• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    PURPOSE: A metal coordination compound, an electroluminescence device containing the compound and an image display apparatus containing the device are provided, wherein the compound is improved in the efficiency of luminescence and shows long-term high luminance. CONSTITUTION: The metal coordination compound is represented by the formula MLmL'n, wherein M is a metal selected from Ir, Pt, Rh or Pd; L and L' are different bidentate ligands each other; and m is 1, 2 or 3, n is 0, 1 or 2, and m+n is 2 or 3. The partial structure MLm is represented by the formula 2; and the partial structure ML'n is represented by the formula 3 or 4. Preferably at least one among the substituents of the cyclic groups, and cyclic groups CyC1 and CyC2 include an aromatic group capable of having the substituent represented by the formula 5.
    公开号:KR20020072215A
    申请号:KR1020020012316
    申请日:2002-03-08
    公开日:2002-09-14
    发明作者:타키구치타카오；오카다신지로；츠보야마아키라；미우라세이시；모리야마타카시；카마타니준；후루고리마나부
    申请人:캐논 가부시끼가이샤；
    IPC主号:
    专利说明:

    Metal coordination compound, light emitting device and display device {METAL COORDINATION COMPOUND, LUMINESCENCE DEVICE AND DISPLAY APPARATUS}
    [8] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic light emitting element (also referred to as an "organic electroluminescent element" or "organic EL element") used in flat light sources, flat panel display devices, and the like. The present invention relates to a novel metal coordination compound and a light emitting device having little change over time by using a metal coordination compound represented by).
    [9] As a conventional example of the organic light emitting element, there is used, for example, light emission of a vacuum deposited anthracene film (Thin Solid Films, 94 (1982) 171). In recent years, however, high-speed response and high-efficiency light emitting devices have been developed in view of the advantages such as the ease of providing a large-area device and the possibility of realizing a desired light emission color and driving at low pressure by the development of various new materials. Extensive research has been conducted for the formation of devices.
    [10] For example, Macromol. Symp. 125, 1-48 (1997), an organic EL device generally includes an organic material layer including a pair of upper and lower electrodes formed on a transparent substrate and a light emitting layer disposed between the electrodes. Has a composition.
    [11] In the light emitting layer, for example, an aluminum quinolinol complex (including Alq3 described later as a representative example) having electron transport characteristics and light emission characteristics is used, and for example, a triphenyldiamine derivative (for a hole transport layer) is used. As a representative example, a material having an electron donor such as α-NPD described later is used.
    [12] This device has a current rectifying characteristic in which holes are injected from the anode and electrodes are injected from the cathode when an electric field is applied between the electrodes.
    [13] The injected holes and electrons recombine in the emission layer to form excitons, and the excitons are emitted when they are transitioned to the ground state.
    [14] In this process, the excited state includes a singlet (single line) state and a triplet (triple line) state, wherein the transition from the former to the ground state is called fluorescence, and the transition from the latter is called phosphorescence. The materials in these states are called singlet exciter and triplet exciter, respectively.
    [15] Most of the organic light emitting devices studied so far use fluorescence generated by the transition of the singlet exciter to the ground state. On the other hand, recently, a device using phosphorescence through triplet excitons has been studied.
    [16] As a representative document,
    [17] Paper 1: Improved Energy Transfer in Electron Phosphors (D.F. O'Brien, et al., Applied Physics Letters, Vol. 74, No. 3, p. 422 (1999));
    [18] Paper 2: Highly Efficient Green Organic Light Emitting Device Based on Electron Phosphor (M.A. Baldo, et al., Applied Physics Letters, Vol. 75, No. 1, p. 4 (1999))
    [19] Etc. can be mentioned.
    [20] In these papers, a structure comprising four organic layers sandwiched between electrodes, and the materials used therein, include a carrier transport material and a phosphorescent material, whose names and structures are indicated below with abbreviations:
    [21] Alq3: aluminum quinolinol complex
    [22] α-NPD: N4, N4'-di-naphthalen-1-yl-N4, N4'-diphenyl-biphenyl-4,4'-diamine
    [23] CBP: 4,4'-N, N'-dicarbazole-biphenyl
    [24] BCP: 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
    [25] PtOEP: Platinum-octaethylporphyrin complex
    [26] Ir (ppy) 3 : Iridium-phenylpyrimidine complex
    [27]
    [28] In both papers 1 and 2, a hole transport layer made of α-NPD, an electron transport layer made of Alq3, an exciton diffusion preventing layer made of BCP, and CBP as a main component are dispersed as a phosphor in a mixture therein. A structure exhibiting a high efficiency, including a light emitting layer composed of about 6% of PtOEP or Ir (ppy) 3, has been reported.
    [29] Such phosphorescent materials are particularly attracting attention because they are expected to provide high luminous efficiency in principle for the following reasons. Specifically, excitons formed by carrier recombination consist of a ratio of 1: 3 to singlet excitons and triplet excitons. Conventional organic EL devices use fluorescence whose luminous efficiency is limited to 25% at most, whereas using fluorescence generated from triplet excitons, at least three times the efficiency is expected and high energy singlet state Considering the transition due to the intersystem crossing from the triplet state to the triplet state, even 100%, i.e., 4 times, efficiency is expected in principle.
    [30] However, like the fluorescent device, such an organic light emitting device using phosphorescence generally requires further improvement in terms of deterioration of luminous efficiency and device stability.
    [31] Although the reason for the said deterioration is not fully understood, the present inventors thought that it was based on the mechanism of phosphorescence.
    [32] When the light emitting layer is composed of a host material having a carrier transfer function and a phosphorescent guest material, the phosphorescent process through the triplet exciter may include the following unit process:
    [33] 1. transmission of excitons and holes in the light emitting layer,
    [34] 2. formation of host excitons;
    [35] 3. Excitation energy transfer between host molecules
    [36] 4. transfer of excitation energy from the host to the guest,
    [37] 5. Guest Leaflet Formation of excitations and
    [38] 6. Guest triplet Transition and phosphorescence of excitation ground.
    [39] Desired energy transfer in each unit process and in luminescence occurs in competition with various energy deactivation processes.
    [40] Needless to say, the light emission efficiency of the organic light emitting element is increased by increasing the light emission quantum yield of the light emitting center material.
    [41] In phosphorescent materials in particular, this may be attributable to the lifetime of triplet excitons longer than three orders of magnitude of singlet excitons. Specifically, since it is kept in a high energy excitation state for a long time, it reacts with the surrounding material to cause polymer formation between excitons, so that the inactivation process is likely to occur, which leads to material change and deterioration of life.
    [42] It is desired that the light emitting device exhibit high efficiency light emission and exhibit high stability. In particular, it is also strongly desired to provide a luminescent material compound which is not liable to cause energy inactivation in the long life of the excited energy state and which is chemically stable to provide a longer device life.
    [43] Therefore, the main object of the present invention is to provide a light emitting material that exhibits high light emission efficiency and maintains high light emission for a long time, and to provide a light emitting device and a display device using the light emitting material.
    [44] In the present invention, a novel light emitting metal complex compound containing a aromatic group of formula (5) shown below is used as a light emitting material, particularly as a metal complex, particularly iridium as a core metal, as part of a ligand, or as a substituent of a ligand.
    [45] More specifically, the present invention provides the following formula (1) as a light emitting material:
    [46] ML m L ' n (1)
    [47] Wherein M is a metal atom of Ir, Pt, Rh or Pd; L and L 'are different bidentate ligands; m is 1, 2 or 3, n is 0, 1 or 2, provided that m + n is 2 or 3; Substructure ML m is represented by the formula (2) shown below, and substructure ML ' n is represented by the following formula (3) or (4):
    [48]
    [49] [Wherein, CyN1 and CyN2 are each a ring group which may have a substituent, including a nitrogen atom, which is bonded to the metal atom M through the nitrogen atom; CyC1 and CyC2 are each a cyclic group which may have a substituent which is bonded to the metal atom M through the carbon atom including the carbon atom, except that the cyclic group CyN1 and the cyclic group CyC1 are bonded to each other through a covalent bond, Cyclic group CyN2 and cyclic group CyC2 are bonded to each other through a covalent bond;
    [50] Arbitrary substituents on the ring group include a halogen atom, a cyano group, a nitro group, a trialkylsilyl group wherein the alkyl group is a linear or branched alkyl group having 1 to 8 carbon atoms independently, and an alkyl group is -O-, -S-,- One or more non-adjacent methylene groups which may be substituted with CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C— may also include an alkyl group. Is a linear or branched alkyl group having 1 to 20 carbon atoms which may include a hydrogen atom which may be substituted with a fluorine atom as needed, or a substituent (halogen atom, cyano atom, nitro atom, alkyl group is -O-, -S May include one or more non-adjacent two or more methylene groups which may be substituted with —, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C—, Also, the alkyl group may be a straight or branched alkyl group having 1 to 20 carbon atoms which may include a hydrogen atom which may be substituted with a fluorine atom if necessary). Is selected from the group which direction,
    [51] E and G are independently a linear or branched alkyl group having 1 to 20 carbon atoms, or a substituent (halogen atom, cyano atom, nitro atom, alkyl group independently, in which the alkyl group may include a hydrogen atom which may be substituted with a fluorine atom). Trialkylsilyl groups, which are linear or branched alkyl groups having 1 to 8 carbon atoms, and alkyl groups are -O-, -S-, -CO-, -CO-O-, -O-CO-, -CH = CH- or- 1 to 20 carbon atoms which may include one or two or more non-adjacent methylene groups which may be substituted with C≡C-, and an alkyl group may include a hydrogen atom which may be substituted with a fluorine atom as necessary. Aromatic straight chain or branched alkyl group);
    [52] At least one of the arbitrary substituents of a cyclic group, a cyclic group CyC1 and CyC2 is following formula (5):
    [53]
    [54] [The aromatic group of formula (5) is bonded to CyN1, CyN2, CyC1 or CyC2 through a single bond when the aromatic group is any substituent of the ring group, and the aromatic group of the formula (5), the aromatic group is CyC1 or In the case of CyC2, it is bonded with the metal atom M through a single bond;
    [55] Y is C═O, CRR ′, C═C (CN) 2 , O or S (wherein R and R ′ are independently a hydrogen atom, a straight or branched alkyl group having 1 to 8 carbon atoms, an alkyl group is —O—, It may contain one or more than two non-contiguous methylene groups which may be substituted by -S-, -CO-, -CO-O-, -O-CO-, -CH = CH- or -C≡C- And a linear or branched alkyl group having 1 to 20 carbon atoms which may include a hydrogen atom which may be substituted with a fluorine atom, if necessary, or a substituent (halogen atom, cyano atom, nitro atom, alkyl group- One or two or more non-contiguous methylene groups which may be substituted by O-, -S-, -CO-, -CO-O-, -O-CO-, -CH = CH- or -C≡C- And an alkyl group, which may be a linear or branched alkyl group having 1 to 20 carbon atoms, which may include a hydrogen atom which may be substituted with a fluorine atom if necessary);
    [56] Arbitrary substituents of the formula (5) include a trialkylsilyl group in which a halogen atom, a cyano group, a nitro group, and an alkyl group are each independently a linear or branched alkyl group having 1 to 8 carbon atoms, and an alkyl group is -O-, -S-. May include one or more than two non-adjacent methylene groups which may be substituted by -CO-, -CO-O-, -O-CO-, -CH = CH- or -C≡C-, and , A linear or branched alkyl group having 1 to 20 carbon atoms which may include a hydrogen atom which may be substituted with a fluorine atom, if necessary, or a substituent (halogen atom, cyano atom, nitro atom, alkyl group is -O-, It may contain one or more than two non-contiguous methylene groups which may be substituted by -S-, -CO-, -CO-O-, -O-CO-, -CH = CH- or -C≡C- And an alkyl group is a straight or branched alkyl group having 1 to 20 carbon atoms which may include a hydrogen atom which may be substituted with a fluorine atom if necessary. It provides a metal coordination compound, which is selected from an aromatic group, provided that adjacent pairs of substituents can combine to form a ring structure;
    [57] Preferred embodiments of the metal coordination compound of formula (1) according to the present invention include the following examples:
    [58] A metal coordination compound having a partial structure ML ' n represented by the formula (3) in the formula (1).
    [59] A metal coordination compound having a partial structure ML ' n represented by the formula (4) in the formula (1).
    [60] N in the formula (1) is 0, wherein the metal coordination compound.
    [61] A metal coordination compound, wherein the group Y in the formula (5) is C = O or CRR '.
    [62] The cyclic group CyC1 in the formula (2) and CyC2 in the formula (3) have a corresponding aromatic ring group which may have a substituent under the condition that the aromatic ring group may include one or two CH groups which may be substituted with nitrogen atoms. Are independently selected from phenyl group, thienyl group, thianaphthyl group, naphthyl group, pyrenyl group, 9-fluorenyl group, fluorenyl group, dibenzofuryl group, dibenzothiethyl group or carbazolyl group, in particular phenyl group or Metal coordination compound, characterized in that selected from 2-fluorenyl group.
    [63] Cyclic group CyN1 in Formula (2) and CyN2 in Formula (3) are aromatic ring groups which may have a substituent, and are metals selected from pyridyl, pyridazinyl and pyrimidinyl groups independently. Coordination compounds.
    [64] Said CyN1, CyN2, CyC1 and CyC2 are independently unsubstituted or a halogen atom and a linear or branched alkyl group having 1 to 20 carbon atoms, wherein the alkyl group is -O-, -S-, -CO-,- One or more nonadjacent two or more methylene groups which may be substituted with CO—O—, —O—CO—, —CH═CH— or —C≡C—, or substituents [halogen atoms or carbon atoms of 1 to 20 Linear or branched alkyl groups (where the alkyl group may include one or more adjacent two or more methylene groups which may be substituted with -O-, and furthermore, a hydrogen atom in which the alkyl group may be substituted with a fluorine atom as necessary). And divalent aromatic groups which may have a divalent aromatic group}.
    [65] M in said Formula (1) is iridium, The metal coordination compound characterized by the above-mentioned.
    [66] Formula (6):
    [67]
    [68] Wherein X is CRR ', O or S [wherein R and R' are independently of the formula: C n H 2n + 1- (wherein n is an integer from 1 to 20 and the alkyl group is substituted with -O-) One or more non-adjacent two or more methylene groups which may be included, and may further include a hydrogen atom which may be substituted with a fluorine atom if necessary).
    [69] R2 is a hydrogen atom; Fluorine atoms; Formula: C n H 2n + 1- (where n is an integer from 1 to 20, wherein the alkyl group may comprise one or more nonadjacent two or more methylene groups which may be substituted by -O-, A linear or branched alkyl group of a hydrogen atom which may be substituted with a fluorine atom if necessary); Phenyl group which may have a substituent; 9,9-dialkylfluorenyl group, wherein the alkyl group is, independently, a formula: C n H 2n + 1- (wherein n is an integer of 1 to 20, and the alkyl group may be substituted with -O- A single or non-adjacent two or more methylene groups, and may further include a hydrogen atom which may be substituted with a fluorine atom if necessary). Dibenzofuranyl group which may have a substituent; And a dibenzothienyl group which may have a substituent; Optional substituents of the phenyl group, 9,9-dialkylfluorenyl group, dibenzofuranyl group and dibenzothienyl group may be a fluorine atom or a formula: C n H 2n + 1- (where n is an integer of 1 to 20). The alkyl group may include one or two or more non-adjacent methylene groups which may be substituted with -O-, and may further include a hydrogen atom which may be substituted with a fluorine atom as necessary. Or a branched alkyl group}.
    [70] In addition, the present invention provides an electroluminescent device comprising a light emitting unit comprising a pair of electrodes disposed on a substrate and at least one organic compound disposed between the electrodes, wherein the organic compound is represented by the above formula. An electroluminescent device comprising the metal coordination compound represented by (1) is provided.
    [71] The light emitting device according to claim 1, wherein light is applied by applying a voltage between the electrodes.
    [72] In the preferred embodiment of the electroluminescent element, the electroluminescent element is characterized by emitting phosphorescence by applying a voltage between the electrodes.
    [73] The present invention also provides an image display apparatus comprising the electroluminescent element and means for supplying an electric signal to the electroluminescent element.
    [74] The above and other objects, features, advantages, and the like of the present invention will become apparent upon consideration of the following description of preferred embodiments of the present invention taken in conjunction with the accompanying drawings.
    [1] 1 (a), 1 (b) and 1 (c) each show an embodiment of a light emitting device according to the present invention.
    [2] 2 is a schematic view showing a panel structure including a light emitting element and a driving means;
    [3] <Description of the symbols for the main parts of the drawings>
    [4] 11: metal electrode 12: light emitting layer
    [5] 13: hole transport layer 14: transparent electrode
    [6] 15: transparent substrate 16: electron transport layer
    [7] 17: exciton diffusion prevention layer
    [75] EMBODIMENT OF THE INVENTION Hereinafter, the preferred embodiment example of this invention is described in detail.
    [76] The basic structure of the organic light emitting (EL) device formed according to the present invention is shown in Figs. 1 (a), 1 (b) and 1 (c).
    [77] As shown in these figures, an organic light emitting element generally includes a transparent electrode 14 having a thickness of 50 to 200 nm, a plurality of organic film layers, and a metal electrode formed on the transparent substrate 15 to cover the organic layer ( 11).
    [78] FIG. 1A shows an example of the embodiment in which the organic light emitting element is composed of the light emitting layer 12 and the hole transport layer 13. The transparent electrode 14 may be made of ITO or the like having a large working function to facilitate hole injection from the transparent electrode 14 into the hole transport layer 13. The metal electrode 11 is made of a metal material having a small working function such as aluminum, magnesium or an alloy of these elements in order to facilitate electron injection into the organic light emitting element.
    [79] The light emitting layer 12 consists of the compound (metal coordination compound) by this invention. The hole transport layer 13 may be made of, for example, a triphenyldiamine derivative represented by the above α-NPD and a material having an electron donating as needed.
    [80] The device configured as described above exhibits a current rectifying characteristic, and when an electric field is applied between the metal electrode 11 as a cathode and the transparent electrode 14 as an anode, electrons are injected from the metal electrode 11 into the light emitting layer 12. Holes are injected from the transparent electrode 15. The injected holes and electrons are recombined in the light emitting layer 12 to form excitons having a high energy potential, causing light emission during the transition to the ground state. At this time, the hole transport layer 13 functions as an electron shielding layer to increase the recombination efficiency at the boundary between the light emitting layer 12 and the hole transport layer 13, thereby providing an improved luminous efficiency.
    [81] In addition, in the structure of FIG. 1 (b), the electron transport layer 16 is disposed between the metal electrode 11 and the light emitting layer 12 in FIG. As a result, the light emitting function is separated from the electron transfer function and the hole transfer function to provide a structure that exhibits more effective carrier shielding properties, thereby increasing the luminous efficiency. The electron transport layer 16 may contain, for example, an oxadiazole derivative.
    [82] FIG. 1C is a four-layer structure including a hole transport layer 13, a light emitting layer 12, an exciton diffusion preventing layer 17, and an electron transport layer 16 sequentially from the transparent electrode 14 side as an anode. Another preferred form is shown.
    [83] The light emitting material used in the present invention is the most suitable metal coordination compound represented by the above formulas (1) to (5), produces high-efficiency light emission, maintains high light emission for a long time, and has little deterioration due to current passing.
    [84] The metal coordination compound of the present invention emits phosphorescence, and its lowest excited state is regarded as π-π * excited state in the MLCT * (metal-to-ligand charge transfer) excited state or triplet state. Phosphorescence is generated at the transition to the ground state.
    [85] Hereinafter, some characteristics and properties measuring methods described herein will be described for characterizing the light emitting material of the present invention.
    [86] (1) discrimination between phosphorescence and fluorescence
    [87] The identification of phosphorescence is performed according to whether or not inactivation by oxygen has occurred. After aeration with oxygen or nitrogen, the sample compound solution in chloroform is irradiated with light to generate light. The luminescence is determined to be phosphorescence when luminescence due to the compound is hardly observed for the solution vented with oxygen and luminescence is confirmed for the solution vented with nitrogen. Phosphorescence of the whole compound of this invention was confirmed by this method unless there is particular notice.
    [88] (2) The phosphorescence yield (ratio of relative quantum yield, ie, the ratio of the quantum yield Φ (st) of the sample to the quantum yield Φ (sample) of the standard sample) is
    [89] Φ (sample) / Φ (st) = [Sem (sample) / Iabs (sample)] / [Sem (st) / Iabs (st)]
    [90] [Wherein Iabs (st) represents the absorption coefficient at the excitation wavelength of the standard sample; Sem (st) is the emission spectrum broad intensity when excited at the same wavelength; Iabs (sample) is the absorption coefficient at the excitation wavelength of the compound of interest; Sem indicates the emission spectrum broad intensity when excited at the same wavelength ].
    [91] The phosphorescence yield value described here is a relative value with respect to the phosphorescence yield phi = 1 of Ir (ppy) 3 as a standard sample.
    [92] (3) The measurement method of phosphorescent life is as follows.
    [93] The sample compound is dissolved in chloroform, spin-coated to a thickness of about 0.1 占 퐉 on a quartz substrate, and pulsating nitrogen laser light is exposed at an excitation wavelength of 337 nm at room temperature using a light emitting lifetime meter (manufactured by Hamamatsu Photonics). After completion of the excitation pulse, the attenuation characteristic of the luminous intensity is measured.
    [94] When the initial luminous intensity is expressed as I 0 , the luminous intensity after t (seconds) is based on the emission lifetime τ (seconds).
    [95] I = I 0 · exp (-t / τ)
    [96] Express according to.
    [97] The light emitting material (metal coordination compound) of the present invention exhibited a high phosphorescence quantum yield of 0.11 to 0.9 and a short phosphorescence life of 0.1 to 40 µsec. Short phosphorescence lifetime is a condition that causes little energy inactivation and exhibits improved luminous efficiency. Specifically, when the phosphorescence lifetime is long, the number of triplet state molecules held for luminescence is increased, and the inactivation process is likely to occur, particularly at low current density, resulting in low luminous efficiency. The material of the present invention has a relatively short phosphorescence lifetime showing a high phosphorescence quantum yield and is therefore suitable as a light emitting material for EL devices.
    [98] As a result of various studies by the present inventors, it has been found that an organic EL device using the metal coordination compound of formula (1) as a main light emitting material generates high efficiency light emission, maintains high light emission for a long time, and has little deterioration due to current passing.
    [99] In the formula (1) representing the metal coordination compound of the present invention, n is preferably 0 or 1, more preferably 0. Moreover, partial structure ML'n may contain the aromatic group represented by said Formula (5) preferably. In Formula (5), Y may preferably be C = O or CRR '. When Y is CRR '(R and R' are CH 3 ), the metal coordination compound represented by the formula (1) preferably does not have to have a substituent. In particular, when CyC1 is FL2 (described below) (where R and R 'are CH 3 and CyN1 is Pi), R1 to R4 (as substituents for Pi and FL2) are preferably hydrogen atoms at the same time. .
    [100] In the present invention, by incorporating the aromatic group of formula (5) into the metal coordination compound of formula (1), it is possible to control the emission wavelength (especially to provide a long emission wavelength). The presence of the aromatic group of the formula (5) is effective for increasing the solubility of the metal coordination compound of the present invention in an organic solvent, thereby facilitating recrystallization or purification by column chromatography. As a result, the metal coordination compound of the present invention is suitable as a light emitting material for organic EL devices.
    [101] In addition, as shown in the Examples shown below, the metal coordination compound of the present invention was proved to exhibit excellent stability in the continuous current passing test. This is considered to be due to the incorporation of the aromatic group of formula (5) into the molecular structure of the metal coordination compound of formula (1) according to the present invention. Specifically, the intermolecular interaction of the metal coordination compound having the host material, for example, by the change of the intermolecular interaction caused by the introduction of the aromatic group of the formula (5), forms the excitons associated with thermal inactivation. By suppressing this, it is possible to reduce the quenching process and improve the phosphorescence yield and device characteristics.
    [102] The light emitting device according to the present invention is disposed between two electrodes facing each other with a layer of the metal coordination compound of formula (1) as shown in Figs. 1 (a), 1 (b) and 1 (c). And an electroluminescent element of the type which emits light by applying a voltage between these electrodes.
    [103] For application to a display device, a driving method using a thin film transistor (TFT) driving circuit by active matrix design may be used. Hereinafter, the embodiment which uses the element of this invention in combination with an active-matrix board | substrate is briefly described referring FIG.
    [104] 2 shows an example of an embodiment of a panel structure provided with an EL element and driving means. The panel has a scan signal driver, a data signal driver and a current supply source connected to the gate select line, the data signal line and the current supply line, respectively. A display pixel electrode is arranged at each intersection of the gate selection line and the data signal line. The scan signal driver sequentially selects the gate signal lines G1, G2, G3, ..., Gn, and in synchronization with this, an image signal is supplied from the data signal driver to display an image.
    [105] By driving the display panel including the light emitting layer containing the light emitting material of the present invention, it is possible to provide a stable display device even when displaying a good image quality for a long time.
    [106] Some synthetic routes for providing the metal coordination compound represented by the above formula (1) are exemplified below with reference to, for example, an iridium coordination compound (m + m = 3):
    [107]
    [108] Other metal coordination compounds (M = Pt, Rh and Pd) can also be synthesized in the same manner.
    [109] Some specific structural examples of the metal coordination compound used in the present invention are shown in Tables 1 to 42 below, but these are only representative examples, but are not limited thereto. In Tables 1 to 42, "No" represents exemplary compound numbers, and Pi to CZ for CyN1, CyN2, CyC1, and CyC2 shown in Tables 1 to 42 represent the partial structures shown below.
    [110]
    [111] Incidentally, the aromatic groups Ph2 to DBT3 as substituents for CyN1, CyN2, CyC1 and CyC2 shown in Tables 1 to 42 show the partial structures shown below, except that the substituents R5 to R8 of the aromatic groups are particularly indicated. If not present, a hydrogen atom is represented.
    [112]
    [113]
    [114]
    [115]
    [116]
    [117]
    [118]
    [119]
    [120]
    [121]
    [122]
    [123]
    [124]
    [125]
    [126]
    [127]
    [128]
    [129]
    [130]
    [131]
    [132]
    [133]
    [134]
    [135]
    [136]
    [137]
    [138]
    [139]
    [140]
    [141]
    [142]
    [143]
    [144]
    [145]
    [146]
    [147]
    [148]
    [149]
    [150]
    [151]
    [152]
    [153]
    [154]
    [155] EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated more concretely based on an Example.
    [156] Example 1 (Example Synthesis of Compound No. 23)
    [157]
    [158] Into a 30-liter flask with three inlets, 307.3 g (960 mM) of 2-iodo-9,9-dimethylfluorene and 10 liters of dry THF (tetrahydrofuran) were added and cooled to -72 to 70 DEG C under stirring in an argon atmosphere. It was. The n-butyllithium 1.6M solution in hexane was dripped at the obtained mixture for 1 hour, and also it stirred at this temperature for 2 hours. Then, the solution of 209.5 g (2016 mM) of trimethyl borate in 1.3 L of dry THF was dripped at this system under stirring at -73 to -71 degreeC for 2 hours. The reaction mixture was left overnight in an ice-water bath, and 1.6 L of 4N hydrochloric acid was added to the mixture at 0 to -7 ° C for 0.5 hour, and then stirred at room temperature for 1 hour, followed by extraction with toluene. The organic layer was washed with saturated brine, and then the solution was distilled off under reduced pressure to obtain a residue. Hexane was added to this residue, heated, and cooled to precipitate crystals. The crystals were recovered by filtration and purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 1/1), and then from chloroform-hexane mixture solution, toluene, ethyl acetate-toluene-THF mixture solution and toluene. Sequential recrystallization gave 32.0 g (yield: 14.0%) of 2- (9,9-dimethylfluorenyl) boronic acid (colorless crystals).
    [159]
    [160] In a 300 ml flask with three inlets, 8.5 g (53.8 mM) of 2-bromopyridine, 12.8 g (53.8 mM) of 2- (9,9-dimethylfluorenyl) boronic acid, 55 ml of toluene, 27 ml of ethanol and 55 ml of 2M aqueous sodium carbonate solution was added thereto, stirred at room temperature under a nitrogen stream, and thereto was added 1.97 g (1.70 mM) of tetrakis (triphenylphosphine) palladium (0). Thereafter, the mixture was refluxed under stirring for 5.5 hours under a nitrogen stream, and after the reaction, the reaction mixture was cooled and extracted by addition of cold water and toluene. The organic layer was washed with water until neutral, and the solvent was removed under reduced pressure to obtain a residue. The residue was purified by silica gel column chromatography (eluent: toluene / THF = 10/1) and (hexane / ethyl acetate = 8/1) to give 2- {2- (9,9-dimethylfluorenyl )} 12.2 g (yield: 83.6%) of pyridine (light brown viscous liquid) was obtained.
    [161]
    [162] In a 100 ml flask having four inlets, 50 ml of glycerol was added and heated to 130 to 140 ° C. for 2 hours under stirring and nitrogen foaming. Then, the mixture was left to 100 ° C to cool the glycerol, followed by 1.69 g (6.23 mM) of 2- {2- (9,9-dimethylfluorenyl)} pyridine and 0.50 g (1.02 mM) of iridium (III) acetylacetonate. After the addition, the mixture was heated at 176 to 219 캜 for 5 hours under stirring and a stream of nitrogen. The reaction product was cooled to room temperature, poured into 300 mL of 1N hydrochloric acid to form a precipitate, filtered and washed with water, and dried at 100 ° C. under reduced pressure for 5 hours. The precipitate was purified by silica gel column chromatography using chloroform as eluent to give 0.17 g of tris [2- (9,9-dimethylfluoren-2-yl) pyridine-C 3 , N] iridium (III) in orange powder. (Yield = 21.3%) was obtained. According to matrix-assisted laser desorption ionization-time of fight mass spectroscopy (MALDI-TOF MS), the compound exhibited M + (mass number of the corresponding cation formed by removal of one electron) of 1003.4.
    [163] The toluene solution of the compound showed a luminescence spectrum showing λ max (maximum emission wavelength) = 545 nm and quantum yield 0.23.
    [164] In addition, the compound (Example Compound No. 23) exhibited good synthetic yield and quantum yield, and thus is the most suitable light emitting material in the present invention.
    [165] Example 2 (Example Compound No. 43)
    [166]
    [167] In a three-necked 100 ml flask, 1.18 g (4.98 mM) of 2,5-dibromopyridine, 3.57 g (15.0 mM) of 2- (9,9-dimethylfluorenyl) boronic acid prepared in Example 1 , 10 ml of toluene, 5 ml of ethanol, and 10 ml of 2M aqueous sodium carbonate solution were added, stirred at room temperature under a nitrogen stream, and 0.35 g (0.30 mM) of tetrakis (triphenylphosphine) palladium (0) was added thereto. Thereafter, the mixture was refluxed under stirring for 12 hours under a nitrogen stream, and after completion of the reaction, the reaction mixture was cooled in an ice bath to precipitate crystals, followed by filtration and washing with water. 100 ml of methanol was added to this crystal, washed with water at room temperature under stirring, and recovered by filtration. The obtained crystals were purified by silica gel column chromatography (eluent: chloroform) to obtain 2.10 g (yield: 91.0%) of 2- {2- (9,9-dimethylfluorenyl)} pyridine (colorless crystals).
    [168]
    [169] In a 100 ml flask having four inlets, 50 ml of glycerol was added and heated to 130 to 140 ° C. for 2 hours under stirring and nitrogen foaming. Then, the mixture was left to 100 ° C to cool the glycerol and 1.85 g (3.99 mM) of 2- {2- (9,9-dimethylfluorenyl)} pyridine and 0.40 g (0.82 mM) of iridium (III) acetylacetonate. After the addition, the mixture was heated at 180 to 235 ° C for 5 hours under stirring and nitrogen stream. The reaction product was cooled to room temperature, poured into 300 mL of 1N hydrochloric acid to form a precipitate, filtered and washed with water, and dried at 100 ° C. under reduced pressure for 5 hours. The precipitate was purified by silica gel column chromatography using chloroform as eluent to give red powder tris [2,5-bis (9,9-dimethylfluoren-2-yl) pyridine-C 3 , N] iridium (III). ) 0.10 g (yield = 7.7%) was obtained. According to MALDI-TOF MS, the compound showed an M + of 1589.6.
    [170] The toluene solution of the compound exhibited a light emission spectrum showing λ max = 591 nm and a quantum yield of 0.12.
    [171] Examples 3-11
    [172] Each light emitting device having the layer structure shown in FIG. 1 (b) was manufactured by the following method.
    [173] On a 1.1 mm thick glass substrate (transparent substrate 15), a 100 nm thick film (transparent electrode 14) made of indium tin oxide (ITO) was formed by sputtering, and then patterned, each having a width of 100 nm, A striped electrode including 100 lines having a distance of 10 nm (ie, electrode pitch 110 nm) from an adjacent line was formed.
    [174] Thus, three organic layers and two metal electrode layers shown below were sequentially formed on the substrate on which ITO was formed by vacuum (vapor) deposition using resistance heating in a vacuum chamber (10 -4 Pa).
    [175] Organic Layer 1 (hole transport layer 13) (40 nm): α-NPD
    [176] Organic layer 2 (light emitting layer 12) (30 nm): Co-deposited film of CBP: metal complex (metal coordination compound shown in Table 45) (95: 5 by weight)
    [177] Organic layer 3 (electron transport layer 16) (30 nm): Alq3
    [178] Metal Electrode Layer 1 (Metal Electrode 11) (15 nm): Al-Li Alloy (Li = 1.8 wt%)
    [179] Metal Electrode Layer 2 (Metal Electrode 11) (100 nm): Al
    [180] The deposited metal electrode layers 1 and 2 (the Al-Li layer and the Al layer) each have a stripe electrode pattern including 100 lines having a width of 100 nm and an interval of 10 nm (electrode pitch = 110 nm). And a matrix of pixels having an effective electrode area of 3 mm2 each consisting of 20 ITO lines tied together at the lead-out and 15 Al (Al-Li) lines tied together at the lead-out, crossing at right angles to the stripe pattern of the ITO electrode. Form.
    [181] Each light emitting device thus produced was taken out of the vacuum chamber and subjected to a continuous energy (current pass) test in an atmosphere of dry nitrogen gas to remove device deterioration factors such as oxygen and moisture (water content).
    [182] The continuous energyification test was performed by continuously applying a voltage at a constant current density of 70 mA / cm 2 to a light emitting device having an ITO (transparent) electrode (as an anode) and an Al (metal) electrode (as a cathode), and then time-lapsed. The luminance (brightness) according to the measurement was measured to determine the time (luminance half life) required to reduce the initial luminance (60 to 220 cd / cm 2) to 1/2 thereof.
    [183] The results are shown in Table 45 below.
    [184] Comparative Example 1
    [185] In Examples 3 to 11, Ir complexes (Ir (ppy) 3 ) wherein the metal coordination compounds shown in Table 45 are shown below:
    [186]
    [187] A light emitting device of Comparative Example was manufactured and evaluated in the same manner as in Examples 3 to 11 except for changing to.
    [188] The results are shown in Table 45 below.
    [189] Example numberExample Compound NumberLuminance Half Life (Hr) Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 162343547299118153440Ir (ppy) 3 700850950 800 850 750 600 700 650 350
    [190] As is apparent from Table 45, the light emitting device using the metal coordination compound of formula (1) according to the present invention provides longer luminance half life than the conventional light emitting device using Ir (ppy) 3, and thus the present invention. Based on the good stability of the metal coordination compound of formula (1), an EL device having high durability (brightness stability) is obtained.
    [191] Example 12
    [192] The color organic EL display device shown in Fig. 2 was manufactured according to the following method.
    [193] The active matrix substrate basically has a planar structure similarly to the structure described in US Pat. No. 6,114,715.
    [194] Specifically, a top gate TFT of polycrystalline silicon is formed on a 1.1 mm thick glass substrate by a conventional method, and thereon, having contact holes for electrical connection with a pixel electrode (anode) in each source region. A planarization film was formed.
    [195] On the active matrix substrate, a 700 nm-thick pixel electrode (anode) made of ITO having a large working function was formed in a predetermined pattern. On this ITO electrode, a predetermined organic layer and an Al electrode (cathode) of 100 nm thickness were sequentially formed by vacuum deposition by a hard mask, and then patterned to form a matrix of color pixels (128 x 128 pixels).
    [196] Each organic layer corresponding to tricolor (red (R), green (G), and blue (B)) consisted of the following layers.
    [197] <R pixel area>
    [198] α-NPD (40 nm) / CBP: Exemplified compound No. 487 (93: 7 parts by weight) (30 nm) / BCP (20 nm) / Alq 3 (40 nm)
    [199] <G pixel area>
    [200] α-NPD (50 nm) / Alq3 (50 nm)
    [201] <B pixel area>
    [202] α-NPD (50 nm) / BCP (20 nm) / Alq3 (50 nm)
    [203] When the color organic EL display device thus produced is driven, the desired color image data can be stably displayed with good image quality.
    [204] Example 13 (Synthesis of Example Compound No. 24)
    [205] The following compounds were easily synthesized in the same manner as in Example 1 except that 2-chloro-5-trifluoromethylpyridine (manufactured by Tokyo Kasei Co., Ltd.) was used instead of 2-bromopyridine in Example 1.
    [206] Tris [2- (9,9-dimethylfluoren-2-yl) -5-trifluoromethylpyridine-C 3 , N] iridium (III).
    [207] Example 14 (Synthesis of Example Compound No. 25)
    [208] Example 1 except that 2-chloro-4,5-bis (trifluoromethyl) pyridine (manufactured by Oakwood Products Inc.) was used in place of 2-bromopyridine in Example 1. In the same manner, the following compounds were easily synthesized.
    [209] Tris [2- (9,9-dimethylfluoren-2-yl) -4,5-bis (trifluoromethyl) pyridine-C 3 , N] iridium (III).
    [210] Example 15 (Synthesis of Example Compound No. 26)
    [211] The following compounds were easily synthesized in the same manner as in Example 1 except that 2-chloro-5-methylpyridine (manufactured by Aldrich) was used instead of 2-bromopyridine in Example 1.
    [212] Tris [2- (9,9-dimethylfluoren-2-yl) -5-methylpyridine-C 3 , N] iridium (III).
    [213] Example 16 (Synthesis of Example Compound No. 28)
    [214] 2-bromo-9 from 2-bromofluorene and iodoethane in the same manner as described in Example 1 on page 32 of Japanese Patent Laid-Open No. 11-510535 (corresponding to U.S. Patent No. 5,708,130). 9-diethylfluorene was synthesized, modified with 2- (9,9-diethylfluorenyl) borate as in Example 1 (of the present application), and then reacted with 2-bromopyridine to react with 2- { 2- (9,9-diethylfluorenyl) pyridine} was synthesized, and then the following compounds were readily prepared in the same manner as in Example 1 except that the reaction was carried out with acetylacetic acid iridium (III) in the same manner as in Example 1. Synthesized
    [215] Tris [2- (9,9-diethylfluoren-2-yl) pyridine-C 3 , N] iridium (III).
    [216] Example 17 (Synthesis of Example Compound No. 29)
    [217] The following compounds were easily synthesized in the same manner as in Example 16 except that 1-iodopropane (manufactured by Aldrich) was used instead of the iodoethane in Example 16.
    [218] Tris {2- [9,9-di (1-propyl) fluoren-2-yl] methylpyridine-C 3 , N} iridium (III).
    [219] Example 18 (Synthesis of Example Compound No. 30)
    [220] The following compounds were easily synthesized in the same manner as in Example 16 except that 1-iodobutane (manufactured by Aldrich) was used instead of the iodoethane in Example 16.
    [221] Tris {2- [9,9-di (1-butyl) fluoren-2-yl] pyridine-C 3 , N} iridium (III).
    [222] Example 19 (Synthesis of Example Compound No. 31)
    [223] The following compounds were easily synthesized in the same manner as in Example 16 except that 1-iodopentane (manufactured by Aldrich) was used instead of the iodoethane in Example 16.
    [224] Tris {2- [9,9-di (1-pentyl) fluoren-2-yl] pyridine-C 3 , N} iridium (III).
    [225] Example 20 (Synthesis of Example Compound No. 32)
    [226] The following compounds were readily synthesized in the same manner as in Example 16 except that 1-iodohexane (manufactured by Aldrich) was used instead of the iodoethane in Example 16.
    [227] Tris {2- [9,9-di (1-hexyl) fluoren-2-yl] pyridine-C 3 , N} iridium (III).
    [228] Example 21 (Synthesis of Example Compound No. 33)
    [229] The following compounds were easily synthesized in the same manner as in Example 1 except that 1-iodoheptane (manufactured by Aldrich) was used instead of the iodoethane in Example 16.
    [230] Tris {2- [9,9-di (1-heptyl) fluoren-2-yl] pyridine-C 3 , N} iridium (III).
    [231] Example 22 (Synthesis of Example Compound No. 34)
    [232] The following compounds were easily synthesized in the same manner as in Example 16 except that 1-iodooctane (manufactured by Aldrich) was used instead of the iodoethane in Example 16.
    [233] Tris {2- [9,9-di (1-octyl) fluoren-2-yl] pyridine-C 3 , N} iridium (III).
    [234] Example 23 (Synthesis of Example Compound No. 35)
    [235] 1-iododecane (manufactured by Aldrich) was used in place of iodoethane in Example 16, and 2-chloro-5-trifluoromethylpyridine (manufactured by Tokyo Kasei Co., Ltd.) was used instead of 2-bromopyridine. ), The following compounds were easily synthesized in the same manner as in Example 16.
    [236] Tris {2- [9,9-di (1-decyl) fluoren-2-yl] -5-trifluoromethylpyridine-C 3 , N} iridium (III).
    [237] Example 24 (Synthesis of Example Compound No. 37)
    [238] The following compounds were readily synthesized in the same manner as in Example 16, except that 1-iodoeichoic acid (manufactured by Aldrich) was used instead of the iodoethane in Example 16.
    [239] Tris {2- [9,9-di (1-eicosyl) fluoren-2-yl] pyridine-C 3 , N} iridium (III).
    [240] Example 25 (Synthesis of Example Compound No. 44)
    [241] The following compound in the same manner as in Example 2, except that 2- (9,9-diethylfluorenyl) boronic acid was used instead of 2- (9,9-dimethylfluorenyl) boronic acid in Example 2 Was easily synthesized.
    [242] Tris [2,5-bis (9,9-diethylfluoren-2-yl) pyridine-C 3 , N} iridium (III).
    [243] Example 26 (Synthesis of Example Compound No. 45)
    [244] The same procedure as in Example 2 except that 2- [9,9-di (1-pentyl) fluorenyl] boronic acid was used instead of 2- (9,9-dimethylfluorenyl) boronic acid in Example 2. The following compounds were easily synthesized in the manner.
    [245] Tris {2,5-bis [9,9-di (1-pentyl) fluoren-2-yl] pyridine-C 3 , N} iridium (III).
    [246] Example 27 (Synthesis of Example Compound No. 47)
    [247] Except for using 2- [9,9-di (1-pentadedecyl) fluorenyl] boronic acid in place of 2- (9,9-dimethylfluorenyl) boronic acid in Example 2, In the same manner, the following compounds were easily synthesized.
    [248] Tris {2,5-bis [9,9-di (1-pentadedecyl) fluoren-2-yl] pyridine-C 3 , N} iridium (III).
    [249] Example 28 (Synthesis of Example Compound No. 146)
    [250] The following compound in the same manner as in Example 1 except that dibenzofuran-4-boronic acid (produced by Frontier Scientific) was used in place of 2- (9,9-dimethylfluorenyl) boronic acid in Example 1. Was easily synthesized.
    [251] Tris [2- (dibenzofuran-4-yl) pyridine-C 3 , N] iridium (III).
    [252] Example 29 (Synthesis of Example Compound No. 147)
    [253] In the same manner as in Example 1, except that dibenzothiophene-4-boronic acid (manufactured by Frontier Scientific) was used instead of 2- (9,9-dimethylfluorenyl) boronic acid in Example 1. Compounds were easily synthesized.
    [254] Tris [2- (benzothiophen-4-yl) pyridine-C 3 , N] iridium (III).
    [255] Example 30 (Synthesis of Example Compound No. 149)
    [256] The following compound in the same manner as in Example 2, except that dibenzofuran-4-boronic acid (manufactured by Frontier Scientific) was used instead of 2- (9,9-dimethylfluorenyl) boronic acid in Example 1. Was easily synthesized.
    [257] Tris [2,5-bis (dibenzofuran-4-yl) pyridine-C 3 , N] iridium (III).
    [258] Example 31 (Synthesis of Example Compound No. 150)
    [259] In the same manner as in Example 2, except that dibenzothiophene-4-boronic acid (manufactured by Frontier Scientific) was used instead of 2- (9,9-dimethylfluorenyl) boronic acid in Example 2. Compounds were easily synthesized.
    [260] Tris [2,5-bis (benzothiophen-4-yl) pyridine-C 3 , N] iridium (III).
    [261] Example 32
    [262] The organic EL device shown in Fig. 1 (c) was manufactured by the following method.
    [263] Charge transfer of α-NPD to 40 nm thickness by vacuum deposition (10 -4 Pa) at a deposition rate of 0.1 nm / sec on a 100 nm thick patterned ITO electrode (anode) formed on a 1.1 mm thick alkali-free glass substrate. A layer was formed. The iridium complex of CBP: Exemplified Compound No. 23 was subjected to resonance co-deposition at a deposition rate of 0.1 nm / sec (for CBP) and 0.09 nm / sec (for iridium complex) by controlling the heating conditions of the deposition vessel on this charged transport layer. A light emitting layer (co-deposited film) having a thickness of (93: 7 parts by weight) was formed. On this light emitting layer, 40 nm-thick excitus diffusion prevention layer of BCP (Batocuproin) by vacuum deposition at a deposition rate of 0.1 nm / sec or 20 nm-thick electron transfer of Alq3 by vacuum deposition at a deposition rate of 0.1 nm / sec. A layer was formed. Thereafter, a 150 nm thick aluminum electrode (cathode) was formed by vacuum deposition at a deposition rate of 0.1 nm / second as the electron transport layer.
    [264] The organic EL device thus produced exhibited an emission spectrum of 12.4 lm / W at a luminance of 100 cd / m 2, an emission efficiency of 13.6 lm / W at a luminance of 600 cd / m 2, and an EL spectrum showing λ max = 545 nm. .
    [265] Example 33
    [266] Instead of tris [2- (9,9-dimethylfluoren-2-yl) pyridine-C 3 , N] iridium (III) synthesized in Example 1 (Example Compound No. 23), tris [2,5-bis ( An organic EL device was fabricated and evaluated in the same manner as in Example 32 except that 9,9-dimethylfluoren-2-yl) -pyridine-C 3 , N] iridium (III) (Example Compound No. 43) was used. .
    [267] The organic EL device thus obtained exhibited an emission spectrum of 2.4 lm / W at a luminance of 100 cd / m 2, a emission efficiency of 1.9 lm / W at a luminance of 300 cd / m 2, and an EL spectrum showing λ max = 590 nm.
    [268] Example 34 (Synthesis of Example Compound No. 54)
    [269] In Example 1, the following compound was easily synthesize | combined similarly to Example 1 except having used 4-phenyl- 1-bromopyridine (made by General-Ethymidiate, Canada) instead of 2-bromopyridine.
    [270] Tris [2- (9,9-dimethylfluoren-2-yl) -4-phenylpyridine-C 3 , N] iridium (III).
    [271] As described above, according to the present invention, the metal coordination compound of the formula (1) characterized by the aromatic group of the formula (5) as a partial structure is an excellent material showing a high emission quantum efficiency. The electroluminescent device (light emitting device) of the present invention using the metal coordination compound of the formula (1) as a light emitting central material can not only enable high efficiency light emission, but also maintain high brightness for a long time, and also deteriorate due to current passing. Less is an excellent device. In addition, the display device using the electroluminescent element of the present invention exhibits excellent display performance.
    权利要求:
    Claims (16)
    [1" claim-type="Currently amended] Formula (1):
    ML m L ' n (1)
    Wherein M is a metal atom of Ir, Pt, Rh or Pd; L and L 'are two different bidentate ligands; m is 1, 2 or 3, n is 0, 1 or 2, provided that m + n is 2 or 3; Substructure ML m is represented by the formula (2) shown below, and substructure ML ' n is represented by the following formula (3) or (4):

    [Wherein, CyN1 and CyN2 are each a ring group which may have a substituent, including a nitrogen atom, which is bonded to the metal atom M through the nitrogen atom; CyC1 and CyC2 are each a cyclic group which may have a substituent which is bonded to the metal atom M through the carbon atom including the carbon atom, except that the cyclic group CyN1 and the cyclic group CyC1 are bonded to each other through a covalent bond, Cyclic group CyN2 and cyclic group CyC2 are bonded to each other through a covalent bond;
    Arbitrary substituents on the ring group include a halogen atom, a cyano group, a nitro group, a trialkylsilyl group wherein the alkyl group is a linear or branched alkyl group having 1 to 8 carbon atoms independently, and an alkyl group is -O-, -S-,- One or more non-adjacent methylene groups which may be substituted with CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C— may also include an alkyl group. Is a linear or branched alkyl group having 1 to 20 carbon atoms which may include a hydrogen atom which may be substituted with a fluorine atom, or a substituent (halogen atom, cyano atom, nitro atom, alkyl group is -O-, -S May include one or more non-adjacent two or more methylene groups which may be substituted with —, —CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C—, Also, the alkyl group may be a straight or branched alkyl group having 1 to 20 carbon atoms which may include a hydrogen atom which may be substituted with a fluorine atom if necessary). Is selected from the group which direction,
    E and G are independently a linear or branched alkyl group having 1 to 20 carbon atoms, or a substituent (halogen atom, cyano atom, nitro atom, alkyl group independently, in which the alkyl group may include a hydrogen atom which may be substituted with a fluorine atom). Trialkylsilyl groups, which are linear or branched alkyl groups having 1 to 8 carbon atoms, and alkyl groups are -O-, -S-, -CO-, -CO-O-, -O-CO-, -CH = CH- or- 1 to 20 carbon atoms which may include one or two or more non-adjacent methylene groups which may be substituted with C≡C-, and an alkyl group may include a hydrogen atom which may be substituted with a fluorine atom as necessary. Aromatic straight chain or branched alkyl group);
    At least one of the arbitrary substituents of a cyclic group, and cyclic groups CyC1 and CyC2 are following formula (5):

    [The aromatic group of formula (5) is bonded to CyN1, CyN2, CyC1 or CyC2 through a single bond when the aromatic group is any substituent of the ring group, and the aromatic group of the formula (5), the aromatic group is CyC1 or In the case of CyC2, it is bonded with the metal atom M through a single bond;
    Y is C═O, CRR ′, C═C (CN) 2 , O or S (wherein R and R ′ are independently a hydrogen atom, a straight or branched alkyl group having 1 to 8 carbon atoms, an alkyl group is —O—, It may contain one or more than two non-contiguous methylene groups which may be substituted by -S-, -CO-, -CO-O-, -O-CO-, -CH = CH- or -C≡C- And a linear or branched alkyl group having 1 to 20 carbon atoms which may include a hydrogen atom which may be substituted with a fluorine atom, if necessary, or a substituent (halogen atom, cyano atom, nitro atom, alkyl group- One or two or more non-contiguous methylene groups which may be substituted by O-, -S-, -CO-, -CO-O-, -O-CO-, -CH = CH- or -C≡C- And an alkyl group, which may be a linear or branched alkyl group having 1 to 20 carbon atoms, which may include a hydrogen atom which may be substituted with a fluorine atom if necessary);
    Arbitrary substituents of the formula (5) include a trialkylsilyl group in which a halogen atom, a cyano group, a nitro group, and an alkyl group are each independently a linear or branched alkyl group having 1 to 8 carbon atoms, and an alkyl group is -O-, -S-. May include one or more than two non-adjacent methylene groups which may be substituted by -CO-, -CO-O-, -O-CO-, -CH = CH- or -C≡C-, and , A linear or branched alkyl group having 1 to 20 carbon atoms which may include a hydrogen atom which may be substituted with a fluorine atom, if necessary, or a substituent (halogen atom, cyano atom, nitro atom, alkyl group is -O-, It may contain one or more than two non-contiguous methylene groups which may be substituted by -S-, -CO-, -CO-O-, -O-CO-, -CH = CH- or -C≡C- And an alkyl group is a straight or branched alkyl group having 1 to 20 carbon atoms which may include a hydrogen atom which may be substituted with a fluorine atom if necessary. Selected from an aromatic group, provided that an adjacent pair of substituents may combine to form a ring structure.
    [2" claim-type="Currently amended] The metal coordination compound according to claim 1, which contains a partial structure ML ' n represented by the formula (3) in the formula (1).
    [3" claim-type="Currently amended] The metal coordination compound according to claim 1, which contains a partial structure ML ' n represented by the formula (4) in the formula (1).
    [4" claim-type="Currently amended] The metal coordination compound according to claim 1, wherein n in Formula (1) is 0.
    [5" claim-type="Currently amended] The metal coordination compound according to claim 1, wherein the group Y in the formula (5) is C = O or CRR '.
    [6" claim-type="Currently amended] The cyclic group CyC1 and CyC2 according to claim 1, wherein the cyclic group CyC1 and CyC2 are independently a phenyl group which may have a substituent under the condition that the aromatic ring group may include one or two CH groups which may be substituted with a nitrogen atom. , A metal coordination compound selected from thienyl, thianaphthyl, naphthyl, pyrenyl, 9-fluorenyl, fluorenyl, dibenzofuryl, dibenzothiethyl or carbazolyl.
    [7" claim-type="Currently amended] The metal coordination compound according to claim 1, wherein the ring groups CyC1 and CyC2 are independently a phenyl group or a 2-fluorenyl group.
    [8" claim-type="Currently amended] The metal coordination compound according to claim 1, wherein the ring groups CyN1 and CyN2 are aromatic ring groups which may have a substituent, and are independently selected from a pyridyl group, a pyridazinyl group, and a pyrimidinyl group.
    [9" claim-type="Currently amended] The metal coordination compound according to claim 1, wherein the aromatic ring group is a pyridyl group.
    [10" claim-type="Currently amended] The method of claim 1, wherein the CyN1, CyN2, CyC1 or CyC2 is independently unsubstituted, or a halogen atom and a linear or branched alkyl group having 1 to 20 carbon atoms (where the alkyl group is -O-, -S-,- One or more non-adjacent two or more methylene groups, or substituents [halogen atoms, or], which may be substituted by CO—, —CO—O—, —O—CO—, —CH═CH— or —C≡C—. A straight or branched alkyl group having 1 to 20 carbon atoms, wherein the alkyl group may include one or two or more non-adjacent methylene groups which may be substituted with -O-, and the alkyl group may be substituted with a fluorine atom as necessary. And a divalent aromatic group which may have a hydrogen atom, which may include a hydrogen atom, wherein the metal coordination compound has a substituent.
    [11" claim-type="Currently amended] The metal coordination compound according to claim 1, wherein M in the formula (1) is iridium.
    [12" claim-type="Currently amended] The method according to claim 1, wherein the following formula (6):

    Wherein X is CRR ', O or S [wherein R and R' are independently of the formula: C n H 2n + 1- (wherein n is an integer from 1 to 20 and the alkyl group is substituted with -O-) One or more non-adjacent two or more methylene groups which may be included, and may further include a hydrogen atom which may be substituted with a fluorine atom if necessary).
    R2 is a hydrogen atom; Fluorine atoms; Formula: C n H 2n + 1- (where n is an integer from 1 to 20, wherein the alkyl group may comprise one or more nonadjacent two or more methylene groups which may be substituted by -O-, A linear or branched alkyl group of a hydrogen atom which may be substituted with a fluorine atom if necessary); Phenyl group which may have a substituent; 9,9-dialkylfluorenyl group wherein the alkyl group is, independently, a formula: C n H 2n + 1- (wherein n is an integer of 1 to 20, and the alkyl group may be substituted with -O- A single or non-adjacent two or more methylene groups, and may further include a hydrogen atom which may be substituted with a fluorine atom if necessary); Dibenzofuranyl group which may have a substituent; And a dibenzothienyl group which may have a substituent; Optional substituents of the phenyl group, 9,9-dialkylfluorenyl group, dibenzofuranyl group and dibenzothienyl group may be a fluorine atom or a formula: C n H 2n + 1- (where n is an integer of 1 to 20). The alkyl group may include one or two or more non-adjacent methylene groups which may be substituted with -O-, and may further include a hydrogen atom which may be substituted with a fluorine atom as necessary. Or a branched alkyl group}.
    [13" claim-type="Currently amended] An electroluminescent device comprising a light emitting unit comprising a pair of electrodes disposed on a substrate and at least one organic compound disposed between the electrodes,
    An electroluminescent element comprising the metal coordination compound represented by formula (1) according to claim 1.
    [14" claim-type="Currently amended] The method of claim 13, wherein the light is emitted by applying a voltage between the electrodes.
    Electroluminescent device, characterized in that.
    [15" claim-type="Currently amended] The electroluminescent device according to claim 13, wherein phosphorescence is performed by applying a voltage between the electrodes.
    [16" claim-type="Currently amended] An image display apparatus comprising the electroluminescent element according to claim 13 and means for supplying an electrical signal to the electroluminescent element.
    类似技术:
    公开号 | 公开日 | 专利标题
    JP6639546B2|2020-02-05|L2MX-type complexes as phosphorescent dopants for organic LEDs
    JP6251299B2|2017-12-20|Phosphorescent substance
    JP6203793B2|2017-09-27|Methyl-D3 substituted iridium complex
    JP6586140B2|2019-10-02|Blue emitter with high efficiency based on imidazo [1,2-f] phenanthridine iridium complex
    KR20190057044A|2019-05-27|Novel heteroleptic iridium complexes
    KR102043585B1|2019-11-11|Heteroleptic iridium complexes as dopants
    JP2017081935A|2017-05-18|PHENYL AND FLUORENYL SUBSTITUTED PHENYL-PYRAZOLE COMPLEXES OF IRIDIUM |
    JP5981603B2|2016-08-31|Heteroleptic iridium complex
    JP6581169B2|2019-09-25|Phosphorescent substance
    US10069089B2|2018-09-04|Organic metal complex, and organic light emitting device and display apparatus using the same
    JP6077579B2|2017-02-08|Triphenylene host in phosphorescent light-emitting diodes
    JP6219466B2|2017-10-25|Phosphorescent substance
    JP2019194223A|2019-11-07|Phosphorescent materials
    JP2019196403A|2019-11-14|Tetradentate platinum complexes
    KR102049706B1|2019-11-28|High efficiency yellow light emitters for oled devices
    JP5972884B2|2016-08-17|Organic electroluminescence device
    JP6025959B2|2016-11-16|2-Azatriphenylene materials for organic light-emitting diodes
    JP6316351B2|2018-04-25|Pyridylcarbene phosphor photoluminescent material
    JP5982264B2|2016-08-31|New heteroleptic iridium complexes
    JP5448274B2|2014-03-19|Light emitting element, light emitting device, and electronic device
    JP5577370B2|2014-08-20|Stable and efficient electroluminescent material
    US20150076478A1|2015-03-19|Luminescence device and display apparatus
    TWI423982B|2014-01-21|Organometallic complex and light emitting element, light emitting device, and electronic device using the organometallic complex
    EP1963346B1|2012-08-22|Organometallic complex and light-emitting element, light-emitting device and electronic device using the same
    US7250512B2|2007-07-31|Electroluminescent iridium compounds having red-orange or red emission and devices made with such compounds
    同族专利:
    公开号 | 公开日
    US6921915B2|2005-07-26|
    EP1238981A3|2002-10-30|
    JP4307000B2|2009-08-05|
    JP2002332291A|2002-11-22|
    EP1238981A2|2002-09-11|
    DE60204612T2|2006-05-11|
    US20030068535A1|2003-04-10|
    CN1374315A|2002-10-16|
    EP1238981B1|2005-06-15|
    DE60204612D1|2005-07-21|
    KR100488869B1|2005-05-17|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-03-08|Priority to JPJP-P-2001-00064254
    2001-03-08|Priority to JP2001064254
    2002-02-20|Priority to JPJP-P-2002-00042522
    2002-02-20|Priority to JP2002042522A
    2002-03-08|Application filed by 캐논 가부시끼가이샤
    2002-09-14|Publication of KR20020072215A
    2005-05-17|Application granted
    2005-05-17|Publication of KR100488869B1
    优先权:
    申请号 | 申请日 | 专利标题
    JPJP-P-2001-00064254|2001-03-08|
    JP2001064254|2001-03-08|
    JPJP-P-2002-00042522|2002-02-20|
    JP2002042522A|JP4307000B2|2001-03-08|2002-02-20|Metal coordination compound, electroluminescent element and display device|
    [返回顶部]