Patent Grant
11512105
This application claims the priority and the benefit of Korean Patent Application No. 10-2019-0044480, filed on Apr. 16, 2019, in the Korean Intellectual Property Office, and all the benefits accruing therefrom under 35 U.S.C. § 119, the contents of which in their entirety are herein incorporated by reference.
An embodiment relates to an organometallic compound, an organic light-emitting device including the organometallic compound, and a diagnostic composition including the organometallic compound.
Organic light-emitting devices are self-emission devices, which have excellent characteristics in terms of a viewing angle, response time, brightness, driving voltage, and response speed, and produce full-color images.
In an example, an organic light-emitting device includes an anode, a cathode, and an organic layer between the anode and the cathode, wherein the organic layer includes an emission layer. A hole transport region may be between the anode and the emission layer, and an electron transport region may be between the emission layer and the cathode. Holes provided from the anode may move toward the emission layer through the hole transport region, and electrons provided from the cathode may move toward the emission layer through the electron transport region. The holes and the electrons recombine in the emission layer to produce excitons. These excitons transit from an excited state to a ground state, thereby generating light.
Luminescent compounds may be used to monitor, sense, or detect a variety of biological materials including cells and proteins. An example of the luminescent compounds is a phosphorescent luminescent compound.
Aspects of the present disclosure provide a novel organometallic compound, an organic light-emitting device including the same, and a diagnostic composition including the novel organometallic compound.
Additional aspects will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments.
An aspect of the present disclosure provides an organometallic compound represented by Formula 1 below:
M(L1)n1(L2)n2. Formula 1
In Formula 1,
M may be a transition metal,
L1 may be a ligand represented by Formula 2,
n1 may be 1, 2, or 3, wherein, when n1 is 2 or more, two or more L1(s) may be identical to or different from each other,
L2 may be a monodentate ligand, a bidentate ligand, a tridentate ligand, or a tetradentate ligand,
n2 may be 0, 1, 2, 3, or 4, wherein, when n2 is 2 or more, two or more L2(s) may be identical to or different from each other, and
L1 and L2 may be different from each other:
In Formula 2,
X1 may be C, N, Si, or P,
X21 may be C or N,
ring CY1 and ring CY21 may each independently be a C5-C30 carbocyclic group or a C2-C30 heterocyclic group,
X2 and X3 may each independently be O, S, Se, or C(R2), wherein X2 or X3 may be O, S, or Se,
X4 may be N or C(R4),
X5 may be N or C(R5),
R1, R2, R4, R5, and R21 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C2-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C2-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C7-C60 arylalkyl group (e.g., a substituted or unsubstituted phenyl(C1-C20 alkyl) group), a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted C2-C60 heteroarylalkyl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, —N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —B(Q6)(Q7), —P(═O)(Q8)(Q9) or —P(Q8)(Q9),
a1 and a21 may each independently be an integer from 0 to 20,
ring CY1 and R2 may not be linked to each other, and R1 and R2 may not be linked to each other,
L11 may be a C5-C30 carbocyclic group that is unsubstituted or substituted with at least one R10a group or a C2-C30 heterocyclic group that is unsubstituted or substituted with at least one R10a group,
b11 may be an integer from 0 to 10, wherein, when b11 is 0, a group represented by *-(L11)b11-*′ may be a single bond, and when b11 is 2 or more, two or more L11(s) may be identical to or different from each other,
two or more of a plurality of neighboring R21(s) may optionally be linked to form a C5-C30 carbocyclic group that is unsubstituted or substituted with at least one R10a group or a C2-C30 heterocyclic group that is unsubstituted or substituted with at least one R10a group,
R10a may be the same as defined in connection with R21,
* and *′ each indicate a binding site to M in Formula 1,
a substituent(s) of the substituted C5-C30 carbocyclic group, the substituted C2-C30 heterocyclic group, the substituted C1-C60 alkyl group, the substituted C2-C60 alkenyl group, the substituted C2-C60 alkynyl group, the substituted C1-C60 alkoxy group, the substituted C3-C10 cycloalkyl group, the substituted C2-C10 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C2-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C7-C60 arylalkyl group (e.g., the substituted phenyl(C1-C20 alkyl) group), the substituted C2-C60 heteroarylalkyl group, the substituted heteroaryl group, the substituted monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group may be:
deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, or a C1-C60 alkoxy group;
a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, or a C1-C60 alkoxy group, each substituted with deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C2-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group, a phenyl(C1-C20 alkyl) group, a C1-C60 heteroaryl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic condensed heteropolycyclic group, —N(Q11)(Q12), —Si(Q13)(Q14)(Q15), —B(Q16)(Q17), —P(═O)(Q18)(Q19), or any combination thereof;
a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C2-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group (e.g., a phenyl(C1-C20 alkyl) group), a C60 heteroaryl group, a monovalent non-aromatic condensed polycyclic group, or a monovalent non-aromatic condensed heteropolycyclic group;
a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C2-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group (e.g., a phenyl(C1-C20 alkyl) group), a C60 heteroaryl group, a monovalent non-aromatic condensed polycyclic group, or a monovalent non-aromatic condensed heteropolycyclic group, each substituted with deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C2-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group (e.g., a phenyl(C1-C20 alkyl) group), a C1-C60 heteroaryl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic condensed heteropolycyclic group, —N(Q21)(Q22), —Si(Q23)(Q24)(Q25), —B(Q26)(Q27), —P(═O)(Q28)(Q29), or any combination thereof;
—N(Q31)(Q32), —Si(Q33)(Q34)(Q35), —B(Q36)(Q37), or —P(═O)(Q38)(Q39); or any combination thereof, and
Q1 to Q9, Q11 to Q19, Q21 to Q29, and Q31 to Q39 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C2-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryl group substituted with a C1-C60 alkyl group, a C6-C60 aryl group, or any combination thereof, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group (e.g., a phenyl(C1-C20 alkyl) group), a C1-C60 heteroaryl group, a monovalent non-aromatic condensed polycyclic group, or a monovalent non-aromatic condensed heteropolycyclic group.
Another aspect of the present disclosure provides an organic light-emitting device including: a first electrode; a second electrode; and an organic layer between the first electrode and the second electrode and including an emission layer, wherein the organic layer includes at least one organometallic compound represented by Formula 1.
The organometallic compound represented by Formula 1 included in the emission layer of the organic layer may act as a dopant.
Another aspect of the present disclosure provides a diagnostic composition including at least one organometallic compound represented by Formula 1.
These and/or other aspects will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with FIGURE which is a schematic cross-sectional view of an organic light-emitting device according to an embodiment.
Reference will now be made in detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described below, by referring to the FIGURES, to explain aspects of the present description. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
It will be understood that when an element is referred to as being “on” another element, it can be directly on the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.
It will be understood that, although the terms “first,” “second,” “third” etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, “a first element,” “component,” “region,” “layer,” or “section” discussed below could be termed a second element, component, region, layer, or section without departing from the teachings herein.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms, including “at least one,” unless the content clearly indicates otherwise. “At least one” is not to be construed as limiting “a” or “an.” “Or” means “and/or.” As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. It will be further understood that the terms “comprises” and/or “comprising,” or “includes” and/or “including” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of another feature, region, integer, step, operation, element, component, and/or groups thereof.
Furthermore, relative terms, such as “lower” or “bottom” and “upper” or “top,” may be used herein to describe one element's relationship to another element as illustrated in the FIGURES. It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation depicted in the FIGURES. For example, if the device in one of the FIGURES is turned over, elements described as being on the “lower” side of other elements would then be oriented on “upper” sides of the other elements. The exemplary term “lower,” can therefore, encompasses both an orientation of “lower” and “upper,” depending on the particular orientation of the FIGURE. Similarly, if the device in one of the FIGURES is turned over, elements described as “below” or “beneath” other elements would then be oriented “above” the other elements. The exemplary terms “below” or “beneath” can, therefore, encompass both an orientation of above and below.
“About” or “approximately” as used herein is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” can mean within one or more standard deviations, or within ±30%, 20%, 10%, or 5% of the stated value.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Exemplary embodiments are described herein with reference to cross section illustrations that are schematic illustrations of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as flat may, typically, have rough and/or nonlinear features. Moreover, sharp angles that are illustrated may be rounded. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.
An aspect of the present disclosure provides an organometallic compound represented by Formula 1 below:
M(L1)n1(L2)n2. Formula 1
M in Formula 1 may be a transition metal.
For example, M may be a first-row transition metal, a second-row transition metal, or a third-row transition metal of the Periodic Table of Elements.
In an embodiment, M may be iridium (Ir), platinum (Pt), osmium (Os), titanium (Ti), zirconium (Zr), hafnium (Hf), europium (Eu), terbium (Tb), thulium (Tm), or rhodium (Rh).
In an embodiment, M may be Ir, Pt, Os, or Rh, but embodiments of the present disclosure are not limited thereto.
L1 in Formula 1 may be a ligand represented by Formula 2, and n1 in Formula 1 indicates the number of L1 in Formula 1 and may be 1, 2, or 3. When n1 is 2 or more, two or more L1(s) may be identical to or different from each other:
Formula 2 may be the same as described below.
For example, n1 may be 1 or 2.
L2 in Formula 1 may be a monodentate ligand, a bidentate ligand, a tridentate ligand, or a tetradentate ligand, and n2 in Formula 1 indicates the number of L2 and may be 0, 1, 2, 3, or 4. When n2 is 2 or more, two or more L2(s) may be identical to or different from each other. L2 may be the same as described below.
For example, n2 in Formula 1 may be 1 or 2.
In Formula 1, L1 and L2 may be different from each other.
In an embodiment, M may be Ir or Os, and the sum of n1 and n2 may be 3 or 4; or M may be Pt, and the sum of n1 and n2 may be 2.
In Formula 2, X1 may be C, N, Si, or P, and X21 may be C or N.
For example, in Formula 2, X21 may be C.
In Formula 2, ring CY1 and ring CY21 may each independently be a C5-C30 carbocyclic group or a C2-C30 heterocyclic group.
For example, ring CY1 and ring CY21 may each independently be i) a first ring, ii) a second ring, iii) a condensed ring in which at least two first rings are condensed with each other, iv) a condensed ring in which at least two second rings are condensed with each other, or v) a condensed ring in which at least one first ring and at least one second ring are condensed with each other.
The first ring may be a cyclopentane group, a cyclopentadiene group, a furan group, a thiophene group, a pyrrole group, a silole group, an indene group, a benzofuran group, a benzothiophene group, an indole group, a benzosilole group, an oxazole group, an isoxazole group, an oxadiazole group, an isoxadiazole group, an oxatriazole group, an isoxatriazole group, a thiazole group, an isothiazole group, a thiadiazole group, an isothiadiazole group, a thiatriazole group, an isothiatriazole group, a pyrazole group, an imidazole group, a triazole group, a tetrazole group, an azasilole group, a diazasilole group, or a triazasilole group.
The second ring may be an admantane group, a norbornane group, a norbornene group, a cyclohexane group, a cyclohexene group, a benzene group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, or a triazine group.
In an embodiment, ring CY1 and ring CY21 may each independently be a cyclopentene group, a cyclohexene group, a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a cyclopentadiene group, a 1,2,3,4-tetrahydronaphthalene group, a thiophene group, a furan group, an indole group, a benzoborole group, a benzophosphole group, an indene group, a benzosilole group, a benzogermole group, a benzothiophene group, a benzoselenophene group, a benzofuran group, a carbazole group, a dibenzoborole group, a dibenzophosphole group, a fluorene group, a dibenzosilole group, a dibenzogermole group, a dibenzothiophene group, a dibenzoselenophene group, a dibenzofuran group, a dibenzothiophene 5-oxide group, a 9H-fluorene-9-one group, a dibenzothiophene 5,5-dioxide group, an azaindole group, an azabenzoborole group, an azabenzophosphole group, an azaindene group, an azabenzosilole group, an azabenzogermole group, an azabenzothiophene group, an azabenzoselenophene group, an azabenzofuran group, an azacarbazole group, an azadibenzoborole group, an azadibenzophosphole group, an azafluorene group, an azadibenzosilole group, an azadibenzogermole group, an azadibenzothiophene group, an azadibenzoselenophene group, an azadibenzofuran group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isoxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, a benzothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, or a 5,6,7,8-tetrahydroquinoline group, but embodiments of the present disclosure are not limited thereto.
In an embodiment, ring CY1 may be a cyclopentane group, a cyclohexane group, a cycloheptane group, a cyclooctane group, an adamantane group, a norbornane group, a norbornene group, a cyclopentene group, a cyclohexene group, a cycloheptene group, a benzene group, a naphthalene group, a fluorene group, a phenanthrene group, an anthracene group, a fluoranthene group, a triphenylene group, a pyrene group, a chrysene group, a pyrrole group, a thiophene group, a furan group, an imidazole group, a pyrazole group, a thiazole group, an isothiazole group, an oxazole group, an isoxazole group, a pyridine group, a pyrazine group, a pyrimidine group, a pyridazine group, an isoindole group, an indole group, an indazole group, a purine group, a quinoline group, an isoquinoline group, a benzoquinoline group, a quinoxaline group, a quinazoline group, a cinnoline group, a carbazole group, a phenanthroline group, a benzimidazole group, a benzofuran group, a benzothiophene group, an isobenzothiazole group, a benzoxazole group, an isobenzoxazole group, a triazole group a tetrazole group, an oxadiazole group, a triazine group, a dibenzofuran group, a dibenzothiophene group, a dibenzosilole group, a benzocarbazole group, a dibenzocarbazole group, an imidazopyridine group, or an imidazopyrimidine group, but embodiments of the present disclosure are not limited thereto.
In Formula 2, X2 and X3 may each independently be O, S, Se, or C(R2), wherein X2 or X3 may be O, S, or Se.
For example, in Formula 2, i) X2 may be O, S, or Se, and X3 may be C(R2); or ii) X2 may be C(R2), and X3 may be O, S, or Se.
In Formula 2, X4 may be N or C(R4), and X5 may be N or C(R5).
For example, X4 may be C(R4), and X5 may be C(R5).
In Formula 2, R1, R2, R4, R5, R21, and R10a may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C2-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C2-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C7-C60 arylalkyl group (e.g., a substituted or unsubstituted phenyl(C1-C20 alkyl) group), a substituted or unsubstituted C1-C60 heteroaryl group, substituted or unsubstituted C2-C60 heteroarylalkyl group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, —N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —B(Q6)(Q7), —P(═O)(Q8)(Q9) or —P(Q8)(Q9), wherein Q1 to Q9 are each the same as described above.
For example, R1, R2, R4, R5, R21, and R10a may each independently be:
hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, —SF5, a C1-C20 alkyl group, or a C1-C20 alkoxy group;
a C1-C20 alkyl group or a C1-C20 alkoxy group, each substituted with deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C10 alkyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a bicyclo[1.1.1]pentyl group, a bicyclo[2.1.1]hexyl group, a bicyclo[2.2.1]heptyl group, a bicyclo[2.2.2]octyl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a pyridinyl group, a pyrimidinyl group, or any combination thereof; a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a bicyclo[1.1.1]pentyl group, a bicyclo[2.1.1]hexyl group, a bicyclo[2.2.1]heptyl group, a bicyclo[2.2.2]octyl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a pyrrolyl group, a thiophenyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an isoindolyl group, an indolyl group, an indazolyl group, a purinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a carbazolyl group, a phenanthrolinyl group, a benzimidazolyl group, a benzofuranyl group, a benzothiophenyl group, an isobenzothiazolyl group, a benzoxazolyl group, an isobenzoxazolyl group, a triazolyl group, a tetrazolyl group, an oxadiazolyl group, a triazinyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, an imidazopyridinyl group, or an imidazopyrimidinyl group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C20 alkyl group, a C1-C20 alkoxy group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a cyclooctenyl group, a bicyclo[1.1.1]pentyl group, a bicyclo[2.1.1]hexyl group, a bicyclo[2.2.1]heptyl group, a bicyclo[2.2.2]octyl group, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a pyrrolyl group, a thiophenyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an isoindolyl group, an indolyl group, an indazolyl group, a purinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a carbazolyl group, a phenanthrolinyl group, a benzimidazolyl group, a benzofuranyl group, a benzothiophenyl group, an isobenzothiazolyl group, a benzoxazolyl group, an isobenzoxazolyl group, a triazolyl group, a tetrazolyl group, an oxadiazolyl group, a triazinyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, an imidazopyridinyl group, an imidazopyrimidinyl group, —Si(Q33)(Q34)(Q35), or any combination thereof; or
—N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —B(Q6)(Q7), —P(═O)(Q8)(Q9), or —P(Q8)(Q9), and
Q1 to Q9 and Q33 to Q35 may each independently be:
—CH3, —CD3, —CD2H, —CDH2, —CH2CH3, —CH2CD3, —CH2CD2H, —CH2CDH2, —CHDCH3, —CHDCD2H, —CHDCDH2, —CHDCD3, —CD2CD3, —CD2CD2H, or —CD2CDH2; or an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a phenyl group, or a naphthyl group, each unsubstituted or substituted with deuterium, a C1-C10 alkyl group, a phenyl group, or any combination thereof, but embodiments of the present disclosure are not limited thereto.
In Formula 2, a1 and a21 each indicate the number of R1 and the number of R21, respectively, and may each independently be an integer from 0 to 20 (for example, an integer from 0 to 10 or an integer from 0 to 5). When a1 is 2 or more, two or more R1(s) may be identical to or different from each other, and when a21 is 2 or more, two or more R21(s) may be identical to or different from each other.
In Formula 2, ring CY1 and R2 are not linked to each other, and R1 and R2 are not linked to each other.
In an embodiment, a group represented by
in Formula 2 may be a C53-C10 cycloalkenyl group, a C2-C10 heterocycloalkenyl group, a C6-C30 aryl group, a C2-C30 heteroaryl group, a monovalent non-aromatic condensed polycyclic group, or a monovalent non-aromatic condensed heteropolycyclic group, each unsubstituted or substituted with R1(s) in the number of a1.
In Formula 2, R1 and R2 may each independently be:
hydrogen, deuterium, —F, —Cl, —Br, —I, a cyano group, or —SF5; or
a C1-C60 alkyl group, a C1-C60 alkoxy group, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, or a C2-C10 heterocycloalkenyl group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a cyano group, a C1-C20 alkyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a norbornyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridinyl group, a pyrimidinyl group, or any combination thereof, and
a1 may be an integer from 0 to 10.
Detailed descriptions of a1, R1, a C1-C60 alkyl group, a C1-C60 alkoxy group, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C2-C10 heterocycloalkenyl group, a C6-C30 aryl group, a C2-C30 heteroaryl group, a monovalent non-aromatic condensed polycyclic group, and a monovalent non-aromatic condensed heteropolycyclic group are the same as described above.
In an embodiment, a group represented by
in Formula 2 may be a phenyl group, a biphenyl group, a naphthyl group, a fluorenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a pyrrolyl group, a thiophenyl group, a furanyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, an oxazolyl group, an isoxazolyl group, a pyridinyl group, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group, an isoindolyl group, an indolyl group, an indazolyl group, a purinyl group, a quinolinyl group, an isoquinolinyl group, a benzoquinolinyl group, a quinoxalinyl group, a quinazolinyl group, a cinnolinyl group, a carbazolyl group, a phenanthrolinyl group, a benzimidazolyl group, a benzofuranyl group, a benzothiophenyl group, an isobenzothiazolyl group, a benzoxazolyl group, an isobenzoxazolyl group, a triazolyl group, a tetrazolyl group, an oxadiazolyl group, a triazinyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, an imidazopyridinyl group, or an imidazopyrimidinyl group, each unsubstituted or substituted with R1(s) in the number of a1.
In Formula 2, R1 and R2 may each independently be:
hydrogen, deuterium, —F, —Cl, —Br, —I, a cyano group, or —SF5; or
a methyl group, an ethyl group, a propyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonanyl group (an n-nonyl group), an isononanyl group (an isononyl group), a sec-nonanyl group (a sec-nonyl group), a tert-nonanyl group (a tert-nonyl group), an n-decanyl group, an isodecanyl group, a sec-decanyl group, a tert-decanyl group, a C1-C10 alkoxy, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a norbornyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, or a cycloheptenyl group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a cyano group, a C1-C20 alkyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a norbornyl group, a norbornenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridinyl group, a pyrimidinyl group, or any combination thereof, and
a1 may be an integer from 0 to 5, but embodiments of the present disclosure are not limited thereto.
In an embodiment, a group represented by
in Formula 2 may be a group represented by one of Formulae 10-13(1) to 10-13(18) or 10-13:
In Formulae 10-13(1) to 10-13(18) and 10-13, R1a to R1e are each independently the same as defined in connection with R1, wherein R1a to R1e are not each hydrogen, and * indicates a binding site to a neighboring atom (e.g., carbon atom).
For example, a group represented by
in Formula 2 may be a group represented by one of Formulae 10-13 to 10-240, wherein R1, R2, R4, R5, R21, and R10a may each independently be hydrogen, deuterium, —F, a cyano group, a nitro group, —SF5, —CH3, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a group represented by one of Formulae 9-1 to 9-19, a group represented by one of Formulae 10-1 to 10-240, or —Si(Q3)(Q4)(Q5) (wherein Q3 to Q5 are the same as described above), but embodiments of the present disclosure are not limited thereto:
In Formulae 9-1 to 9-19 and 10-1 to 10-240, * indicates a binding site to a neighboring atom, Ph indicates a phenyl group, and TMS indicates a trimethylsilyl group.
In Formula 2, L11 may be a C5-C30 carbocyclic group that is unsubstituted or substituted with at least one R10a or a C2-C30 heterocyclic group that is unsubstituted or substituted with at least one R10a, wherein R10a is the same as described above.
For example, L11 may be a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a cyclopentadiene group, a thiophene group, a furan group, an indole group, a benzoborole group, a benzophosphole group, an indene group, a benzosilole group, a benzogermole group, a benzothiophene group, a benzoselenophene group, a benzofuran group, a carbazole group, a dibenzoborole group, a dibenzophosphole group, a fluorene group, a dibenzosilole group, a dibenzogermole group, a dibenzothiophene group, a dibenzoselenophene group, a dibenzofuran group, a dibenzothiophene 5-oxide group, a 9H-fluorene-9-one group, a dibenzothiophene 5,5-dioxide group, an azaindole group, an azabenzoborole group, an azabenzophosphole group, an azaindene group, an azabenzosilole group, an azabenzogermole group, an azabenzothiophene group, an azabenzoselenophene group, an azabenzofuran group, an azacarbazole group, an azadibenzoborole group, an azadibenzophosphole group, an azafluorene group, an azadibenzosilole group, an azadibenzogermole group, an azadibenzothiophene group, an azadibenzoselenophene group, an azadibenzofuran group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isoxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, or a benzothiadiazole group, each unsubstituted or substituted with at least one R10a group, but embodiments of the present disclosure are not limited thereto.
In Formula 2, b11 indicates the number of L11, and may be an integer from 0 to 10, wherein, when b11 is 0, a group represented by *-(L11)b11-*′ may be a single bond, and when b11 is 2 or more, two or more L11(s) may be identical to or different from each other. For example, b11 may be 0, 1, 2, or 3, but embodiments of the present disclosure are not limited thereto.
In Formula 2, two or more of a plurality of neighboring R21(s) may optionally be linked to form a C5-C30 carbocyclic group that is unsubstituted or substituted with at least one R10a group or a C2-C30 heterocyclic group that is unsubstituted or substituted with at least one R10a group (for example, a benzene group, a cyclopentane group, a cyclopentadiene group, a furan group, a thiophene group, a pyrrole group, a silole group, an indene group, a benzofuran group, a benzothiophene group, an indole group, or a benzosilole group, each unsubstituted or substituted with at least one R10a group), wherein R10a is the same as defined in connection with R21. Detailed descriptions of a C5-C30 carbocyclic group and a C2-C30 heterocyclic group are the same as described above.
In Formula 2, * and *′ each indicate a binding site to M in Formula 1.
In an embodiment, a group represented by
in Formula 2 may be a group represented by one of Formulae CY21-1 to CY21-25:
In Formulae CY21-1 to CY21-25,
X21 and R21 may each independently be the same as described herein,
X22 may be C(R22)(R23), N(R22), O, S, or Si(R22)(R23),
R22 to R29 may each independently be the same as defined in connection with R21,
a26 may be an integer from 0 to 6,
a24 may be an integer from 0 to 4,
a23 may be an integer from 0 to 3,
a22 may be an integer from 0 to 2,
*″ indicates a binding site to a carbon atom of a neighboring 6-membered ring in Formula 2, and
* indicates a binding site to M in Formula 1.
In an embodiment, a group represented by
in Formula 2 may be a group represented by one of Formulae CY21(1) to CY21(56) or a group represented by one of Formulae CY21-20 to CY21-25:
In Formulae CY21(1) to CY21(56),
X21 and R21 may each independently be the same as described herein,
R21a to R21d may each independently be the same as defined in connection with R21, wherein R21 and R21a to R21d are not each hydrogen,
*″ indicates a binding site to a carbon atom of a neighboring 6-membered ring in Formula 2, and
* indicates a binding site to M in Formula 1.
In an embodiment, a group represented by
in Formula 2 may be a group represented by one of Formulae CY21(1), CY21(3), or CY21(10) or a group represented by one of Formulae CY21-20 to CY21-25, but embodiments of the present disclosure are not limited thereto. For example, in Formula CY21(10), R21a and R21b may be identical to or different from each other. In an embodiment, in Formula CY21(10), R21a and R21b may be different from each other, and the number of carbon atoms included in R21a may be larger than the number of carbon atoms included in R21b.
In an embodiment, in Formula 1, L1 may be a ligand represented by Formula 2A or 2B, but embodiments of the present disclosure are not limited thereto:
In Formulae 2A and 2B, X1, X21, ring CY1, ring CY21, X4, X5, R1, R2, R21, a1, a21, L11, b11, *, and *′ may each independently be the same as described herein, wherein X2 and X3 may each independently be O, S, or Se.
In Formula 1, L2 may be a bidentate ligand linked to M of Formula 1 via O, S, N, C, P, Si, or As.
In an embodiment, in Formula 1, L2 may be a bidentate ligand represented by Formula 3:
In Formula 3,
X31 and X32 may each independently be O, S, N, C, P, Si, or As,
indicates an arbitrary atom group linking X31 and X32 to each other, and
* and *′ each indicate a binding site to M in Formula 1.
For example, in Formula 3, i) X31 and X32 may each be O; ii) X31 may be O, and X32 may be N, or iii) X31 may be N, and X32 may be C, but embodiments of the present disclosure are not limited thereto.
In an embodiment, in Formula 1, L2 may be a monodentate ligand, for example, I−, Br−, C1−, sulfide, nitrate, azide, hydroxide, cyanate, isocyanate, thiocyanate, water, acetonitrile, pyridine, ammonia, carbon monoxide, P(Ph)3, P(Ph)2CH3, PPh(CH3)2, P(CH3)3, or any combination thereof, but embodiments of the present disclosure are not limited thereto.
In an or more embodiment, in Formula 1, L2 may be a bidentate ligand, for example, oxalate, acetylacetonate, picolinic acid, 1,2-bis(diphenylphosphino)ethane, 1,1-bis(diphenylphosphino)methane, glycinate, ethylenediamine, or any combination thereof, but embodiments of the present disclosure are not limited thereto.
In an or more embodiment, in Formula 1, L2 may be a group represented by one of Formulae 3A to 3F:
In Formulae 3A to 3F,
Y13 may be O, N, N(Z1), P(Z1)(Z2), or As(Z1)(Z2),
Y14 may be O, N, N(Z3), P(Z3)(Z4), or As(Z3)(Z4),
T11 may each independently be a single bond, a double bond, *—C(Z11)(Z12)—*′, *—C(Z11)═C(Z12)—*′, *═C(Z11)—*′, *—C(Z11)═*′, *═C(Z11)—C(Z12)═C(Z13)—*′, *—C(Z11)═C(Z12)—C(Z13)═*′, *—N(Z11)—*′, or a C5-C30 carbocyclic group that is unsubstituted or substituted with at least one Z11 group,
a11 may be an integer from 1 to 10,
Y11 and Y12 may each independently be C or N,
T21 may be a single bond, a double bond, O, S, C(Z11)(Z12), Si(Z11)(Z12), or N(Z11),
ring CY11 and ring CY12 may each independently be a C5-C30 carbocyclic group or a C2-C30 heterocyclic group,
A1 may be P or As,
Z1 to Z4 and Z11 to Z13 may each independently be the same as defined in connection with R21,
d1 and d2 may each independently be an integer from 0 to 10, and
* and *′ each indicate a binding site to M in Formula 1.
In Formulae 3A to 3F, the C5-C30 carbocyclic group and the C2-C30 heterocyclic group may each independently be the same as defined in connection with ring CY21.
For example, a moiety represented by
in Formula 3D may be a group represented by one of Formulae CY11-1 to CY11-34, and/or
a moiety represented by
in Formulae 3C and 3D may be a group represented by one of Formulae CY12-1 to CY12-34:
In Formulae CY11-1 to CY11-34 and CY12-1 to CY12-34,
X31 may be O, S, N(Z11), C(Z11)(Z12), or Si(Z11)(Z12),
X41 may be O, S, N(Z21), C(Z21)(Z22), or Si(Z21)(Z22),
Y11, Y12, Z1, and Z2 may each independently be the same as described herein,
Z11 to Z18 and Z21 to Z28 may each independently be the same as defined in connection with R21,
d12 and d22 may each independently be an integer from 0 to 2,
d13 and d23 may each independently be an integer from 0 to 3,
d14 and d24 may each independently be an integer from 0 to 4,
d15 and d25 may each independently be an integer from 0 to 5,
d16 and d26 may each independently be an integer from 0 to 6, and
in Formulae CY11-1 to CY11-34 and CY12-1 to CY12-34, * and *′ each indicate a binding site to M in Formula 1, and *″ indicates a binding site to a neighboring atom in Formula 3C or a binding site to T21 in Formula 3D.
In an embodiment, in Formula 1, L2 may be a group represented by one of Formulae 3-1(1) to 3-1(66) or one of 3-1(301) to 3-1(309), but embodiments of the present disclosure are not limited thereto:
In Formulae 3-1(1) to 3-1(66) and 3-1(301) to 3-1(309),
X41 may be O, S, N(Z21), C(Z21)(Z22), or Si(Z21)(Z22),
Z1 to Z4, Z1a, Z1b, Z1c, Z1d, Z2a, Z2b, Z2c, Z2d, Z11 to Z14, Z21 and Z22 may each independently be the same as defined in connection with R21,
d14 may be an integer from 0 to 4,
d26 may be an integer from 0 to 6, and
* and *′ each indicate a binding site to M in Formula 1.
In an embodiment, the organometallic compound represented by Formula 1 may emit red light or green light. In an embodiment, the organometallic compound represented by Formula 1 may emit red light or green light, each having a maximum emission wavelength of about 500 nm or more, for example, about 500 nm or more and about 650 nm or less.
The terms “an azaindole group, an azabenzoborole group, an azabenzophosphole group, an azaindene group, an azabenzosilole group, an azabenzogermole group, an azabenzothiophene group, an azabenzoselenophene group, an azabenzofuran group, an azacarbazole group, an azadibenzoborole group, an azadibenzophosphole group, an azafluorene group, an azadibenzosilole group, an azadibenzogermole group, an azadibenzothiophene group, an azadibenzoselenophene group, an azadibenzofuran group, an azadibenzothiophene 5-oxide group, an aza-9H-fluorene-9-one group, and an azadibenzothiophene 5,5-dioxide group” as used herein each refer to a heterocyclic group having the same backbone as “an indole group, a benzoborole group, a benzophosphole group, an indene group, a benzosilole group, a benzogermole group, a benzothiophene group, a benzoselenophene group, a benzofuran group, a carbazole group, a dibenzoborole group, a dibenzophosphole group, a fluorene group, a dibenzosilole group, a dibenzogermole group, a dibenzothiophene group, a dibenzoselenophene group, a dibenzofuran group, a dibenzothiophene 5-oxide group, a 9H-fluorene-9-one group, and a dibenzothiophene 5,5-dioxide group” in which at least one carbon atom constituting the cyclic groups is substituted with N.
In an embodiment, the organometallic compound represented by Formula 1 may be one of Compounds 1 to 420, but embodiments of the present disclosure are not limited thereto:
L1 of the organometallic compound represented by Formula 1 may be a ligand represented by Formula 2, and n1 which indicates the number of L1 may be 1, 2, or 3. That is, the organometallic compound essentially includes, as ligands linked to metal M, at least one ligand represented by Formula 2.
X2 and X3 in the ligand represented by Formula 2 are each independently O, S, Se, or C(R2), wherein X2 or X3 is O, S, or Se. That is, in Formula 2, the 5-membered ring (see Formula 2′) does not include *═N—*′ (* and *′ each indicate a binding site to a neighboring atom) as a ring-forming atom, and includes O, S, or Se. In addition, in Formula 2, the 5-membered ring is condensed with the 6-membered ring while sharing carbon 1 and carbon 2 (see Formula 2′). A reduction in the intermolecular bonding force of the organometallic compound represented by Formula 1 may be prevented. Therefore, a reduction in the lifespan of an electronic device, for example, an organic light-emitting device, which includes the organometallic compound represented by Formula 1, may be prevented.
The ligand represented by Formula 2 includes “ring CY1”. Therefore, a transition dipole moment increases in an alignment axis direction of Formula 1, and the alignment of the organometallic compound represented by Formula 1 may be improved, thereby increasing the luminescence efficiency of an electronic device, for example, an organic light-emitting device, which includes the organometallic compound represented by Formula 1.
Meanwhile, in Formula 2, ring CY1 and R2 are not linked to each other, and R1 and R2 are not linked to each other. Therefore, it is possible to prevent a transition dipole moment of Formula 1 from deviating to a direction other than the alignment axis direction of Formula 1, thereby increasing the luminescence efficiency of an electronic device, for example, an organic light-emitting device, which includes the organometallic compound represented by Formula 1.
A highest occupied molecular orbital (HOMO) energy level, a lowest unoccupied molecular orbital (LUMO) energy level, and a triplet (Ti) energy level of some compounds of the organometallic compound represented by Formula 1 are evaluated by a density functional theory (DFT) of Gaussian program with molecular structure optimization based on B3LYP, and results are shown in Table 1.
Referring to Table 1, it is confirmed that the organometallic compound represented by Formula 1 has such electrical characteristics that are suitable for use in an electronic device, for example, an organic light-emitting device, for use as a dopant.
Synthesis methods of the organometallic compound represented by Formula 1 may be understood by one of ordinary skill in the art by referring to Synthesis Examples provided below.
Therefore, the organometallic compound represented by Formula 1 may be suitable for use in an organic layer of an organic light-emitting device, for example, for use as a dopant in an emission layer of the organic layer. Another aspect of the present disclosure provides an organic light-emitting device including: a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode and including an emission layer, wherein the organic layer includes at least one organometallic compound represented by Formula 1.
The organic light-emitting device may have, due to the inclusion of an organic layer including the organometallic compound represented by Formula 1, a low driving voltage, high external quantum luminescence efficiency, a low roll-off ratio, and a long lifespan.
The organometallic compound represented by Formula 1 may be used between a pair of electrodes of an organic light-emitting device. For example, the organometallic compound represented by Formula 1 may be included in the emission layer. In this regard, the organometallic compound may act as a dopant, and the emission layer may further include a host (that is, an amount of the organometallic compound represented by Formula 1 is smaller than an amount of the host). The emission layer may emit, for example, green light or red light.
The expression “(an organic layer) includes at least one organometallic compound represented by Formula 1” as used herein may include a case in which “(an organic layer) includes identical organometallic compounds represented by Formula 1” and a case in which “(an organic layer) includes two or more different organometallic compounds represented by Formula 1”.
For example, the organic layer may include, as the organometallic compound represented by Formula 1, only Compound 1. In this regard, Compound 1 may exist only in the emission layer of the organic light-emitting device. In an embodiment, the organic layer may include, as the organometallic compound represented by Formula 1, Compound 1 and Compound 2. In this regard, Compound 1 and Compound 2 may exist in an identical layer (for example, Compound 1 and Compound 2 all may exist in an emission layer).
The first electrode may be an anode, which is a hole injection electrode, and the second electrode may be a cathode, which is an electron injection electrode; or the first electrode may be a cathode, which is an electron injection electrode, and the second electrode may be an anode, which is a hole injection electrode.
For example, the organic light-emitting device, the first electrode is an anode, and the second electrode is a cathode, and the organic layer further includes a hole transport region disposed between the first electrode and the emission layer and an electron transport region disposed between the emission layer and the second electrode, and the hole transport region includes a hole injection layer, a hole transport layer, an electron blocking layer, or any combination thereof, and the electron transport region includes a hole blocking layer, an electron transport layer, an electron injection layer, or any combination thereof.
The term “organic layer” as used herein refers to a single layer and/or a plurality of layers disposed between the first electrode and the second electrode of an organic light-emitting device. The “organic layer” may include, in addition to an organic compound, an organometallic complex including metal.
FIGURE is a schematic cross-sectional view of an organic light-emitting device 10 according to an embodiment. Hereinafter, the structure of an organic light-emitting device according to an embodiment and a method of manufacturing an organic light-emitting device according to an embodiment will be described in connection with the FIGURE. The organic light-emitting device 10 includes a first electrode 11, an organic layer 15, and a second electrode 19, which are sequentially stacked.
A substrate may be additionally disposed under the first electrode 11 or above the second electrode 19. For use as the substrate, any substrate that is used in the organic light-emitting device art may be used, and the substrate may be a glass substrate or a transparent plastic substrate, each having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water resistance.
The first electrode 11 may be formed by depositing or sputtering a material for forming the first electrode 11 on the substrate. The first electrode 11 may be an anode. The material for forming the first electrode 11 may be a material with a high work function to facilitate hole injection. The first electrode 11 may be a reflective electrode, a semi-reflective electrode, or a transmissive electrode. The material for forming the first electrode may be, for example, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), or zinc oxide (ZnO). In an embodiment, the material for forming the first electrode 11 may be a metal or a metal alloy, such as magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), or magnesium-silver (Mg—Ag).
The first electrode 11 may have a single-layered structure or a multi-layered structure including two or more layers. For example, the first electrode 11 may have a three-layered structure of ITO/Ag/ITO, but the structure of the first electrode 11 is not limited thereto.
The organic layer 15 is disposed on the first electrode 11.
The organic layer 15 may include a hole transport region, an emission layer, and an electron transport region.
The hole transport region may be disposed between the first electrode 11 and the emission layer.
The hole transport region may include a hole injection layer, a hole transport layer, an electron blocking layer, a buffer layer, or any combination thereof.
The hole transport region may include only either a hole injection layer or a hole transport layer. In an embodiment, the hole transport region may have a hole injection layer/hole transport layer structure or a hole injection layer/hole transport layer/electron blocking layer structure, which are sequentially stacked in this stated order from the first electrode 11.
When the hole transport region includes a hole injection layer, the hole injection layer may be formed on the first electrode 11 by using a suitable method, for example, vacuum deposition, spin coating, casting, and/or Langmuir-Blodgett (LB) deposition.
When a hole injection layer is formed by vacuum deposition, the deposition conditions may vary according to a material that is used to form the hole injection layer, and the structure and thermal characteristics of the hole injection layer. For example, the deposition conditions may include a deposition temperature of about 100° C. to about 500° C., a vacuum pressure of about 10−8 torr to about 10−3 torr, and a deposition rate of about 0.01 Å/sec to about 100 Å/sec. However, the deposition conditions are not limited thereto.
When the hole injection layer is formed using spin coating, coating conditions may vary according to the material used to form the hole injection layer, and the structure and thermal properties of the hole injection layer. For example, a coating speed may be from about 2,000 rpm to about 5,000 rpm, and a temperature at which a heat treatment is performed to remove a solvent after coating may be from about 80° C. to about 200° C. However, the coating conditions are not limited thereto.
Conditions for forming a hole transport layer and an electron blocking layer may be understood by referring to conditions for forming the hole injection layer.
The hole transport region may include, for example, m-MTDATA, TDATA, 2-TNATA, NPB, β-NPB, TPD, spiro-TPD, spiro-NPB, methylated-NPB, TAPC, HMTPD, 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphor sulfonic acid (PANI/CSA), polyaniline/poly(4-styrenesulfonate) (PANI/PSS), a compound represented by Formula 201 below, a compound represented by Formula 202 below, or any combination thereof:
In Formula 201, Ar101 and Ar102 may each independently be a phenylene group, a pentalenylene group, an indenylene group, a naphthylene group, an azulenylene group, a heptalenylene group, an acenaphthylene group, a fluorenylene group, a phenalenylene group, a phenanthrenylene group, an anthracenylene group, a fluoranthenylene group, a triphenylenylene group, a pyrenylene group, a chrysenylene group, a naphthacenylene group, a picenylene group, a perylenylene group, or a pentacenylene group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C3-C10 cycloalkyl group, a C3-C10 cycloalkenyl group, a C2-C10 heterocycloalkyl group, a C2-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group (e.g., a phenyl(C1-C20 alkyl) group), a C1-C60 heteroaryl group, a C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic condensed heteropolycyclic group, or any combination thereof.
In Formula 201, xa and xb may each independently be an integer from 0 to 5, or may be 0, 1, or 2. For example, xa may be 1, and xb may be 0, but embodiments of the present disclosure are not limited thereto.
In Formulae 201 and 202, R101 to R108, R111 to R119, and R121 to R124 may each independently be:
hydrogen, deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C10 alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, pentyl group, a hexyl group, and the like), or a C1-C10 alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, and the like);
a C1-C10 alkyl group or a C1-C10 alkoxy group, each substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, or any combination thereof; or
a phenyl group, a naphthyl group, an anthracenyl group, a fluorenyl group, or a pyrenyl group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C10 alkyl group, a C1-C10 alkoxy group, or any combination thereof,
but embodiments of the present disclosure are not limited thereto.
In Formula 201, R109 may be a phenyl group, a naphthyl group, an anthracenyl group, or a pyridinyl group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C20 alkyl group, a C1-C20 alkoxy group, a phenyl group, a naphthyl group, an anthracenyl group, a pyridinyl group, or any combination thereof.
In an embodiment, the compound represented by Formula 201 may be represented by Formula 201A below, but embodiments of the present disclosure are not limited thereto:
Detailed descriptions of R101, R111, R112, and R109 in Formula 201A are the same as described above.
For example, the compound represented by Formula 201, and the compound represented by Formula 202 may include Compounds HT1 to HT20 but are not limited thereto:
A thickness of the hole transport region may be from about 100 Å to about 10,000 Å, for example, about 100 Å to about 1,000 Å. When the hole transport region includes a hole injection layer, a hole transport layer, or any combination thereof, a thickness of the hole injection layer may be in a range of about 100 Å to about 10,000 Å, for example, about 100 Å to about 1,000 Å, and a thickness of the hole transport layer may be in a range of about 50 Å to about 2,000 Å, for example about 100 Å to about 1,500 Å. When the thicknesses of the hole transport region, the hole injection layer, and the hole transport layer are within these ranges, satisfactory hole transporting characteristics may be obtained without a substantial increase in driving voltage.
The hole transport region may further include, in addition to these materials, a charge-generation material for the improvement of conductive properties. The charge-generation material may be homogeneously or non-homogeneously dispersed in the hole transport region.
The charge-generation material may be, for example, a p-dopant. The p-dopant may be a quinone derivative, a metal oxide, a cyano group-containing compound, or any combination thereof, but embodiments of the present disclosure are not limited thereto. Non-limiting examples of the p-dopant are a quinone derivative, such as tetracyanoquinodimethane (TCNQ) or 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinodimethane (F4-TCNQ); a metal oxide, such as a tungsten oxide or a molybdenum oxide; and a cyano group-containing compound, such as Compound HT-D1 below, but are not limited thereto:
The hole transport region may include a buffer layer.
Also, the buffer layer may compensate for an optical resonance distance according to a wavelength of light emitted from the emission layer, and thus, efficiency of a formed organic light-emitting device may be improved.
Meanwhile, when the hole transport region includes an electron blocking layer, a material for the electron blocking layer may be materials for the hole transport region described above, materials for a host to be explained later, or any combination thereof. However, the material for the electron blocking layer is not limited thereto. For example, when the hole transport region includes an electron blocking layer, a material for the electron blocking layer may be mCP, which will be explained later.
Then, an emission layer may be formed on the hole transport region by vacuum deposition, spin coating, casting, LB deposition, or the like. When the emission layer is formed by vacuum deposition or spin coating, the deposition or coating conditions may be similar to those applied in forming the hole injection layer although the deposition or coating conditions may vary according to a compound that is used to form the emission layer.
The emission layer may include a host and a dopant, and the dopant may include the organometallic compound represented by Formula 1.
The host may include TPBi, TBADN, ADN (also referred to as “DNA”), CBP, CDBP, TCP, mCP, one of Compounds H50 to H52, or any combination thereof:
When the organic light-emitting device is a full-color organic light-emitting device, the emission layer may be patterned into a red emission layer, a green emission layer, and/or a blue emission layer. In an embodiment, due to a stacked structure including a red emission layer, a green emission layer, and/or a blue emission layer, the emission layer may emit white light.
When the emission layer includes a host and a dopant, an amount of the dopant may be in a range of about 0.01 parts by weight to about 15 parts by weight based on 100 parts by weight of the host, but embodiments of the present disclosure are not limited thereto.
A thickness of the emission layer may be in a range of about 100 Å to about 1,000 Å, for example, about 200 Å to about 600 Å. When the thickness of the emission layer is within this range, excellent light-emission characteristics may be obtained without a substantial increase in driving voltage.
Then, an electron transport region may be disposed on the emission layer.
The electron transport region may include a hole blocking layer, an electron transport layer, an electron injection layer, or any combination thereof.
For example, the electron transport region may have a hole blocking layer/electron transport layer/electron injection layer structure, or an electron transport layer/electron injection layer structure, but the structure of the electron transport region is not limited thereto. The electron transport layer may have a single-layered structure or a multi-layered structure including two or more different materials.
Conditions for forming the hole blocking layer, the electron transport layer, and the electron injection layer which constitute the electron transport region may be understood by referring to the conditions for forming the hole injection layer.
When the electron transport region includes a hole blocking layer, the hole blocking layer may include, for example, BCP, Bphen, BAlq, or any combination thereof, but embodiments of the present disclosure are not limited thereto:
A thickness of the hole blocking layer may be from about 20 Å to about 1,000 Å, for example, about 30 Å to about 300 Å. When the thickness of the hole blocking layer is within these ranges, the hole blocking layer may have excellent hole blocking characteristics without a substantial increase in driving voltage.
The electron transport layer may include BCP, Bphen, Alq3, BAlq, TAZ, NTAZ, or any combination thereof:
In an embodiment, the electron transport layer may include one of ET1 to ET25, but embodiments of the present disclosure are not limited thereto:
A thickness of the electron transport layer may be from about 100 Å to about 1,000 Å, for example, about 150 Å to about 500 Å. When the thickness of the electron transport layer is within the range described above, the electron transport layer may have satisfactory electron transport characteristics without a substantial increase in driving voltage.
Also, the electron transport layer may further include, in addition to the materials described above, a metal-containing material.
The metal-containing material may include a Li complex. The Li complex may include, for example, Compound ET-D1 (LiQ), ET-D2, or any combination thereof:
The electron transport region may include an electron injection layer that promotes flow of electrons from the second electrode 19 thereinto.
The electron injection layer may include LiF, NaCl, CsF, Li2O, BaO, or any combination thereof.
A thickness of the electron injection layer may be from about 1 Å to about 100 Å, for example, about 3 Å to about 90 Å. When a thickness of the electron injection layer is within these ranges, satisfactory electron injection characteristics may be obtained without substantial increase in driving voltage.
The second electrode 19 is disposed on the organic layer 15. The second electrode 19 may be a cathode. A material for forming the second electrode 19 may be a metal, an alloy, an electrically conductive compound, or any combination thereof, which have a relatively low work function. For example, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), or magnesium-silver (Mg—Ag) may be used as the material for forming the second electrode 19. To manufacture a top-emission type light-emitting device, a transmissive electrode formed using ITO or IZO may be used as the second electrode 19.
Hereinbefore, the organic light-emitting device according to an embodiment has been described in connection with the FIGURE.
Another aspect of the present disclosure provides a diagnostic composition including at least one organometallic compound represented by Formula 1.
The organometallic compound represented by Formula 1 provides high luminescence efficiency. Accordingly, a diagnostic composition including the organometallic compound may have high diagnostic efficiency.
The diagnostic composition may be used in various applications including a diagnosis kit, a diagnosis reagent, a biosensor, and a biomarker.
The term “C1-C60 alkyl group” as used herein refers to a linear or branched saturated aliphatic hydrocarbon monovalent group having 1 to 60 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isoamyl group, and a hexyl group. The term “C1-C60 alkylene group” as used herein refers to a divalent group having the same structure as the C1-C60 alkyl group.
The term “C1-C60 alkoxy group” as used herein refers to a monovalent group represented by —OA101 (wherein A101 is the C1-C60 alkyl group), and examples thereof include a methoxy group, an ethoxy group, and an isopropyloxy group.
The term “C2-C60 alkenyl group” as used herein refers to a hydrocarbon group having at least one carbon-carbon double bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof include an ethenyl group, a propenyl group, and a butenyl group. The term “C2-C60 alkenylene group” as used herein refers to a divalent group having the same structure as the C2-C60 alkenyl group.
The term “C2-C60 alkynyl group” as used herein refers to a hydrocarbon group having at least one carbon-carbon triple bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof include an ethynyl group, and a propynyl group. The term “C2-C60 alkynylene group” as used herein refers to a divalent group having the same structure as the C2-C60 alkynyl group.
The term “C3-C10 cycloalkyl group” as used herein refers to a monovalent saturated hydrocarbon monocyclic group having 3 to 10 carbon atoms, and non-limiting examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. The term “C3-C10 cycloalkylene group” as used herein refers to a divalent group having the same structure as the C3-C10 cycloalkyl group.
The term “C2-C10 heterocycloalkyl group” as used herein refers to a monovalent saturated monocyclic group having N, O, P, Si, Se, S, or a combination thereof and 2 to 10 carbon atoms as ring-forming atoms, and non-limiting examples thereof include a tetrahydrofuranyl group and a tetrahydrothiophenyl group. The term “C2-C10 heterocycloalkylene group” as used herein refers to a divalent group having the same structure as the C2-C10 heterocycloalkyl group.
The term “C3-C10 cycloalkenyl group” as used herein refers to a monovalent monocyclic group that has 3 to 10 carbon atoms and at least one carbon-carbon double bond in the ring thereof and no aromaticity, and non-limiting examples thereof include a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group. The term “C3-C10 cycloalkenylene group” as used herein refers to a divalent group having the same structure as the C3-C10 cycloalkenyl group.
The term “C2-C10 heterocycloalkenyl group” as used herein refers to a monovalent monocyclic group that has N, O, P, Si, Se, S, or any combination thereof and 2 to 10 carbon atoms as ring-forming atoms, and at least one double bond in its ring. Examples of the C2-C10 heterocycloalkenyl group are a 2,3-dihydrofuranyl group, and a 2,3-dihydrothiophenyl group. The term “C2-C10 heterocycloalkenylene group” as used herein refers to a divalent group having the same structure as the C2-C10 heterocycloalkenyl group.
The term “C6-C60 aryl group” as used herein refers to a monovalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms, and the term “C6-C60 arylene group” as used herein refers to a divalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms. Non-limiting examples of the C6-C60 aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, and a chrysenyl group. When the C6-C60 aryl group and the C6-C60 arylene group each include two or more rings, the rings may be fused to each other.
The term “C7-C60 arylalkyl group” as used herein refers to an alkylene group substituted with an aryl group. A non-limiting example of a C7-C60 arylalkyl group includes a —CH2-phenyl (i.e., benzyl) group and a CH2-naphthyl group.
The term “phenyl(C1-C20 alkyl) group” as used herein refers to an alkylene group substituted with a phenyl group. Non-limiting examples of a phenyl(C1-C20 alkyl) group include a —CH2-phenyl (i.e., benzyl) group and a (CH2)3-phenyl group.
The term “C1-C60 heteroaryl group” as used herein refers to a monovalent group having a heterocyclic aromatic system that has N, O, P, Si, Se, S, or any combination thereof and 1 to 60 carbon atoms as ring-forming atoms. The term “C1-C60 heteroarylene group” as used herein refers to a divalent group having a heterocyclic aromatic system that has N, O, P, Si, Se, S, or any combination thereof and 1 to 60 carbon atoms as ring-forming atoms. Non-limiting examples of the C1-C60 heteroaryl group include a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, and an isoquinolinyl group. When the C1-C60 heteroaryl group and the C1-C60 heteroarylene group each include two or more rings, the rings may be fused to each other.
The term “C2-C60 heteroarylalkyl group” as used herein refers to an alkylene group substituted with a heteroaryl group. A non-limiting example of a C2-C60 heteroarylalkyl group includes a —CH2-pyridyl group.
The term “C6-C60 aryloxy group” as used herein indicates —OA102 (wherein A102 is the C6-C60 aryl group), and the term “C6-C60 arylthio group” as used herein indicates —SA103 (wherein A103 is the C6-C60 aryl group).
The term “monovalent non-aromatic condensed polycyclic group” as used herein refers to a monovalent group (for example, having 8 to 60 carbon atoms) having two or more rings condensed to each other, only carbon atoms as ring-forming atoms, and no aromaticity in its entire molecular structure. Examples of the monovalent non-aromatic condensed polycyclic group include a fluorenyl group. The term “divalent non-aromatic condensed polycyclic group” as used herein refers to a divalent group having the same structure as the monovalent non-aromatic condensed polycyclic group.
The term “monovalent non-aromatic condensed heteropolycyclic group” as used herein refers to a monovalent group (for example, having 2 to 60 carbon atoms) having two or more rings condensed to each other, a heteroatom selected from N, O, P, Si, and S, other than carbon atoms, as a ring-forming atom, and no aromaticity in its entire molecular structure. Non-limiting examples of the monovalent non-aromatic condensed heteropolycyclic group include a carbazolyl group. The term “divalent non-aromatic condensed heteropolycyclic group” as used herein refers to a divalent group having the same structure as the monovalent non-aromatic condensed heteropolycyclic group.
The term “C5-C30 carbocyclic group” as used herein refers to a saturated or unsaturated cyclic group having, as a ring-forming atom, 5 to 30 carbon atoms only. The C5-C30 carbocyclic group may be a monocyclic group or a polycyclic group.
The term “C2-C30 heterocyclic group” as used herein refers to a saturated or unsaturated cyclic group having N, O, Si, P, Se, S, or any combination thereof and 1 to 30 carbon atoms as ring-forming atoms. The C2-C30 heterocyclic group may be a monocyclic group or a polycyclic group.
A substituent of the substituted C5-C30 carbocyclic group, the substituted C2-C30 heterocyclic group, the substituted C1-C60 alkyl group, the substituted C2-C60 alkenyl group, the substituted C2-C60 alkynyl group, the substituted C1-C60 alkoxy group, the substituted C3-C10 cycloalkyl group, the substituted C2-C10 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C2-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C7-C60 arylalkyl group (e.g., the substituted phenyl(C1-C20 alkyl) group), the substituted C1-C60 heteroaryl group, the substituted C2-C60 heteroarylalkyl group, the substituted monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group may be:
deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, or a C1-C60 alkoxy group;
a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, or a C1-C60 alkoxy group, each substituted with deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C2-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group (e.g., a phenyl(C1-C20 alkyl) group), a C1-C60 heteroaryl group, C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic condensed heteropolycyclic group, —N(Q11)(Q12), —Si(Q13)(Q14)(Q15), —B(Q16)(Q17), —P(═O)(Q18)(Q19), or any combination thereof;
a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C2-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C7-C60 arylalkyl group (e.g., a phenyl(C1-C20 alkyl) group), a C6-C60 aryloxy group, a C6-C60 arylthio group, a C1-C60 heteroaryl group, a C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, or a monovalent non-aromatic condensed heteropolycyclic group; a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C2-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group (e.g., a phenyl(C1-C20 alkyl) group), a C60 heteroaryl group, C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, or a monovalent non-aromatic condensed heteropolycyclic group, each substituted with deuterium, —F, —Cl, —Br, —I, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C2-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C7-C60 arylalkyl group (e.g., a phenyl(C1-C20 alkyl) group), a C6-C60 aryloxy group, a C6-C60 arylthio group, a C1-C60 heteroaryl group, C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic condensed heteropolycyclic group, —N(Q21)(Q22), —Si(Q23)(Q24)(Q25), —B(Q26)(Q27), —P(═O)(Q28)(Q29), or any combination thereof;
—N(Q31)(Q32), —Si(Q33)(Q34)(Q35), —B(Q36)(Q37), or —P(═O)(Q38)(Q39); or
any combination thereof.
In the present specification, Q1 to Q9, Q11 to Q19, Q21 to Q29, and Q31 to Q39 may each independently be hydrogen, deuterium, —F, —Br, —I, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C3-C10 cycloalkyl group, a C2-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C2-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C6-C60 aryl group substituted with a C1-C60 alkyl group, a C6-C60 aryl group, or any combination thereof, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C7-C60 arylalkyl group (e.g., a phenyl(C1-C20 alkyl) group), a C1-C60 heteroaryl group, C2-C60 heteroarylalkyl group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic condensed heteropolycyclic group, or any combination thereof.
Hereinafter, a compound and an organic light-emitting device according to embodiments are described in detail with reference to Synthesis Example and Examples. However, the organic light-emitting device is not limited thereto. The wording “B was used instead of A” used in describing Synthesis Examples means that an amount of A used was identical to an amount of B used, in terms of a molar equivalent.
Synthesis of Intermediate L1
6-Chloro-2-phenylfuro[2,3-b]pyridine (2.55 g, 11.1 mmol), phenylboronic acid (2.603 g, 16.64 mmol), Pd(PPh3)4 (1.03 g, 0.89 mmol), and K2CO3 (3.83 g, 27.7 mmol) were mixed with 60 mL of tetrahydrofuran and 30 mL of distilled water, stirred at a temperature of 90° C. for 18 hours, and then cooled to room temperature. An organic layer was extracted from a result obtained therefrom by using ethyl acetate, dried by using anhydrous magnesium sulfate (MgSO4), and filtered to obtain a filtrate. The filtrate was concentrated to obtain a residue. The residue was purified by column chromatography using ethyl acetate:hexane=1:2 (v/v) as an eluent to obtain Intermediate L1 (2.85 g, 83%).
LC-MS m/z=272 (M+H)+.
Synthesis of Intermediate L1-Dimer
Intermediate L1 (1.99 g, 7.32 mmol) and iridium chloride hydrate (1.15 g, 3.25 mmol) were mixed with 21 mL of 2-ethoxyethanol and 7 mL of distilled water, stirred at a temperature of 120° C. for 24 hours under reflux, and then cooled to room temperature. A solid obtained therefrom was filtered, separated, and sufficiently washed in the order of water/methanol/hexane. The solid was dried in a vacuum oven to obtain Intermediate L1-dimer (1.95 g, 78%). The obtained compound was used in the next reaction without additional purification.
Synthesis of Compound 1
Thirty mL of 2-ethoxyethanol was added to Intermediate L1-dimer (1.94 g, 1.26 mmol), acetyl acetone (1.26 g, 12.6 mmol), and Na2CO3 (1.33 g, 12.6 mmol), and stirred at room temperature for 12 hours. An organic layer was extracted from a result obtained therefrom by using ethyl acetate, dried by using anhydrous magnesium sulfate (MgSO4), and filtered to obtain a filtrate. The filtrate was concentrated to obtain a residue. The residue was purified by column chromatography using dichloromethane:hexane=1:4 (v/v) as an eluent to obtain Compound 1 (0.451 g, 22%). The obtained compound was identified by Mass spectroscopy (MS) and HPLC analysis.
HRMS(MALDI-TOF) calcd for C43H31IrN2O4: m/z 832.1913, Found: 832.1913.
Synthesis of Intermediate L16
6-Chloro-2-phenylfuro[2,3-b]pyridine (2.69 g, 11.71 mmol), (3,5-dimethylphenyl)boronic acid (2.64 g, 17.56 mmol), Pd(PPh3)4 (1.08 g, 0.94 mmol), and K2CO3 (4.05 g, 29.3 mmol) were mixed with 60 mL of tetrahydrofuran and 30 mL of distilled water, stirred at a temperature of 90° C. for 18 hours, and then cooled to room temperature. An organic layer was extracted from a result obtained therefrom by using ethyl acetate, dried by using anhydrous magnesium sulfate (MgSO4), and filtered to obtain a filtrate. The filtrate was concentrated to obtain a residue. The residue was purified by column chromatography using ethyl acetate:hexane=1:2 (v/v) as an eluent to obtain Intermediate L16 (1.97 g, 56%).
LC-MS m/z=300 (M+H)+.
Synthesis of Intermediate L16-dimer
Intermediate L16 (1.97 g, 6.82 mmol) and iridium chloride hydrate (1.07 g, 3.03 mmol) were mixed with 21 mL of ethoxyethanol and 7 mL of distilled water, stirred at a temperature of 120° C. for 24 hours under reflux, and then cooled to room temperature. A solid obtained therefrom was filtered, separated, and sufficiently washed in the order of water/methanol/hexane. The solid was dried in a vacuum oven to obtain Intermediate L16-dimer (2.16 g, 86%). The obtained compound was used in a next reaction without additional purification.
Synthesis of Compound 16
Thirty mL of 2-ethoxyethanol was added to Intermediate L16-dimer (2.15 g, 1.31 mmol), acetyl acetone (1.31 g, 13.1 mmol), and Na2CO3 (1.38 g, 13.1 mmol), and stirred at room temperature for 12 hours. An organic layer was extracted from a result obtained therefrom by using ethyl acetate, dried by using anhydrous magnesium sulfate (MgSO4), and filtered to obtain a filtrate. The filtrate was concentrated to obtain a residue. The residue was purified by column chromatography using dichloromethane:hexane=1:4 (v/v) as an eluent to obtain Compound 16 (0.47 g, 20%). The obtained compound was identified by MS and HPLC analysis.
HRMS(MALDI-TOF) calcd for C47H39IrN2O4: m/z 888.2539, Found: 888.2538.
Synthesis of Intermediate L101
Intermediate L101 (2.08 g, 59%) was obtained in the same manner as in Synthesis of Intermediate L1 of Synthesis Example 1, except that 6-chloro-2-phenylthieno[2,3-b]pyridine (2.99 g, 12.2 mmol) was used instead of 6-chloro-2-phenylfuro[2,3-b]pyridine (2.55 g, 11.1 mmol).
LC-MS m/z=288 (M+H)+.
Synthesis of Intermediate L101-dimer
Intermediate L101-dimer (2.16 g, 86%) was obtained in the same manner as in Synthesis of Intermediate L1-dimer of Synthesis Example 1, except that Intermediate L101 (1.97 g, 7.03 mmol) was used instead of Intermediate L1.
Synthesis of Compound 101
Compound 101 (0.47 g, 22%) was obtained in the same manner as in Synthesis of Compound 1 of Synthesis Example 1, except that Intermediate L101-dimer (1.95 g, 1.22 mmol) was used instead of Intermediate L1-dimer. The obtained compound was identified by MS and HPLC analysis.
HRMS(MALDI-TOF) calcd for C43H30IrN2O2S2: m/z 863.1378, Found: 863.1377.
Synthesis of Intermediate L116
Intermediate L116 (3.00 g, 86%) was obtained in the same manner as in Synthesis of Intermediate L16 of Synthesis Example 2, except that 6-chloro-2-phenylthieno[2,3-b]pyridine (2.73 g, 11.1 mmol) was used instead of 6-chloro-2-phenylfuro[2,3-b]pyridine (2.69 g, 11.71 mmol).
LC-MS m/z=316 (M+H)+.
Synthesis of Intermediate L116-dimer
Intermediate L116-dimer (2.16 g, 72%) was obtained in the same manner as in Synthesis of Intermediate L16-dimer of Synthesis Example 2, except that Intermediate L116 (2.48 g, 7.88 mmol) was used instead of Intermediate L16.
Synthesis of Compound 116
Compound 116 (0.47 g, 21%) was obtained in the same manner as in Synthesis of Compound 16 of Synthesis Example 2, except that Intermediate L116-dimer (2.04 g, 1.19 mmol) was used instead of Intermediate L16-dimer. The obtained compound was identified by MS and HPLC analysis.
HRMS(MALDI-TOF) calcd for C47H39IrN2O2 S2: m/z 920.2082, Found: 920.2080.
Synthesis of Intermediate L146
Intermediate L146 (3.30 g, 83%) was obtained in the same manner as in Synthesis of Intermediate L116 of Synthesis Example 4, except that (3-(tert-butyl)-5-methylphenyl)boronic acid (3.23 g, 16.8 mmol) was used instead of (3,5-dimethylphenyl)boronic acid (2.64 g, 17.56 mmol).
LC-MS m/z=358 (M+H)+.
Synthesis of Intermediate L146-dimer
Intermediate L146-dimer (2.60 g, 74%) was obtained in the same manner as in Synthesis of Intermediate L116-dimer of Synthesis Example 4, except that Intermediate L146 (2.99 g, 8.37 mmol) was used instead of Intermediate L116.
Synthesis of Compound 146
Compound 146 (0.48 g, 20%) was obtained in the same manner as in Synthesis of Compound 116 of Synthesis Example 4, except that Intermediate L146-dimer (2.04 g, 1.19 mmol) was used instead of Intermediate L116-dimer. The obtained compound was identified by MS and HPLC analysis.
HRMS(MALDI-TOF) calcd for C47H38IrN2O2 S2: m/z 919.2004, Found: 919.2003.
Synthesis of Intermediate L216
Intermediate L216 (3.00 g, 86%) was obtained in the same manner as in Synthesis of Intermediate L16 of Synthesis Example 2, except that 5-chloro-2-phenylfuro[3,2-b]pyridine (2.69 g, 11.71 mmol) was used instead of 6-chloro-2-phenylfuro[2,3-b]pyridine (2.69 g, 11.71 mmol).
LC-MS m/z=300 (M+H)+.
Synthesis of Intermediate L216-dimer
Intermediate L216-dimer (3.2 g, 91%) was obtained in the same manner as in Synthesis of Intermediate L16-dimer of Synthesis Example 2, except that Intermediate L216 (2.86 g, 9.55 mmol) was used instead of Intermediate L16. The obtained compound was used in a next reaction without additional purification.
Synthesis of Compound 216
Compound 216 (0.75 g, 34%) was obtained in the same manner as in Synthesis of Compound 16 of Synthesis Example 2, except that Intermediate L216-dimer (2.04 g, 1.24 mmol) was used instead of Intermediate L16-dimer. The obtained compound was identified by MS and HPLC analysis.
HRMS(MALDI-TOF) calcd for C47H39IrN2O4: m/z 888.2539, Found: 888.2539.
Synthesis of Intermediate L316
Intermediate L316 (3.01 g, 76%) was obtained in the same manner as in Synthesis of Intermediate L16 of Synthesis Example 2, except that 5-chloro-2-phenylthieno[3,2-b]pyridine (3.12 g, 12.7 mmol) was used instead of 5-chloro-2-phenylfuro[2,3-c]pyridine (2.69 g, 11.71 mmol).
LC-MS m/z=316 (M+H)+.
Synthesis of Intermediate L316-dimer
Intermediate L316-dimer (2.60 g, 74%) was obtained in the same manner as in Synthesis of Intermediate L16-dimer of Synthesis Example 2, except that Intermediate L316 (2.89 g, 9.19 mmol) was used instead of Intermediate L16.
Synthesis of Compound 316
Compound 316 (0.49 g, 20%) was obtained in the same manner as in Synthesis of Compound 16 of Synthesis Example 2, except that Intermediate L316-dimer (2.23 g, 1.30 mmol) was used instead of Intermediate L16-dimer. The obtained compound was identified by MS and HPLC analysis.
HRMS(MALDI-TOF) calcd for C47H39IrN2O2 S2: m/z 920.2082, Found: 920.2080.
CBP and Compound 16 were co-deposited at a weight ratio of 9:1 under a vacuum pressure of 10−7 torr to manufacture a film having a thickness of 40 nm.
A PL spectrum of the film was evaluated at room temperature by using a PicoQuant TRPL measurement system FluoTime 300 and a PicoQuant pumping source PLS340 (excitation wavelength=340 nm, spectral width=20 nm), a wavelength of a main peak of the spectrum was determined, and PLS340 repeatedly measured the number of photons emitted from the film at the wavelength of the main peak due to a photon pulse (pulse width=500 ps) applied to the film according to time based on time-correlated single photon counting (TCSPC), thereby obtaining a sufficiently fittable TRPL curve. A decay time Tdecay of the film was obtained by fitting one or more exponential decay functions to the result obtained therefrom. The function used for fitting is expressed by Equation 10, and the greatest value among the values obtained from each exponential decay function used for fitting was taken as Tdecay. At this time, a baseline or background signal curve was obtained by repeating the same measurement once more for the same measurement time as the measurement time for obtaining the TRPL curve in a dark state (a state in which a pumping signal applied to the predetermined film was blocked), and the baseline or background signal curve was used for fitting as a baseline.
Then, the quantum efficiency of the film was measured by using a Hamamatsu Quantaurus-QY Absolute PL quantum yield spectrometer (provided with a xenon light source, a monochromator, a photonic multichannel analyzer, and an integrating sphere and using PLQY measurement software (Hamamatsu Photonics, Ltd., Shizuoka, Japan)). Upon measurement of the quantum efficiency, the excitation wavelength was measured while scanning from 320 nm to 380 nm at an interval of 10 nm, and the greatest value was taken as the quantum efficiency (Φ).
The radiative decay rate (kr) of Compound 1 was obtained by substituting Tdecay and Φ into Equation 11, and results thereof are shown in Table 2.
kr=Φ/Tdecay Equation 11
The measurement of the radiative decay rate was repeated on Compounds 101, 116, 146, 216, 316, A1, A2, B, C1, C2 and D, and results thereof are shown in Table 2.
From Table 2, it is confirmed that Compounds 16, 101, 116, 146, 216, and 316 have high radiative decay rates, as compared with those of Compounds A1, A2, B, C1, C2, and D.
As an anode, a glass substrate, on which ITO/Ag/ITO were deposited to thicknesses of 70 Å/1,000 Å/70 Å, was cut to a size of 50 mm×50 mm×0.5 mm, sonicated with isopropyl alcohol and pure water each for 5 minutes, and then cleaned by exposure to ultraviolet rays and ozone for 30 minutes. Then, the glass substrate was provided to a vacuum deposition apparatus.
2-TNATA was vacuum-deposited on the anode to form a hole injection layer having a thickness of 600 Å, and 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 1,350 Å.
Then, CBP (host) and Compound 16 (dopant) were co-deposited on the hole transport layer at a weight ratio of 98:2 to form an emission layer having a thickness of 400 Å.
Then, BCP was vacuum-deposited on the emission layer to form a hole blocking layer having a thickness of 50 Å, Alq3 was vacuum-deposited on the hole blocking layer to form an electron transport layer having a thickness of 350 Å, LiF was vacuum-deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and Mg and Ag were co-deposited on the electron injection layer at a weight ratio of 90:10 to form a cathode having a thickness of 120 Å, thereby completing the manufacture of an organic light-emitting device (which emits red light).
Organic light-emitting devices were manufactured in the same manner as in Example 1, except that Compounds shown in Table 3 were each used instead of Compound 16 as a dopant in forming an emission layer.
The driving voltage, maximum value of external quantum efficiency (Max EQE), roll-off ratio, maximum emission wavelength of main peak of EL spectrum, and lifespan (T97) of the organic light-emitting devices manufactured according to Examples 1 to 6 and Comparative Examples A1, A2, B, C1, C2, and D were evaluated, and results thereof are shown in Table 3. A current-voltage meter (Keithley 2400) and a luminance meter (Minolta Cs-1000A) were used as the evaluation devices, and the lifespan (T97) (at 3,500 nit) indicates an amount of time that lapsed when luminance was 97% of initial luminance (100%). The roll-off ratio was calculated by Equation 20:
Roll off ratio={1−(efficiency(at 3,500 nit)/maximum luminescence efficiency)}×100% Equation 20
From Table 3, it is confirmed that the organic light-emitting devices of Examples 1 to 6 emit red light and have improved driving voltage, improved external quantum efficiency, improved roll-off ratio, and improved lifespan characteristics, compared with those of the organic light-emitting devices of Comparative Examples A1, A2, B, C1, C2, and D.
Since the organometallic compound has a high radiative decay rate, an electronic device, for example, an organic light-emitting device, which includes the organometallic compound represented by Formula 1, may have improved driving voltage, improved external quantum luminescence efficiency, improved roll-off ratio, and improved lifespan characteristics. In addition, since the organometallic compound has excellent phosphorescent luminescent characteristics, a diagnostic composition having high diagnostic efficiency may be provided by using the organometallic compound.
It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments.
While embodiments have been described with reference to the FIGURES, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2019-0044480 | Apr 2019 | KR | national |
| Number | Name | Date | Kind |
|---|---|---|---|
| 7445857 | Shen et al. | Nov 2008 | B2 |
| 9359549 | Rayabarapu et al. | Jun 2016 | B2 |
| 9859510 | Boudreault et al. | Jan 2018 | B2 |
| 10003035 | Hwang et al. | Jun 2018 | B2 |
| 10205106 | Stoessel et al. | Feb 2019 | B2 |
| 10340466 | Lin et al. | Jul 2019 | B2 |
| 20110285275 | Huang et al. | Nov 2011 | A1 |
| 20150097169 | Xia et al. | Apr 2015 | A1 |
| 20150171348 | Stoessel et al. | Jun 2015 | A1 |
| 20160164006 | Chao et al. | Jun 2016 | A1 |
| 20170294596 | Ishibe et al. | Oct 2017 | A1 |
| 20190112324 | Kim et al. | Apr 2019 | A1 |
| 20190326527 | Choi et al. | Oct 2019 | A1 |
| 20200328360 | Lee et al. | Oct 2020 | A1 |
| Number | Date | Country |
|---|---|---|
| 3173418 | May 2017 | EP |
| 3626724 | Mar 2020 | EP |
| 3637489 | Apr 2020 | EP |
| 1020120026486 | Mar 2012 | KR |
| 1020150039846 | Apr 2015 | KR |
| 1020160064951 | Jun 2016 | KR |
| 1020170115872 | Oct 2017 | KR |
| 1020190042459 | Apr 2019 | KR |
| 1020190123228 | Oct 2019 | KR |
| 1020200120185 | Oct 2020 | KR |
| I242999 | Dec 1993 | TW |
| 2014023377 | Feb 2014 | WO |
| 2018062758 | Apr 2018 | WO |
| Entry |
|---|
| Chemical Communications (Cambridge, United Kingdom) (2013), 49(15), 1497-1499. |
| Extended European search report issued by the European Patent Office dated Aug. 25, 2020 in the examination of the European Patent Application No. 20168152.5, which corresponds to the U.S. Application above. |
| Tian-Yi Li, et al., Coordination Chemistry Reviews, 374, (2018) 55-92. |
| English Abstract of KR 10-2020-0120185. |
| Number | Date | Country | |
|---|---|---|---|
| 20200331940 A1 | Oct 2020 | US |
