1 described later herein.
The heteroaryl group (occasionally referred to as a heterocyclic group, heteroaromatic cyclic group or aromatic heterocyclic group) herein is exemplified by a heterocyclic group Sub2. The heterocyclic group Sub2 is a group containing, as a hetero atom(s), at least one atom selected from the group consisting of nitrogen, sulfur, oxygen, silicon, selenium atom and germanium atom. The heterocyclic group Sub2 preferably contains, as a hetero atom(s), at least one atom selected from the group consisting of nitrogen, sulfur and oxygen. The heterocyclic group Sub2 preferably has 5 to 30 ring atoms, more preferably 5 to 20 ring atoms, and still more preferably 5 to 14 ring atoms.
The heterocyclic group Sub2 herein are, for instance, at least one group selected from the group consisting of a pyridyl group, pyrimidinyl group, pyrazinyl group, pyridazinyl group, triazinyl group, quinolyl group, isoquinolinyl group, naphthyridinyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, phenanthridinyl group, acridinyl group, phenanthrolinyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, indolyl group, benzimidazolyl group, indazolyl group, imidazopyridinyl group, benzotriazolyl group, carbazolyl group, furyl group, thienyl group, oxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, oxadiazolyl group, thiadiazolyl group, benzofuranyl group, benzothienyl group, benzoxazolyl group, benzothiazolyl group, benzisoxazolyl group, benzisothiazolyl group, benzoxadiazolyl group, benzothiadiazolyl group, dibenzofuranyl group, dibenzothienyl group, piperidinyl group, pyrrolidinyl group, piperazinyl group, morpholyl group, phenazinyl group, phenothiazinyl group, and phenoxazinyl group.
Among the above heterocyclic group Sub2, a 1-dibenzofuranyl group, 2-dibenzofuranyl group, 3-dibenzofuranyl group, 4-dibenzofuranyl group, 1-dibenzothienyl group, 2-dibenzothienyl group, 3-dibenzothienyl group, 4-dibenzothienyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, and 9-carbazolyl group are more preferable. A nitrogen atom in a position 9 of each of 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group and 4-carbazolyl group is preferably substituted by a substituted or unsubstituted aryl group Sub1 or a substituted or unsubstituted heterocyclic group Sub2 described herein.
Herein, the heterocyclic group Sub2 may be a group derived from any one of partial structures represented by formulae (XY-1) to (XY-18) below.
In the formulae (XY-1) to (XY-18), XA and YA each independently represent a hetero atom, and preferably represent an oxygen atom, sulfur atom, selenium atom, silicon atom or germanium atom. The partial structures represented by the formulae (XY-1) to (XY-18) may each have a bond at any position to provide a heterocyclic group, in which the heterocyclic group may be substituted.
Herein, the heterocyclic group Sub2 may be a group represented by one of formulae (XY-19) to (XY-22) below. Further, the position of the bond may be changed as needed.
The alkyl group herein may be any one of a linear alkyl group, branched alkyl group and cyclic alkyl group.
The alkyl group herein is exemplified by an alkyl group Sub3.
The linear alkyl group herein is exemplified by a linear alkyl group Sub31. The branched alkyl group herein is exemplified by a branched alkyl group Sub32.
The cyclic alkyl group herein is exemplified by a cyclic alkyl group Sub33 (also referred to as a cycloalkyl group Sub33).
For instance, the alkyl group Sub3 is at least one group selected from the group consisting of a linear alkyl group Sub31, branched alkyl group Sub32, and cyclic alkyl group Sub33.
Herein, the linear alkyl group Sub31 or branched alkyl group Sub32 preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 10 carbon atoms, and still further more preferably 1 to 6 carbon atoms.
Herein, the cycloalkyl group Sub33 preferably has 3 to 30 ring carbon atoms, more preferably 3 to 20 ring carbon atoms, still more preferably 3 to 10 ring carbon atoms, and still further more preferably 5 to 8 ring carbon atoms.
The linear alkyl group Sub31 or branched alkyl group Sub32 herein is exemplified by at least one group selected from the group consisting of a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, neopentyl group, amyl group, isoamyl group, 1-methylpentyl group, 2-methylpentyl group, 1-pentylhexyl group, 1-butylpentyl group, 1-heptyloctyl group, and 3-methylpentyl group.
The linear alkyl group Sub31 or branched alkyl group Sub32 is still more preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, t-butyl group, n-pentyl group, n-hexyl group, amyl group, isoamyl group and neopentyl group.
The cycloalkyl group Sub33 herein is exemplified by at least one group selected from the group consisting of a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-metylcyclohexyl group, adamantyl group and norbornyl group. Among the cycloalkyl group Sub33, a cyclopentyl group and a cyclohexyl group are still more preferable.
Herein, an alkyl halide group is exemplified by an alkyl halide group Sub4. The alkyl halide group Sub4 is provided by substituting the alkyl group Sub3 with at least one halogen atom, preferably at least one fluorine atom.
Herein, the alkyl halide group Sub4 is exemplified by at least one group selected from the group consisting of a fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, trifluoromethylmethyl group, trifluoroethyl group, and pentafluoroethyl group.
Herein, a substituted silyl group is exemplified by a substituted silyl group Sub5. The substituted silyl group Sub5 is exemplified by at least one group selected from the group consisting of an alkylsilyl group Sub51 and an arylsilyl group Sub52.
Herein, the alkylsilyl group Sub51 is exemplified by a trialkylsilyl group Sub511 having the above-described alkyl group Sub3.
The trialkylsilyl group Sub511 is exemplified by at least one group selected from the group consisting of a trimethylsilyl group, triethylsilyl group, tri-n-butylsilyl group, tri-n-octylsilyl group, triisobutylsilyl group, dimethylethylsilyl group, dimethylisopropylsilyl group, dimethyl-n-propylsilyl group, dimethyl-n-butylsilyl group, dimethyl-t-butylsilyl group, diethylisopropylsilyl group, vinyl dimethylsilyl group, propyldimethylsilyl group, and triisopropylsilyl group. Three alkyl groups Sub3 in the trialkylsilyl group Sub511 may be mutually the same or different.
Herein, the arylsilyl group Sub52 is exemplified by at least one group selected from the group consisting of a dialkylarylsilyl group Sub521, alkyldiarylsilyl group Sub522 and triarylsilyl group Sub523.
The dialkylarylsilyl group Sub521 is exemplified by a dialkylarylsilyl group including two alkyl groups Sub3 and one aryl group Sub1. The dialkylarylsilyl group Sub521 preferably has 8 to 30 carbon atoms.
The alkyldiarylsilyl group Sub522 is exemplified by an alkyldiarylsilyl group including one alkyl group Sub3 and two aryl groups Sub1. The alkyldiarylsilyl group Sub522 preferably has 13 to 30 carbon atoms.
The triarylsilyl group Sub523 is exemplified by a triarylsilyl group including three aryl groups Sub1. The triarylsilyl group Sub523 preferably has 18 to 30 carbon atoms.
Herein, a substituted or unsubstituted alkyl sulfonyl group is exemplified by an alkyl sulfonyl group Sub6. The alkyl sulfonyl group Sub6 is represented by —SO2Rw. Rw in —SO2Rw represents a substituted or unsubstituted alkyl group Sub3 described above.
Herein, an aralkyl group (occasionally referred to as an arylalkyl group) is exemplified by an aralkyl group Sub7. An aryl group in the aralkyl group Sub7 includes, for instance, at least one of the above-described aryl group Sub1 or the above-described heteroaryl group Sub2.
The aralkyl group Sub7 herein is preferably a group having the aryl group Sub1 and is represented by —Z3—Z4. Z3 is exemplified by an alkylene group corresponding to the above alkyl group Sub3. Z4 is exemplified by the above aryl group Sub1. In this aralkyl group Sub7, an aryl moiety has 6 to 30 carbon atoms (preferably 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms) and an alkyl moiety has 1 to 30 carbon atoms (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 6 carbon atoms). The aralkyl group Sub7 is exemplified by at least one group selected from the group consisting of a benzyl group, 2-phenylpropane-2-yl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl-t-butyl group, α-naphthylmethyl group, 1-α-naphthylethyl group, 2-α-naphthylethyl group, 1-α-naphthylisopropyl group, 2-α-naphthylisopropyl group, β-naphthylmethyl group, 1-β-naphthylethyl group, 2-β-naphthylethyl group, 1-β-naphthylisopropyl group, and 2-β-naphthylisopropyl group.
The alkoxy group herein is exemplified by an alkoxy group Sub8. The alkoxy group Sub8 is represented by —OZ1. Z1 is exemplified by the above alkyl group Sub3. The alkoxy group Sub8 preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. The alkoxy group Sub8 is exemplified by at least one group selected from the group consisting of a methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group and hexyloxy group.
Herein, an alkoxy halide group is exemplified by an alkoxy halide group Sub9. The alkoxy halide group Sub9 is provided, for instance, by substituting the alkoxy group Sub8 with at least one halogen atom, preferably at least one fluorine atom.
Herein, an aryloxy group (occasionally referred to as an arylalkoxy group) is exemplified by an arylalkoxy group Sub10. An aryl group in the arylalkoxy group Sub10 includes at least one of the aryl group Sub1 or the heteroaryl group Sub2.
The arylalkoxy group Sub10 herein is represented by —OZ2. Z2 is exemplified by the aryl group Sub1 or the heteroaryl group Sub2. The arylalkoxy group Sub10 preferably has 6 to 30 ring carbon atoms, more preferably 6 to 20 ring carbon atoms. The arylalkoxy group Sub10 is exemplified by a phenoxy group.
Herein, a substituted amino group is exemplified by a substituted amino group Sub11. The substituted amino group Sub11 is exemplified by at least one group selected from the group consisting of an arylamino group Sub111 and an alkylamino group Sub112.
The arylamino group Sub111 is represented by —NHRV1 or —N(RV1)2. RV1 is exemplified by the aryl group Sub1. Two RV1 in —N(RV1)2 are mutually the same or different.
The alkylamino group Sub112 is represented by —NHRV2 or —N(RV2)2. RV2 is exemplified by the alkyl group Sub3. Two RV2 in —N(RV2)2 are mutually the same or different.
Herein, the alkenyl group is exemplified by an alkenyl group Sub12. The alkenyl group Sub12, which is linear or branched, is exemplified by at least one group selected from the group consisting of a vinyl group, propenyl group, butenyl group, oleyl group, eicosapentaenyl group, docosahexaenyl group, styryl group, 2,2-diphenylvinyl group, 1,2,2-triphenylvinyl group, and 2-phenyl-2-propenyl group.
The alkynyl group herein is exemplified by an alkynyl group Sub13. The alkynyl group Sub13 may be linear or branched and is at least one group selected from the group consisting of an ethynyl group, a propynyl group and a 2-phenylethynyl group.
The alkylthio group herein is exemplified by an alkylthio group Sub14.
The alkylthio group Sub14 is represented by —SRV3. RV3 is exemplified by the alkyl group Sub3. The alkylthio group Sub14 preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.
The arylthio group herein is exemplified by an arylthio group Sub15.
The arylthio group Sub15 is represented by —SRV4. RV4 is exemplified by the aryl group Sub1. The arylthio group Sub15 preferably has 6 to 30 ring carbon atoms, more preferably 6 to 20 ring carbon atoms.
Herein, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, among which a fluorine atom is preferable.
A substituted phosphino group herein is exemplified by a substituted phosphino group Sub16. The substituted phosphino group Sub16 is exemplified by a phenyl phosphanyl group.
An arylcarbonyl group herein is exemplified by an arylcarbonyl group Sub17. The arylcarbonyl group Sub17 is represented by —COY′. Y′ is exemplified by the aryl group Sub1. Herein, the arylcarbonyl group Sub17 is exemplified by at least one group selected from the group consisting of a phenyl carbonyl group, diphenyl carbonyl group, naphthyl carbonyl group, and triphenyl carbonyl group.
An acyl group herein is exemplified by an acyl group Sub18. The acyl group Sub18 is represented by —COR′. R′ is exemplified by the alkyl group Sub3. The acyl group Sub18 herein is exemplified by at least one group selected from the group consisting of an acetyl group and a propionyl group.
A substituted phosphoryl group herein is exemplified by a substituted phosphoryl group Sub19. The substituted phosphoryl group Sub19 is represented by a formula (P) below.
In the formula (P), ArP1 and ArP2 are any one substituent selected from the group consisting of the above alkyl group Sub3 and the above aryl group Sub1.
An ester group herein is exemplified by an ester group Sub20. The ester group Sub20 is exemplified by at least one group selected from the group consisting of an alkyl ester group and an aryl ester group.
An alkyl ester group herein is exemplified by an alkyl ester group Sub201. The alkyl ester group Sub201 is represented by —C(═O)ORE. RE is exemplified by a substituted or unsubstituted alkyl group Sub3 described above.
An aryl ester group herein is exemplified by an aryl ester group Sub202. The aryl ester group Sub202 is represented by —C(═O)ORAr. RAr is exemplified by a substituted or unsubstituted aryl group Sub1 described above.
A siloxanyl group herein is exemplified by a siloxanyl group Sub21. The siloxanyl group Sub21 is a silicon compound group through an ether bond. The siloxanyl group Sub21 is exemplified by a trimethylsiloxanyl group.
A carbamoyl group herein is represented by —CONH2.
A substituted carbamoyl group herein is exemplified by a carbamoyl group Sub22. The carbamoyl group Sub22 is represented by —CONH—ArC or —CONH—RC. ArC is exemplified by at least one group selected from the group consisting of a substituted or unsubstituted aryl group Sub1 described above (preferably 6 to 10 ring carbon atoms) and the above-described heteroaryl group Sub2 (preferably 5 to 14 ring atoms). ArC may be a group formed by bonding the aryl group Sub1 and the heteroaryl group Sub2.
RC is exemplified by a substituted or unsubstituted alkyl group Sub3 described above (preferably having 1 to 6 carbon atoms).
Herein, “carbon atoms forming a ring (ring carbon atoms)” mean carbon atoms forming a saturated ring, unsaturated ring, or aromatic ring. “Atoms forming a ring (ring atoms)” mean carbon atoms and hetero atoms forming a hetero ring including a saturated ring, unsaturated ring, or aromatic ring.
Herein, a hydrogen atom includes isotope having different numbers of neutrons, specifically, protium, deuterium and tritium.
In chemical formulae herein, it is assumed that a hydrogen atom (i.e. protium, deuterium and tritium) is bonded to each of bondable positions that are not annexed with signs “R” or the like or “D” representing a deuterium.
Hereinafter, an alkyl group Sub3 means at least one group of a linear alkyl group Sub31, a branched alkyl group Sub32, or a cyclic alkyl group Sub33 described in “Description of Each Substituent.”
Similarly, a substituted silyl group Sub5 means at least one group of an alkylsilyl group Sub51 or an arylsilyl group Sub52.
Similarly, a substituted amino group Sub11 means at least one group of an arylamino group Sub111 or an alkylamino group Sub112.
Herein, a substituent for a “substituted or unsubstituted” group is exemplified by a substituent RF1. The substituent RF1 is at least one group selected from the group consisting of an aryl group Sub1, heteroaryl group Sub2, alkyl group Sub3, alkyl halide group Sub4, substituted silyl group Sub5, alkylsulfonyl group Sub6, aralkyl group Sub7, alkoxy group Sub8, alkoxy halide group Sub9, arylalkoxy group Sub10, substituted amino group Sub11, alkenyl group Sub12, alkynyl group Sub13, alkylthio group Sub14, arylthio group Sub15, substituted phosphino group Sub16, arylcarbonyl group Sub17, acyl group Sub18, substituted phosphoryl group Sub19, ester group Sub20, siloxanyl group Sub21, carbamoyl group Sub22, unsubstituted amino group, unsubstituted silyl group, halogen atom, cyano group, hydroxy group, nitro group, and carboxy group.
Herein, the substituent RF1 for a “substituted or unsubstituted” group may be a diaryl boron group (ArB1ArB2B—). ArB1 and ArB2 are exemplified by the above-described aryl group Sub1. ArB1 and ArB2 in ArB1ArB2B— are the same or different.
Specific examples and preferable examples of the substituent RF1 are the same as those of the substituents described in “Description of Each Substituent” (e.g., an aryl group Sub1, heteroaryl group Sub2, alkyl group Sub3, alkyl halide group Sub4, substituted silyl group Sub5, alkylsulfonyl group Sub6, aralkyl group Sub7, alkoxy group Sub8, alkoxy halide group Sub9, arylalkoxy group Sub10, substituted amino group Sub11, alkenyl group Sub12, alkynyl group Sub13, alkylthio group Sub14, arylthio group Sub15, substituted phosphino group Sub16, arylcarbonyl group Sub17, acyl group Sub18, substituted phosphoryl group Sub19, ester group Sub20, siloxanyl group Sub21, and carbamoyl group Sub22).
The substituent RF1 for a “substituted or unsubstituted” group may be further substituted by at least one group (hereinafter, also referred to as a substituent RF2) selected from the group consisting of an aryl group Sub1, heteroaryl group Sub2, alkyl group Sub3, alkyl halide group Sub4, substituted silyl group Sub5, alkylsulfonyl group Sub6, aralkyl group Sub7, alkoxy group Sub8, alkoxy halide group Sub9, arylalkoxy group Sub10, substituted amino group Sub11, alkenyl group Sub12, alkynyl group Sub13, alkylthio group Sub14, arylthio group Sub15, substituted phosphino group Sub16, arylcarbonyl group Sub17, acyl group Sub18, substituted phosphoryl group Sub19, ester group Sub20, siloxanyl group Sub21, carbamoyl group Sub22, unsubstituted amino group, unsubstituted silyl group, halogen atom, cyano group, hydroxy group, nitro group, and carboxy group. Moreover, a plurality of substituents RF2 may be bonded to each other to form a ring.
“Unsubstituted” for a “substituted or unsubstituted” group means that a group is not substituted by the above-described substituent RF1 but bonded with a hydrogen atom.
Herein, “XX to YY carbon atoms” in the description of “substituted or unsubstituted ZZ group having XX to YY carbon atoms” represent carbon atoms of an unsubstituted ZZ group and do not include carbon atoms of the substituent RF1 of the substituted ZZ group.
Herein, “XX to YY atoms” in the description of “substituted or unsubstituted ZZ group having XX to YY atoms” represent atoms of an unsubstituted ZZ group and do not include atoms of the substituent RF1 of the substituted ZZ group.
The same description as the above applies to “substituted or unsubstituted” in compounds or partial structures thereof described herein.
Herein, when the substituents are bonded to each other to form a ring, the ring is structured to be a saturated ring, an unsaturated ring, an aromatic hydrocarbon ring or a hetero ring.
Herein, examples of the aromatic hydrocarbon group in the linking group include a divalent or multivalent group obtained by eliminating one or more atoms from the above monovalent aryl group Sub1.
Herein, examples of the heterocyclic group in the linking group include a divalent or multivalent group obtained by eliminating one or more atoms from the above monovalent heteroaryl group Sub2.
The compound M3 used for manufacturing the organic EL device is shown below.
Structures of compounds used for manufacturing organic EL devices in Comparatives are shown below.
Structures of other compounds used for manufacturing the organic EL devices in Examples and Comparatives are shown below.
The organic EL devices were manufactured and evaluated as follows.
A glass substrate (size: 25 mm×75 mm×1.1 mm thick, manufactured by Geomatec Co., Ltd.) having an ITO transparent electrode (anode) was ultrasonic-cleaned in isopropyl alcohol for five minutes, and then UV-ozone-cleaned for one minute. The film thickness of ITO was 130 nm.
After the glass substrate having the transparent electrode line was cleaned, the glass substrate was mounted on a substrate holder of a vacuum deposition apparatus. Firstly, a compound HT1 and a compound HA were co-deposited on a surface of the glass substrate where the transparent electrode line was provided in a manner to cover the transparent electrode, thereby forming a 10-nm-thick hole injecting layer. The concentrations of the compound HT and the compound HA in the hole injecting layer were 97 mass % and 3 mass %, respectively.
Next, the compound HT was vapor-deposited on the hole injecting layer to form a 200-nm-thick hole transporting layer.
Next, a compound EBL was vapor-deposited on the hole transporting layer to form a 10-nm-thick electron blocking layer.
Next, a compound RD as the fluorescent compound M1, a compound TADF as the delayed fluorescent compound M2, and a compound M3-1 as the compound M3 were co-deposited on the electron blocking layer to form a 25-nm-thick emitting layer. The concentrations of the compound RD, the compound TADF, and the compound M3-1 in the emitting layer were 1 mass %, 25 mass %, and 74 mass %, respectively.
Next, a compound HBL was vapor-deposited on the emitting layer to form a 10-nm-thick hole blocking layer.
Next, a compound ET was vapor-deposited on the hole blocking layer to form a 30-nm-thick electron transporting layer.
Next, lithium fluoride (LiF) was vapor-deposited on the electron transporting layer to form a 1-nm-thick electron injecting electrode (cathode).
Subsequently, metal aluminum (Al) was vapor-deposited on the electron injectable electrode to form an 80-nm-thick metal Al cathode.
A device arrangement of the organic EL device in Example 1 is roughly shown as follows.
Numerals in parentheses represent a film thickness (unit: nm).
The numerals (97%:3%) represented by percentage in the same parentheses indicate a ratio (mass %) between the compound HT and the compound HA in the hole injecting layer. The numerals (74%:25%:1%) represented by percentage in the same parentheses indicate a ratio (mass %) between the compound M3, the compound M2, and the compound M1 in the emitting layer.
The organic EL devices in Example 2 and Comparative 1 were manufactured in the same manner as in Example 1 except that the compound M3-1 in the emitting layer in Example 1 was replaced by compounds shown in Table 2.
The organic EL devices manufactured in Examples 1, 2 and Comparative 1 were evaluated as follows. Table 2 shows the results. Although a compound Ref-1 used in Comparative 1 does not correspond to the compound M3, the compound Ref-1 is shown in the same column as the compound M3-1 in Example 1 for convenience.
Voltage was applied on an organic EL device such that a current density was 10 mA/cm2, where spectral radiance spectrum was measured by a spectroradiometer CS-2000 (manufactured by Konica Minolta, Inc.). The main peak wavelength λp (unit: nm) was calculated based on the obtained spectral-radiance spectra.
A voltage (unit: V) was measured when current was applied between the anode and the cathode such that a current density was 10 mA/cm2.
Voltage was applied to the organic EL devices such that a current density was 10 mA/cm2, where spectral radiance spectrum was measured by a spectroradiometer CS-2000 (produced by Konica Minolta, Inc.). The external quantum efficiency EQE (unit: %) was calculated based on the obtained spectral radiance spectra, assuming that the spectra was provided under a Lambertian radiation.
The organic EL devices in Examples 1 and 2 exhibited a significantly improved external quantum efficiency EQE as compared with the organic EL device in Comparative 1 using the compound Ref-1 in place of the compound M3 in the emitting layer.
The compound Ref-1 used in Comparative 1 corresponds to a compound having a biscarbazole structure in Patent Literature 2. It is inferred that a luminous efficiency in Comparative 1 is decreased because an absolute value (4.97 eV) of HOMO energy level of the compound Ref-1 is too small as described in Table 1.
Organic EL devices in Example 3 to 6 and Comparative 2 were manufactured in the same manner as in Example 1 except that the compound M3-1 and the compound TADF in the emitting layer in Example 1 were replaced by compounds shown in Table 3.
The organic EL devices manufactured in Examples 3 to 6 and Comparative 2 were measured for the main peak wavelength λp (unit: nm) and the external quantum efficiency EQE (unit: %) in the same manner as in Example 1. Table 3 shows the results. Although the compound Ref-1 used in Comparative 2 does not correspond to the compound M3, the compound Ref-1 is shown in the same column as the compound M3-1 in Example 3 for convenience.
The organic EL devices in Examples 3 to 6 exhibited a significantly improved external quantum efficiency EQE as compared with the organic EL device in Comparative 2 using the compound Ref-1 in place of the compound M3 in the emitting layer.
The compound Ref-1 used in Comparative 2 corresponds to a compound having a biscarbazole structure in Patent Literature 2. It is inferred that a luminous efficiency in Comparative 2 is decreased because an absolute value (4.97 eV) of HOMO energy level of the compound Ref-1 is too small as described in Table 1.
Physical properties of compounds described in Tables 2 and 3 were measured according to the following methods.
Delayed fluorescence was checked by measuring transient PL using a device shown in
The fluorescence spectrum of the sample solution was measured with a spectrofluorometer FP-8600 (produced by JASCO Corporation), and the fluorescence spectrum of a 9,10-diphenylanthracene ethanol solution was measured under the same conditions. Using the fluorescence area intensities of both spectra, the total fluorescence quantum yield was calculated by an equation (1) in Morris et al. J. Phys. Chem. 80 (1976) 969.
Prompt emission was observed immediately when the excited state was achieved by exciting the compound TADF with a pulse beam (i.e., a beam emitted from a pulse laser) having a wavelength to be absorbed by the compound TADF, and Delay emission was observed not immediately when the excited state was achieved but after the excited state was achieved. The delayed fluorescence in Examples means that an amount of Delay emission is 5% or more with respect to an amount of Prompt emission. Specifically, provided that the amount of Prompt emission is denoted by XP and the amount of Delay emission is denoted by XD, the delayed fluorescence means that a value of XD/XP is 0.05 or more.
An amount of Prompt emission, an amount of Delay emission and a ratio between the amounts thereof can be obtained according to the method as described in “Nature 492, 234-238, 2012” (Reference Document 1). The amount of Prompt emission and the amount of Delay emission may be calculated using a device different from one described in Reference Document 1 or one shown in
It was confirmed that the amount of Delay emission was 5% or more with respect to the amount of Prompt emission in the compound TADF.
Specifically, the value of XD/XP was 0.05 or more in the compound TADF. A value of XD/XP was 0.05 or more in a compound TADF2.
A singlet energy S1 of each of the compound M3-1 to the compound M3-5, the compound TADF, the compound TADF2, the compound RD, and Comparative compound Ref-1 was measured according to the above-described solution method.
An energy gap T77K of each of the compound M3-1 to the compound M3-5, the compound TADF, the compound TADF2, and Comparative compound Ref-1 was measured according to the measurement method of the energy gap T77K described in the above “Relationship between Triplet Energy and Energy Gap at 77K.” ΔST was confirmed from the measurement results of T77K and the above values of the singlet energy S1.
A main peak wavelength λ of each of the compound RD, the compound TADF, and the compound TADF2 was measured according to the following method.
A toluene solution of a measurement target compound at a concentration of 5 μmol/L was prepared and put in a quartz cell. An emission spectrum (ordinate axis: luminous intensity, abscissa axis: wavelength) of the thus-obtained sample was measured at a normal temperature (300K). In Examples, the emission spectrum was measured using a spectrophotometer manufactured by Hitachi, Ltd. (device name: F-7000). It should be noted that the machine for measuring the emission spectrum is not limited to the machine used herein. A peak wavelength of the emission spectrum exhibiting the maximum luminous intensity was defined as a main peak wavelength λ.
Compounds M3-1 to M3-11, which were the compound M3, were synthesized.
A synthetic scheme of the compound M3-1 is shown below.
Under nitrogen atmosphere, xylene (100 mL) was added to a mixture of 9-phenyl-9H,9′H-2,4′-bicarbazole (8.17 g, 20.0 mmol), 2-(4′-bromo-[1,1′-biphenyl]-4-yl)dibenzo[b,d]furan (7.99 g, 20.0 mmol), palladium acetate (134.7 mg, 0.60 mmol), tri-tert-butylphosphonium tetrafluoroborate (34.8 mg, 1.20 mmol), and sodium tert-butoxide (5.77 g, 60.0 mmol), and stirred for eight hours at 130 degrees C. After the reaction, a solid was filtrated and recrystallized with toluene to obtain the compound M3-1 (11.8 g, a yield of 81%). The obtained compound was identified as the compound M3-1 by analysis according to Liquid chromatography mass spectrometry (LC-MS).
A synthetic scheme of a compound M3-2 is shown below.
The compound M3-2 was obtained in the same manner as in Synthesis Example 1 except for using 1-(4′-chloro-[1,1′-biphenyl]-4-yl)dibenzo[b,d]furan in place of 2-(4′-bromo-[1,1′-biphenyl]-4-yl)dibenzo[b,d]furan. A yield was 65%. The obtained compound was identified as the compound M3-2 by analysis according to LC-MS.
A synthetic scheme of a compound M3-3 is shown below.
The compound M3-3 was obtained in the same manner as in Synthesis Example 1 except for using 9-(4′-bromo-[1,1′-biphenyl]-4-yl)-9H-carbazole in place of 2-(4′-bromo-[1,1′-biphenyl]-4-yl)dibenzo[b,d]furan. A yield was 91%. The obtained compound was identified as the compound M3-3 by analysis according to LC-MS.
A synthetic scheme of a compound M3-4 is shown below.
The compound M3-4 was obtained in the same manner as in Synthesis Example 1 except for using 9-(4″-chloro-[1,1′: 4′,1″-terphenyl]-4-yl)-9H-carbazole in place of 2-(4′-bromo-[1,1′-biphenyl]-4-yl)dibenzo[b,d]furan. A yield was 77%. The obtained compound was identified as the compound M3-4 by analysis according to LC-MS.
A synthetic scheme of a compound M3-5 is shown below.
The compound M3-5 was obtained in the same manner as in Synthesis Example 1 except for using 9-phenyl-9H,9′H-2,2′-bicarbazole in place of 9-phenyl-9H,9′H-2,4′-bicarbazole. A yield was 49%. The obtained compound was identified as the compound M3-5 by analysis according to LC-MS.
A synthetic scheme of a compound M3-6 is shown below.
The compound M3-6 was obtained in the same manner as in Synthesis Example 1 except for using 9′-phenyl-9H,9′H-2,4′-bicarbazole in place of 9-phenyl-9H,9′H-2,4′-bicarbazole and using 9-(4′-bromo-[1,1′-biphenyl]-4-yl)-9H-carbazole in place of 2-(4′-bromo-[1,1′-biphenyl]-4-yl)dibenzo[b,d]furan. A yield was 90%. The obtained compound was identified as the compound M3-6 by analysis according to LC-MS.
A synthetic scheme of a compound M3-7 is shown below.
The compound M3-7 was obtained in the same manner as in Synthesis Example 1 except for using 9′-phenyl-9H,9′H-2,4′-bicarbazole in place of 9-phenyl-9H,9′H-2,4′-bicarbazole and using 9-(4″-chloro-[1,1′: 4′,1″-terphenyl]-4-yl)-9H-carbazole in place of 2-(4′-bromo-[1,1′-biphenyl]-4-yl)dibenzo[b,d]furan. A yield was 82%. The obtained compound was identified as the compound M3-7 by analysis according to LC-MS.
A synthetic scheme of a compound M3-8 is shown below.
The compound M3-8 was obtained in the same manner as in Synthesis Example 1 except for using 9′-phenyl-9H,9′H-2,4′-bicarbazole in place of 9-phenyl-9H,9′H-2,4′-bicarbazole and using 1-(4′-chloro-[1,1′-biphenyl]-4-yl)dibenzo[b,d]furan in place of 2-(4′-bromo-[1,1′-biphenyl]-4-yl)dibenzo[b,d]furan. A yield was 48%. The obtained compound was identified as the compound M3-8 by analysis according to LC-MS.
A synthetic scheme of a compound M3-9 is shown below.
The compound M3-9 was obtained in the same manner as in Synthesis Example 1 except for using 9′-phenyl-9H,9′H-1,4′-bicarbazole in place of 9-phenyl-9H,9′H-2,4′-bicarbazole and using 1-(4′-chloro-[1,1′-biphenyl]-4-yl)dibenzo[b,d]furan in place of 2-(4′-bromo-[1,1′-biphenyl]-4-yl)dibenzo[b,d]furan. A yield was 33%. The obtained compound was identified as the compound M3-9 by analysis according to LC-MS.
A synthetic scheme of a compound M3-10 is shown below.
The compound M3-10 was obtained in the same manner as in Synthesis Example 1 except for using 9′-phenyl-9H,9′H-1,4′-bicarbazole in place of 9-phenyl-9H,9′H-2,4′-bicarbazole and using 9-(4′-bromo-[1,1′-biphenyl]-4-yl)-9H-carbazole in place of 2-(4′-bromo-[1,1′-biphenyl]-4-yl)dibenzo[b,d]furan. A yield was 85%. The obtained compound was identified as the compound M3-10 by analysis according to LC-MS.
A synthetic scheme of a compound M3-11 is shown below.
The compound M3-11 was obtained in the same manner as in Synthesis Example 1 except for using 9′-phenyl-9H,9′H-1,4′-bicarbazole in place of 9-phenyl-9H,9′H-2,4′-bicarbazole and using 9-(4″-chloro-[1,1′:4′,1″-terphenyl]-4-yl)-9H-carbazole in place of 2-(4′-bromo-[1,1′-biphenyl]-4-yl)dibenzo[b,d]furan. A yield was 85%. The obtained compound was identified as the compound M3-11 by analysis according to LC-MS.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-168512 | Oct 2020 | JP | national |
| 2021-008796 | Jan 2021 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/036657 | 10/4/2021 | WO |
