JP2017502509A - NOVEL ORGANIC ELECTROLUMINESCENT COMPOUND, MULTI-COMPONENT HOST MATERIAL CONTAINING THE SAME AND ORGANIC ELECTROLUMINESCENT DEVICE - Google Patents

Abstract

The present disclosure relates to organic electroluminescent compounds, and multi-component host materials and organic electroluminescent devices containing the same. The organic electroluminescent compound of the present disclosure has good light emission efficiency and can be used as a host of the light emitting layer. By using the organic electroluminescent compound according to the present disclosure, the organic electroluminescent device can have high color purity, low driving voltage, long lifetime, and improved current efficiency and power efficiency. [Selection figure] None

Description

  The present disclosure relates to a novel organic electroluminescent compound, and a multi-component host material and an organic electroluminescent device including the same.

  An electroluminescent (EL) device is a self-luminous device that is advantageous in that it provides a wider viewing angle, a higher contrast ratio, and a faster response time. Organic EL devices were first developed by Eastman Kodak using small aromatic diamine molecules and aluminum complexes as materials for forming the light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].

  In general, an organic EL element has a structure including an anode, a cathode, and an organic layer disposed between the anode and the cathode. Holes and electrons are injected into the organic layer from the anode and the cathode, respectively, and the compound becomes excited by recombination of holes and electrons, and energy decays to the ground state with emission. ease. The organic layer of the organic EL element includes a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like. Materials for preparing the organic layer include hole injection materials, hole transport materials, electron blocking materials, light emitting materials, hole blocking materials, electron transport materials, electron injection materials and the like.

  The most important factor that determines the luminous efficiency of the organic EL element is the luminescent material. The light emitting material needs to have high quantum efficiency, high electron mobility, and high hole mobility. Furthermore, the light emitting layer formed by the light emitting material must be uniform and stable. Depending on the color visualized by the luminescence, the luminescent material can be classified as a blue, green, or red luminescent material, and a yellow or orange luminescent material may further be included therein. Furthermore, depending on the excited state, the luminescent material can be classified as a fluorescent material (singlet state) and a phosphorescent material (triplet state). Fluorescent materials have been widely used for organic EL devices. However, since phosphorescent materials can increase the luminous efficiency for converting electricity into light four times and reduce power consumption to have a longer life compared to fluorescent materials, phosphorescent light emission Material development has been extensively studied.

As red, green, and blue light-emitting materials, bis (2- (2′-benzothienyl) -pyridinato-N, C3 ′) iridium (acetylacetonato) ((acac) Ir (btp) ₂ ), tris ( An iridium (III) complex containing 2-phenylpyridine) iridium (Ir (ppy) ₃ ) and bis (4,6-difluorophenylpyridinato-N, C2) picolinatoiridium (Firpic) is used as a phosphorescent material. Widely known.

  The luminescent material can be prepared by combining a host material and a dopant so as to improve color purity, luminous efficiency, and stability. When a host material / dopant system is used as the luminescent material, their selection is important because the host material greatly affects the efficiency and performance of the EL device. At present, 4,4'-N, N'-dicarbazol-biphenyl (CBP) is the most widely known host material for phosphorescent materials. Recently, Pioneer (Japan) et al. Used bathocproin (BCP) and aluminum (III) bis (2-methyl-8-quinolinate) (4-phenylphenolate) (BAlq), etc., known as hole blocking materials as host materials. Used to develop high performance organic EL devices.

  Conventional phosphorescent host materials provide good luminescent properties, but they have the following disadvantages: (1) High temperature deposition in vacuum due to their low glass transition temperature and poor thermal stability Degradation can occur during the process. (2) The power efficiency of the organic EL element is obtained by [(π / voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage. An organic EL device containing a phosphorescent host material provides a higher current efficiency (cd / A) than a device containing a fluorescent material, but requires a significantly higher driving voltage. Therefore, there is no advantage in terms of power efficiency (lm / W). (3) Furthermore, the operating life of organic EL elements is short, and the luminous efficiency still needs improvement.

  Therefore, in order to provide an organic EL device having good characteristics, a material for preparing an organic layer in the organic EL device, particularly a host or a dopant for preparing a light emitting layer, must be appropriately selected. I must.

  Korean Patent Application Publication No. 10-2010-0105099 discloses a heterocyclic compound having five condensed rings as a host material of a light emitting layer. However, an organic electroluminescence device using the compound of the above-mentioned reference is not satisfactory in terms of power efficiency, light emission efficiency, lifetime, and color purity.

  An object of the present disclosure is to provide an organic electroluminescent compound capable of providing an organic electroluminescent device exhibiting a low driving voltage, a long lifetime, high color purity, and good current efficiency and power efficiency, and a multi-component host material including the same And providing an organic electroluminescent device.

  The present inventor has discovered that the above object can be achieved by an organic electroluminescent compound represented by the following formula 1.

Wherein Ar ₁ represents substituted or unsubstituted (3 to 30 membered) heteroaryl, or substituted or unsubstituted (C6-C30) aryl;

L ₁ represents a single bond, substituted or unsubstituted (C6-C30) arylene, or substituted or unsubstituted (3 to 30 membered) heteroarylene;

  Ring A is

  Ring B is

  Represents;

Y represents O, S, N (R ₆ ), or C (R ₄ ) (R ₅ ); X represents O, S, N (R ₆ ), or C (R ₇ ) (R ₈ ) Provided that X and Y cannot both be N (R ₆ ) at the same time;

R _{1 to} R ₃ are each independently hydrogen, deuterium, halogen, cyano, carboxy, nitro, hydroxy, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C3-C30) cyclo. Alkyl, substituted or unsubstituted (C3-C30) cycloalkenyl, substituted or unsubstituted (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3- 30 membered) representing a heteroaryl, -NR ₉ R ₁₀ , or -SiR ₁₁ R ₁₂ R ₁₃ , or bonded to adjacent substituent (s) to form a substituted or unsubstituted (C3-C30), May form monocyclic or polycyclic alicyclic or aromatic rings;

R _{4 to} R ₁₃ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3 ˜30 membered heteroaryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (5-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl (C1-C30) ) Represents alkyl, -NR < ₁₄ > R < ₁₅ >, -SiR < ₁₆ > R < ₁₇ > R < ₁₈ >, cyano, nitro, or hydroxy, or is combined with adjacent substituent (s) to give substituted or unsubstituted (C3-C30 ) May form monocyclic or polycyclic alicyclic or aromatic rings;

R _{14 to} R ₁₈ have the same definition as R _{4 to} R ₁₃ ;

  The carbon atom (s) of the alicyclic or aromatic ring may be replaced with at least one heteroatom selected from nitrogen, oxygen, and sulfur;

  Heteroaryl (heteroarylene) and heterocycloalkyl contain at least one heteroatom selected from B, N, O, S, P (═O), Si, and P;

a, b, and c each independently represent an integer of 1 to 4; a, b, or c represents an integer of 2 or more, and each of R ₁ , R ₂ , or R ₃ is the same Or may be different;

However, the compound of the above formula 1 is represented by the following formula 2, and the ring that may be formed between any one of R _{1 to} R _{3 and} the adjacent substituent (s) is substituted It should not be a naphthalene ring.

  The organic electroluminescent compound of the present disclosure can provide higher color purity, longer lifetime, and better luminous efficiency compared to conventional compounds. Therefore, an organic electroluminescence device using the compound of the present disclosure as a host material of the light emitting layer has a higher color purity, a lower driving voltage, a longer lifetime, a better luminous efficiency, particularly a better current efficiency and improvement. Power consumption can be shown.

  Hereinafter, the present disclosure will be described in detail. However, the following description is intended to illustrate the present disclosure and is not meant to limit the scope of the present disclosure in any way.

  The present disclosure provides an organic electroluminescent compound of formula 1 above, an organic electroluminescent material comprising the same, and an organic electroluminescent device comprising the material.

  In the present specification, “(C1-C30) alkyl (alkylene)” means a linear or branched alkyl having 1 to 30, preferably 1 to 20, more preferably 1 to 10 carbon atoms ( Alkylene) and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like. "(C2-C30) alkenyl" refers to a straight or branched alkenyl having 2 to 30, preferably 2 to 20, more preferably 2 to 10 carbon atoms, vinyl, 1-propenyl 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-2-butenyl and the like. "(C2-C30) alkynyl" refers to straight or branched chain alkynyl having 2 to 30, preferably 2 to 20, more preferably 2 to 10 carbon atoms, including ethynyl, 1-propynyl 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-pentynyl and the like. “(C 3 -C 30) cycloalkyl” means a monocyclic or polycyclic hydrocarbon having 3 to 30, preferably 3 to 20, more preferably 3 to 7 carbon atoms; Including propyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. “(3-7 membered) heterocycloalkyl” means at least one heteroatom selected from the group consisting of B, N, O, S, P (═O), Si, and P, preferably O, S , N and cycloalkyl having 3 to 7, preferably 5 to 7 ring skeleton atoms, including tetrahydrofuran, pyrrolidine, thiolane, tetrahydropyran and the like. Furthermore, “(C6-C30) aryl (arylene)” is a single group having 6 to 30, preferably 6 to 20, more preferably 6 to 15 ring skeleton carbon atoms derived from an aromatic hydrocarbon. It means a cyclic ring or a condensed ring, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrycenyl, naphthacenyl, fluoranthenyl and the like. “(3-30 membered) heteroaryl (heteroarylene)” is at least one selected from the group consisting of B, N, O, S, P (═O), Si, and P, preferably 1-4. Represents an aryl group containing 3 to 30, preferably 3 to 20, more preferably 3 to 15 ring skeleton atoms containing 1 heteroatom; monocyclic ring or condensed with at least one benzene ring A fused ring, which may be partially saturated and formed by linking at least one heteroaryl or aryl group to the heteroaryl group by a single bond (s), Monocyclic ring heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl Oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and fused ring heteroaryls such as benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl , Benzonaphthofuranyl, benzonaphthofuranylthiophenyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl , Quinoxalinyl, carbazolyl, benzocarbazolyl, naphthyridinyl, phenoxazinyl, carbazolyl, benzo Including the Okisoriru like. Further, “halogen” includes F, Cl, Br, and I.

In the present specification, “substituted” in the expression “substituted or unsubstituted” means that a hydrogen atom of a specific functional group is replaced with another atom or group, that is, a substituent. In the formula 1 of the present _disclosure, Ar _1, L 1, X, Y, and substitutions at _{R 1 ~R 3 (C1-C30} ) alkyl, substituted (C3-C30) cycloalkyl, substituted (C3-C30) cycloalkenyl, Substituted (3-7 membered) heterocycloalkyl, substituted (C6-C30) aryl (arylene), substituted (3-30 membered) heteroaryl (heteroarylene), substituted (C6-C30) aryl (C1-C30) alkyl, Alternatively, the substituted (C3-C30) monocyclic or polycyclic alicyclic or aromatic substituents are each independently deuterium, halogen, cyano, carboxy, nitro, hydroxy, (C1- C30) alkyl, halo (C1-C30) alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C1-C30) alkoxy, ( 1-C30) alkylthio, (C3-C30) cycloalkyl, (C3-C30) cycloalkenyl, (3-7 membered) heterocycloalkyl, (C6-C30) aryloxy, (C6-C30) arylthio, (C6- C30) aryl substituted or unsubstituted (3-30 membered) heteroaryl, (3-30 membered) heteroaryl unsubstituted or substituted (C6-C30) aryl, tri (C1 -C30) alkylsilyl, tri (C6-C30) arylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, (C1-C30) alkyldi (C6-C30) arylsilyl, amino, mono or di ( C1-C30) alkylamino, mono- or di (C6-C30) arylamino, (C1-C3) ) Alkyl (C6-C30) arylamino, (C1-C30) alkylcarbonyl, (C1-C30) alkoxycarbonyl, (C6-C30) arylcarbonyl, di (C6-C30) arylboronyl, di (C1-C30) Selected from the group consisting of alkylboronyl, (C1-C30) alkyl (C6-C30) aryl boronyl, (C6-C30) aryl (C1-C30) alkyl, and (C1-C30) alkyl (C6-C30) aryl Is at least one.

  Preferably, the compound of formula 1 may be represented by any one of formulas 2-5 below:

In the formula, Ar ₁ , L ₁ , X, Y, R _{1 to} R ₃ , a, b, and c are as defined in Formula 1.

Ar ₁ may preferably represent substituted or unsubstituted (5-20 membered) heteroaryl, or substituted or unsubstituted (C6-C20) aryl. The substituent of the substituted group of Ar ₁ may be (C6-C20) aryl, (6-20 membered) heteroaryl, or mono- or di- (C6-C20) arylamino. According to one embodiment of the present disclosure, Ar ₁ may represent a substituted or unsubstituted nitrogen-containing (5-20 membered) heteroaryl; specifically substituted or unsubstituted triazinyl, substituted or non-substituted Substituted pyrimidinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted naphthyridinyl, and substituted or unsubstituted It may be selected from the group consisting of substituted quinoxalinyl. In the above embodiment, the substituent of the substituted group of Ar ₁ may preferably be (C6-C20) aryl or (5-20 membered) heteroaryl, specifically phenyl, naphthyl, biphenyl. , Benzofuranyl, benzothiophenyl, dibenzofuranyl, and dibenzothiophenyl.

L ₁ is preferably a single bond, substituted or unsubstituted (C6-C20) arylene, or substituted or unsubstituted (5-20 membered) heteroarylene; more preferably a single bond, or substituted or unsubstituted. (C6-C20) arylene may be represented. Specifically, L ₁ may represent a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, or substituted or unsubstituted naphthylene.

Preferably, X and Y may each independently be selected from O, S, and N (R ₆ ); provided that both X and Y cannot be N (R ₆ ) at the same time Shall. According to one embodiment of the present disclosure, X and Y may each be independently selected from O and S. According to another embodiment of the present disclosure, X and Y may each be independently selected from O and S, and at least one of X and Y may be S. R ₆ may preferably represent substituted or unsubstituted (C6-C30) aryl, specifically substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted biphenyl. .

R _{1 to} R ₃ are each independently preferably hydrogen, deuterium, substituted or unsubstituted (C1-C20) alkyl, substituted or unsubstituted (C3-C20) cycloalkyl, substituted or unsubstituted. (C6-C30) may represent aryl, substituted or unsubstituted (3-30 membered) heteroaryl, —NR ₉ R ₁₀ , or —SiR ₁₁ R ₁₂ R ₁₃ , or adjacent substituent (s) ) To form a substituted or unsubstituted (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring. More preferably, the monocyclic or polycyclic aromatic ring in the definition of R _{1 to} R ₃ is not a naphthalene ring or a phenanthrene ring. R _{9 to} R ₁₃ may preferably represent substituted or unsubstituted (C 6 -C 30) aryl. Specifically, R _{1 to} R ₃ may represent hydrogen.

According to one embodiment of the present disclosure, Ar ₁ represents substituted or unsubstituted (5-20 membered) heteroaryl, or substituted or unsubstituted (C6-C20) aryl; L ₁ is a single bond, Represents substituted or unsubstituted (C6-C20) arylene or substituted or unsubstituted (5 to 20 membered) heteroarylene; R _{1 to} R ₃ each independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C20) alkyl, substituted or unsubstituted (C3-C20) cycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3 to 30 membered) heteroaryl, —NR ₉ or represents R ₁₀ or _-SiR 11 _R 12 _{R 13,,} or combined with an adjacent substituent (s), a substituted or unsubstituted (C3-C30), mono- Or polycyclic alicyclic or aromatic ring may be formed.

  Compounds represented by Formula 1 include, but are not limited to:

The organic electroluminescent compound of the present disclosure can be prepared by synthetic methods known to those skilled in the art, such as bromination, Suzuki reaction, Buchwald-Hartwig reaction, Ullmann reaction, and the like. For example, a compound of formula 1 can be prepared as follows: a compound of formula A is prepared by preparing a pentacyclic condensed compound represented by formula A and then subjecting the compound of formula A to bromination. A compound of formula B is condensed with an indene ring, an indole ring, a benzofuran ring, or a benzothiophene ring to give a mother nucleus structure of formula 1; then a mother nucleus that was prepared ^* -L ₁ -Ar ₁ Link to the structure, thereby obtaining the compound of formula 1.

In Formulas A and B, X and Y are each independently selected from O, S, N (R ₆ ), C (R ₄ ) (R ₅ ), and C (R ₇ ) (R ₈ ). Also good.

  Methods for preparing the aforementioned compounds of the present disclosure can be illustrated in the following reaction schemes 1-4.

  [Reaction Scheme 1]

  [Reaction Scheme 2]

  [Reaction Scheme 3]

  [Reaction Scheme 4]

In the above reaction schemes 1 to 4, X can be selected from O, S, N (R ₆ ), and C (R ₇ ) (R ₈ ).

  According to another aspect of the present disclosure, an organic electroluminescent material comprising the organic electroluminescent compound of Formula 1 and an organic electroluminescent device comprising the material are provided.

  The material may comprise one or more compounds selected from the organic electroluminescent compounds of formula 1. The material may further comprise conventional compound (s) that have been included for organic electroluminescent materials. The organic electroluminescent material may preferably be a host material. When an organic electroluminescent material is used as the host material, it may further contain a second host material other than the compound of Formula 1 of the present disclosure, and details thereof will be described later.

  The organic electroluminescence element of the present disclosure may include a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, The organic layer may comprise at least one compound of formula 1.

  One of the first and second electrodes may be an anode, and the other may be a cathode. The organic layer may comprise a light emitting layer and is selected from a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, an electron injection layer, an intermediate layer, an electron buffer layer, and a hole blocking layer At least one layer may further be provided.

  The organic electroluminescent compound of Formula 1 of the present disclosure may be included as a host material in the light emitting layer. Preferably, the light emitting layer may further include at least one dopant. Preferably, the light emitting layer may include a second host material in addition to the organic electroluminescent compound of formula 1 (first host material) of the present disclosure. The weight ratio of the first host material to the second host material is in the range of 1:99 to 99: 1, and preferably 30:70 to 70:30, in consideration of driving voltage, lifetime, and luminous efficiency. is there.

  According to another aspect of the present disclosure, a material for preparing an organic electroluminescent device is provided. The material includes a compound of the present disclosure. The material may be a material for preparing a light emitting layer of an organic electroluminescence element. When the compound of this indication is contained in the material for preparing the light emitting layer of an organic electroluminescent element, the compound of this indication may be contained as a host material. When a compound of the present disclosure is included as a host material, the material may further include a second host material. The weight ratio of the compound of the present disclosure to the second host material ranges from 1:99 to 99: 1, and preferably from 30:70 to 70:30, taking into account drive voltage, lifetime, and luminous efficiency. .

  A phosphorescent host material known in the art may be used as the second host material. A compound selected from the group consisting of the compounds of the following formulas 6 to 10 is preferable as the second host material in consideration of driving voltage, lifetime, and luminous efficiency.

  Where Cz represents the following structure:

L ₄ represents a single bond, substituted or unsubstituted (C6-C30) arylene, or substituted or unsubstituted (5-30 membered) heteroarylene; M is substituted or unsubstituted (C6-C30) aryl Or a substituted or unsubstituted (5-30 membered) heteroaryl; Y ₁ and Y ₂ are each independently —O—, —S—, —N (R ₃₁ ) —, or —C ( R ₃₂ ) (R ₃₃ ) —, provided that both Y ₁ and Y ₂ cannot be present simultaneously; X represents O or S; R _{21 to} R ₂₄ are each independently Hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted Properly is unsubstituted (5-30 membered) heteroaryl or _R 25 _R 26 or represents _R 27 Si-,; or combine with adjacent substituents (s), its carbon atom (s) nitrogen May form a monocyclic or polycyclic alicyclic or aromatic ring of (C3-C30), optionally substituted with at least one heteroatom selected from oxygen, oxygen, and sulfur; However, when h in formula 6 or i in formula 7 is 1, R ₂₃ or R ₂₄ does not form a ring containing Y ₁ or Y ₂ in formulas 8 and 9, and R ₂₂ in formula 10 is Not forming an indole ring linked to R ₂₁ of formulas 8 and 9; each of R _{25 to} R ₂₇ is independently substituted or unsubstituted (C1-C30) alkyl, or substituted or unsubstituted ( C6-C30) aryl; R ₁ to R ₃₃ are each independently hydrogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or a substituted or unsubstituted, (5-30 membered) heteroaryl Represents aryl; or in combination with adjacent substituent (s), the carbon atom (s) may be replaced with at least one heteroatom selected from nitrogen, oxygen, and sulfur; C5-C30) may form monocyclic or polycyclic alicyclic or aromatic rings; R ₃₂ and R ₃₃ may be the same or different; heteroaryl (heteroarylene) is Contains at least one heteroatom selected from B, N, O, S, P (═O), Si, and P; h and i each independently represents an integer of 1 to 3; j , K, l, and m independently represents an integer of 0~4; h, i, j, k, l or m is an integer of 2 or more, each of the _{(Cz-L 4),} the (Cz) Each of each of R ₂₁ , each of R ₂₂ , each of R ₂₃ , or each of R ₂₄ may be the same or different.

  Preferably, in formulas 6-10, M may represent a substituted or unsubstituted nitrogen-containing (6-20 membered) heteroaryl. Preferably, the substituent of the substituted group of M is substituted with (C1-C20) alkyl; (C1-C10) alkyl, tri (C6-C13) arylsilyl, or (6-13 membered) heteroaryl. Unsubstituted or substituted (C6-C24) aryl; or (C1-C10) alkyl, tri (C6-C13) arylsilyl, or (C6-C24) aryl unsubstituted or substituted (6- 20-membered) heteroaryl; or tri (C6-C20) arylsilyl. Specifically, M is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, It may represent substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, or substituted or unsubstituted phenanthrolinyl.

Preferably, at least one of R ₂₃ and R ₂₄ of formulas 6 and 7 or at least one of R ₂₁ and R ₂₂ of formulas 8-10 is substituted or unsubstituted carbazolyl, substituted or unsubstituted Benzocarbazolyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted benzonaphththiophenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted benzonaphthofuranyl, substituted or unsubstituted carbazolyl (C6-C18) aryl substituted with, (C6-C18) aryl substituted with substituted or unsubstituted benzocarbazolyl, (C6-C18) aryl substituted with substituted or unsubstituted dibenzothiophenyl, (C6-C18) a substituted with substituted or unsubstituted benzonaphthothiophenyl It may represent a reel, (C6-C18) aryl substituted with substituted or unsubstituted dibenzofuranyl, or (C6-C18) aryl substituted with substituted or unsubstituted benzonaphthofuranyl. When M is aryl, at least one of R ₂₃ and R ₂₄ , or at least one of R ₂₁ and R ₂₂ represents a substituted or unsubstituted nitrogen-containing (6-20 membered) heteroaryl. Or may have a substituted or unsubstituted nitrogen-containing (6-20 membered) heteroaryl as a substituent. Specifically, substituted or unsubstituted nitrogen-containing heteroaryl is substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolyl. , Substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, or substituted or unsubstituted phenanthrolinyl.

  Specifically, the second host material may be represented by Equation 6 above, and more specifically by Equation 11 below.

In the formula, A ₁ and A ₂ each independently represent a substituted or unsubstituted (C 6 -C 30) aryl; provided that the substituents of the substituted groups of A ₁ and A ₂ are nitrogen-containing hetero Shall not be aryl;

L ₂ represents a single bond or a substituted or unsubstituted (C6-C30) arylene;

Z _{1 to} Z ₁₆ are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted. (C2-C30) alkynyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C6-C60) aryl, substituted or unsubstituted (3-30 membered) heteroaryl, substituted or unsubstituted Of tri (C1-C30) alkylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl, substituted or unsubstituted ( C1-C30) alkyldi (C6-C30) arylsilyl, or substituted or unsubstituted mono or di C6-C30) represents arylamino; or substituted or unsubstituted (C3-C30) monocyclic or polycyclic alicyclic ring or aromatic in combination with adjacent substituent (s) A ring may be formed.

  According to one embodiment of the present disclosure, the compound of formula 11 may be represented by any one of the following formulas 12, 13, 14, and 15.

In the formula, A ₁ , A ₂ , L ₂ , and Z _{1 to} Z ₁₆ are as defined in Formula 11 above.

A ₁ and A ₂ are each independently preferably substituted or unsubstituted (C6-C18) aryl, more preferably cyano, halogen, (C1-C6) alkyl, (C6-C12) aryl, Or represents (C6-C18) aryl not substituted or substituted with tri (C6-C12) arylsilyl. Specifically, A ₁ and A ₂ are each independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted Fluorenyl, substituted or unsubstituted benzofluorenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted indenyl, substituted or unsubstituted tritriphenylenyl, substituted or unsubstituted pyrenyl , Substituted or unsubstituted tetracenyl, substituted or unsubstituted perylenyl, substituted or unsubstituted chrycenyl, substituted or unsubstituted phenylnaphthyl, substituted or unsubstituted naphthylphenyl, and substituted or unsubstituted fluoranthenyl May be selected. The substituent of a substituted group such as substituted phenyl of A ₁ and A ₂ may be cyano, halogen, (C1-C6) alkyl, (C6-12) aryl, or tri (C6-C12) arylsilyl. Good.

Z _{1 to} Z ₁₆ are preferably each independently hydrogen, cyano, substituted or unsubstituted (C1-C10) alkyl, substituted or unsubstituted (C6-C20) aryl, substituted or unsubstituted (5 Represents ˜20 membered heteroaryl or substituted or unsubstituted tri (C6-C12) arylsilyl. Z ₁ -Z ₁₆ are each independently and more preferably not substituted with hydrogen; cyano; (C1-C10) alkyl; cyano, (C1-C10) alkyl, or tri (C6-C12) arylsilyl. Or substituted (C6-C20) aryl; (C1-C10) alkyl, (C6-C15) aryl, or tri (C6-C12) arylsilyl unsubstituted or substituted (5-20 membered) ) Heteroaryl; or tri (C6-C12) arylsilyl which is unsubstituted or substituted with (C1-C10) alkyl. Specifically, Z _{1 to} Z ₁₆ are each independently hydrogen or cyano; (C 1 -C 6) alkyl; cyano, (C 1 -C 6) alkyl, or triphenylsilyl is unsubstituted or substituted. (C1-C6) dibenzothiophenyl or dibenzofuranyl, which are unsubstituted or substituted with alkyl, phenyl, biphenyl, naphthyl, or triphenylsilyl; or (C1-C6); C6) may represent triphenylsilyl which is unsubstituted or substituted by alkyl.

L ₂ preferably represents a single bond or a substituted or unsubstituted (C6-C15) arylene. Specifically, L ₂ may represent a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, or substituted or unsubstituted biphenylene.

According to one embodiment of the present disclosure, A ₁ and A ₂ may each independently represent a substituted or unsubstituted (C 6 -C 18) aryl; Z _{1 to} Z ₁₆ are each independently , Hydrogen, cyano, substituted or unsubstituted (C1-C10) alkyl, substituted or unsubstituted (C6-C20) aryl, substituted or unsubstituted (5-20 membered) heteroaryl, or substituted or unsubstituted tri (C6-C12) may be an aryl silyl; _{L 2} is a single bond, or a substituted or unsubstituted (C6-C15) may represent an arylene.

  Specifically, preferred examples of the second host material represented by Formulas 6-10 include, but are not limited to:

  (Wherein TPS represents triphenylsilyl).

  The dopant is preferably at least one phosphorescent dopant. The phosphorescent dopant material of the organic electroluminescence device of the present disclosure is not limited, but may preferably be selected from a metal complex compound of iridium (Ir), osmium (Os), copper (Cu), or platinum (Pt). More preferably, it may be selected from ortho metal complex compounds of iridium (Ir), osmium (Os), copper (Cu), or platinum (Pt), and even more preferably selected from ortho metal iridium complex compounds May be.

  The dopant to be included in the organic electroluminescence device of the present disclosure may be selected from the group consisting of compounds represented by the following formulas 16 to 18.

  Where L is selected from the following structures:

R ₁₀₀ represents hydrogen, substituted or unsubstituted (C 1 -C 30) alkyl, or substituted or unsubstituted (C 3 -C 30) cycloalkyl; R _{101 to} R ₁₀₉ and R _{111 to} R ₁₂₃ are each independently Hydrogen, deuterium, halogen, (C1-C30) alkyl unsubstituted or substituted with halogen, substituted or unsubstituted (C3-C30) cycloalkyl, cyano, substituted or unsubstituted (C6 -C30) aryl or substituted or unsubstituted (represents C1-C30) _alkoxy,; R 106 _{to R 109} may combine with an adjacent substituent (s), a substituted or unsubstituted fused ring, for example, Substituted or unsubstituted fluorene, substituted or unsubstituted dibenzothiophene, or substituted or unsubstituted dibenzofuran May form a; R ₁₂₀ to R ₁₂₃ may combine with an adjacent substituent (s), a substituted or unsubstituted fused ring, for example, may form a substituted or unsubstituted quinoline; R _{124 to} R ₁₂₇ each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, or substituted or unsubstituted (C 6 -C 30) aryl; R _{124 to} R ₁₂₇ combines with adjacent substituent (s) to form a substituted or unsubstituted fused ring, eg, substituted or unsubstituted fluorene, substituted or unsubstituted dibenzothiophene, or substituted or unsubstituted dibenzofuran Each of R _{201 to} R ₂₁₁ is independently or not substituted with hydrogen, deuterium, halogen, halogen ( C1-C30) alkyl, substituted or unsubstituted (C3-C30) cycloalkyl, or substituted or unsubstituted (C6-30) aryl, wherein R _{208 to} R ₂₁₁ are adjacent substituent (s) May be joined to form a substituted or unsubstituted fused ring, eg, substituted or unsubstituted fluorene, substituted or unsubstituted dibenzothiophene, or substituted or unsubstituted dibenzofuran; f and g are each independently And when f or g is an integer of 2 or more, each of R ₁₀₀ may be the same or different; n represents an integer of 1 to 3.

  Specifically, the phosphorescent dopant material includes:

  According to another aspect of the present disclosure, an organic electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises one or more light-emitting layers. At least one light-emitting layer includes one or more dopant compounds and two or more host compounds; the first host compound of the two or more host compounds is an organic electroluminescent compound represented by Formula 1 An organic electroluminescent device is provided.

  When the organic electroluminescence device includes two host compounds, the weight ratio of the first host material to the second host material is 1:99 to 99: 1 in consideration of driving voltage, lifetime, and luminous efficiency. And preferably in the range of 30:70 to 70:30.

  According to one embodiment of the present disclosure, in the organic electroluminescence device, the first host compound of two or more host compounds may be the organic electroluminescence compound represented by Formula 1, and the second host The compound may be selected from compounds represented by Formulas 6-10.

  According to another embodiment of the present disclosure, in the organic electroluminescent device, the first host compound of the two or more host compounds may be an organic electroluminescent compound represented by Formula 1, and the second The host compound may be a compound represented by Formula 11.

  According to another embodiment of the present disclosure, in the organic electroluminescent device, the one or more dopant compounds may be selected from compounds represented by Formulas 12-15.

  The organic electroluminescent element of this indication contains the compound of Formula 1 in an organic layer. The organic electroluminescent device of the present disclosure may further include at least one compound selected from the group consisting of arylamine compounds and styrylarylamine compounds.

  In the organic electroluminescence device of the present disclosure, in addition to the compound of Formula 1, the organic layer includes a Group 1 metal, a second metal, a fourth transition metal, a fifth transition metal, a lanthanide, and a periodic table. It may further include at least one metal selected from the group consisting of organic metals of d transition metals, or at least one complex compound containing a metal.

  Furthermore, the organic electroluminescence device of the present disclosure further includes at least one light emitting layer containing a blue electroluminescence compound, a red electroluminescence compound, or a green electroluminescence compound known in the art in addition to the compound of the present disclosure. As a result, white light can be emitted. If necessary, the device may further comprise an orange light emitting layer or a yellow light emitting layer.

In the organic electroluminescence device of the present disclosure, preferably, at least one layer selected from a chalcogenide layer, a metal halide layer, and a metal oxide layer (hereinafter referred to as a “surface layer”) has one or both of them. It may be disposed on the inner surface (s) of the electrode (s). Specifically, a silicon or aluminum chalcogenide (including oxide) layer is preferably disposed on the anode surface of the electroluminescent media layer, and the metal halide or metal oxide layer is preferably electroluminescent. It is disposed on the cathode surface of the medium layer. Such a surface layer provides operational stability for the organic electroluminescent device. Preferably, the chalcogenide includes SiO _X (1 ≦ X ≦ 2), AlO _X (1 ≦ X ≦ 1.5), SiON, SiAlON, etc .; the metal halide is LiF, MgF ₂ , CaF ₂ , rare earth metal Metal oxide includes Cs ₂ O, Li ₂ O, MgO, SrO, BaO, CaO and the like.

  In the organic electroluminescence device of the present disclosure, the mixed region of the electron transport compound and the reducing dopant or the mixed region of the hole transport compound and the oxidizing dopant may be disposed on the surface of at least one of the pair of electrodes. Good. In this case, since the electron transport compound is reduced to an anion, it becomes easy to inject and transport electrons from the mixed region to the electroluminescent medium. Furthermore, since the hole transport compound is oxidized to cations, it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium. Preferably, the oxidizing dopant includes various Lewis acids and acceptor compounds, and the reducing dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals, and mixtures thereof. The reducing dopant layer may have two or more light emitting layers and may be used as a charge generation layer for preparing an electroluminescent device that emits white light.

  In order to form each layer of the organic electroluminescent device of the present disclosure, dry film forming methods such as vacuum deposition, sputtering, plasma and ion plating, or ink jet printing, nozzle printing, slot coating, spin coating, dip coating, and A wet film formation method such as a flow coating method can be used.

  When the wet film-forming method is used, a thin film can be formed by dissolving or diffusing the material forming each layer in any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, or the like. The solvent can be any solvent capable of dissolving or diffusing the material forming each layer and having no problem in film forming ability.

  In the organic electroluminescent device of the present disclosure, two or more host compounds for the light emitting layer may be co-evaporated or mixed-evaporated. In this specification, co-evaporation means that two or more materials are deposited as a mixture by introducing each of two or more materials into a respective crucible container and applying an electric current to the container for each material to be deposited. Process. In this specification, mixed vapor deposition refers to mixing two or more materials by mixing two or more materials in a crucible container before vapor deposition and applying an electric current to the container such that the mixture is vapor deposited. Means the process deposited as.

  By using the organic electroluminescent element of the present disclosure, a display system or a lighting system can be produced.

Hereinafter, the organic electroluminescent compound of the present disclosure, the method for preparing the compound, and the light emission characteristics of the device will be described in detail with reference to the following examples.

  Example 1: Preparation of compounds C-1 and C-3

Preparation of Compound 1-1 Compound 4-bromodibenzothiophene (50 g, 189.98 mmol), 2-methylthiophenylboronic acid (31.9 g, 189.89 mmol), tetrakis (triphenylphosphine) palladium (11 g, 9.499 mmol) , Sodium carbonate (60 g, 576.94 mmol), toluene (900 mL), ethanol (280 mL), and distilled water (280 mL) were introduced into the reaction vessel, and the mixture was stirred at 120 ° C. for 3 hours. After the reaction, the mixture was washed with distilled water and extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate, and the solvent was removed therefrom by a rotary evaporator. The product was purified by column chromatography to give compound 1-1 (58 g, 99%).

Preparation of Compound 1-2 After dissolving Compound 1-1 (58 g, 189.98 mmol) in tetrahydrofuran (THF) (500 mL) and acetic acid (580 mL), hydrogen peroxide (35%) (23 mL) was gradually added dropwise. Added to the mixture. The mixture was stirred at room temperature for 10 hours. After the reaction, the mixture was concentrated to remove the solvent, and extracted with dichloromethane and pure water. The remaining water was removed from the resulting organic layer using magnesium sulfate, then the organic layer was dried, concentrated and used directly in the next reaction.

Preparation of Compound 1-3 After dissolving Compound 1-2 (58 g) in trifluoromethanesulfonic acid (300 mL), the mixture was stirred at room temperature for 2 days, then pyridine (600 mL) / pure water (1.5 mL). Added dropwise to the solution. The mixture was heated and refluxed at 120 ° C. for 4 hours. After the reaction, the mixture was extracted with dichloromethane. The obtained organic layer was purified by column chromatography to obtain compound 1-3 (15.4 g, 28%).

Preparation of Compound 1-4 Compound 1-3 (15.4 g, 53.03 mmol) was dissolved in chloroform (550 mL), and then the mixture was cooled to 0 ° C. Bromine (2.7 mL, 53.03 mmol) was gradually added dropwise. After the reaction, the mixture was gradually heated to room temperature and stirred for 8 hours, after which bromine was removed from the mixture with sodium thiosulfate solution, the product was filtered and compound 1-4 (12.8 g, 65.4%) was obtained.

Preparation of Compound 1-5 Compound 1-4 (12.8 g, 34.66 mmol), chloroaniline (4.7 mL, 45.06 mmol), palladium acetate (0.31 g, 45.06 mmol), t-butylphosphine (50 %) (1.4 mL, 2.77 mmol) and sodium t-butoxide (8.3 g, 86.65 mmol) were introduced into toluene (170 mL) and the mixture was stirred at reflux for 1 day. After the reaction, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The obtained organic layer was distilled under reduced pressure and purified by column chromatography to obtain compound 1-5 (13.7 g, 77%).

Preparation of Compound 1-6 Compound 1-5 (13.7 g, 32.94 mmol), palladium acetate (0.4 g, 1.646 mmol), tricyclohexylphosphonium tetrafluoroborate (C ₁₈ H ₃₄ P.BF ₄ ) ( After introducing 1.21 g, 3.29 mmol), cesium carbonate (32.1 g, 98.82 mmol), and dimethylacetamide (DMA) (250 mL) into the reaction vessel, the mixture was stirred at 180 ° C. for 7 hours. After the reaction, the mixture was extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate, distilled under reduced pressure, and purified by column chromatography to obtain compound 1-6 (5.6 g, 45%).

Preparation of Compound C-1 Compound 1-6 (5 g, 13.17 mmol), Compound 1-7 (4.6 g, 15.81 mmol), Palladium acetate (1.2 g, 5.27 mmol), 50% t-butylphosphine (5 mL, 10.54 mmol) and cesium carbonate (13 g, 39.5 mmol) were dissolved in toluene (65 mL), and then the mixture was refluxed at 130 ° C. for 3 hours. After the reaction, the mixture was extracted with dichloromethane / pure water and purified by column chromatography to obtain compound C-1 (4.4 g, 57%).

  UV: 319 nm, PL: 525 nm, melting point: 261 ° C., MS / EIMS measured value 584; calculated value 583

Preparation of Compound C-3 Compound 1-6 (1.6 g, 4.21 mmol) and compound 1-8 (1.7 g, 6.32 mmol) were dissolved in dimethylformamide (DMF) (30 mL), and then NaH (0 0.5 g, 12.63 mmol, 60% in mineral oil) was added to the mixture. The mixture was stirred at room temperature for 12 hours and methanol and distilled water were added thereto. The obtained solid was filtered under reduced pressure and purified by column chromatography to obtain compound C-3 (1.4 g, 54%).

  UV: 342 nm, PL: 528 nm, melting point: 360 ° C., MS / EIMS measured value 611; calculated value 610

  Example 2: Preparation of compounds C-9 and C-11

Preparation of Compound 2-1 Compound 4-bromodibenzofuran (50 g, 202.35 mmol), 2-methylthiophenylboronic acid (34 g, 202.35 mmol), tetrakis (triphenylphosphine) palladium (11.7 g, 10.117 mmol), Sodium carbonate (64 g, 607.06 mmol), toluene (1000 mL), ethanol (300 mL), and distilled water (300 mL) were introduced into the reaction vessel, and then the mixture was stirred at 120 ° C. for 3 hours. After the reaction, the mixture was washed with distilled water and extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed therefrom by a rotary evaporator. The product was purified by column chromatography to give compound 2-1 (58 g, 99%).

Preparation of Compound 2-2 Compound 2-1 (58 g, 202.35 mmol) was dissolved in THF (580 mL) and acetic acid (580 mL), and then hydrogen peroxide (35%) (26 mL) was gradually added dropwise to the mixture. It was. The mixture was stirred at room temperature for 10 hours, concentrated to remove the solvent, and then extracted with dichloromethane and pure water. The remaining water was removed from the obtained organic layer using magnesium sulfate, concentrated, and used directly in the next reaction.

Preparation of Compound 2-3 Compound 2-2 was added thereto while stirring a solution of pyridine (600 mL) / pure water (1.5 mL). The mixture was then heated and refluxed at 120 ° C. for 4 hours. After the reaction, the mixture was extracted with dichloromethane, and the resulting organic layer was subjected to column chromatography to obtain compound 2-3 (48.6 g, 93%).

Preparation of Compound 2-4 After dissolving Compound 2-3 (43.6 g, 158.9 mmol) in chloroform (800 mL), the mixture was cooled to 0 ° C. Bromine (8.55 mL, 166.87 mmol) was slowly added dropwise to the mixture. After the addition, the mixture was gradually heated to room temperature and stirred for 8 hours. After the reaction, bromine was removed from the mixture using a sodium thiosulfate solution. The product was filtered to give compound 2-4 (44 g, 70%).

Preparation of Compound 2-5 Compound 2-4 (20 g, 56.62 mmol), chloroaniline (7.7 mL, 73.61 mmol), palladium acetate (0.5 g, 2.26 mmol), t-butylphosphine (50%) After introducing (2.2 mL, 4.53 mmol) and sodium t-butoxide (13.6 g, 141.55 mmol) into toluene (280 mL), the mixture was stirred at reflux for 1 day. After the reaction, the mixture was cooled to room temperature and extracted with distilled water and ethyl acetate. The obtained organic layer was distilled under reduced pressure and purified by column chromatography to obtain compound 2-5 (11 g, 48.6%).

Preparation of Compound 2-6 Compound 2-5 (11 g, 27.5 mmol), palladium acetate (0.3 g, 1.37 mmol), C ₁₈ H ₃₄ P.I. After introducing BF ₄ (1 g, 2.75 mmol), cesium carbonate (26 g, 82.5 mmol), and DMA (135 mL) into the reaction vessel, the mixture was stirred at 180 ° C. for 7 hours. After the reaction, the mixture was extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate, distilled under reduced pressure, and purified by column chromatography to obtain compound 2-6 (4 g, 40%).

Preparation of Compound C-9 Compound 2-6 (3.5 g, 9.63 mmol), Compound 1-7 (2.78 g, 11.55 mmol), Palladium acetate (0.86 g, 3.85 mmol), 50% t- After butylphosphine (3.7 mL, 7.704 mmol, and cesium carbonate (9.4 g, 28.8 mmol) were dissolved in toluene (100 mL), the mixture was refluxed for 3 hours at 130 ° C. After the reaction, the mixture was dichloromethane. / Extracted with pure water and purified by column chromatography to give compound C-9 (2.5 g, 46%).

  UV: 296 nm, PL: 535 nm, melting point: 290 ° C., MS / EIMS measured value 568; calculated value 567

Preparation of Compound C-11 Compound 2-6 (3 g, 8.2 mmol) and compound 1-8 (2.65 g, 9.9 mmol) were dissolved in dimethylformamide (DMF) (40 mL), and then NaH (1 g, 24 .76 mmol, 60% in mineral oil) was added to it. The mixture was stirred at room temperature for 12 hours and methanol and distilled water were added to the mixture. The obtained solid was filtered under reduced pressure and purified by column chromatography to obtain compound C-11 (3.1 g, 63%).

  UV: 342 nm, PL: 532 nm, melting point: 353 ° C., MS / EIMS measured value 595; calculated value 594

  Example 3: Preparation of compound C-15

Preparation of Compound 1-1 After introducing benzo [b] [1] benzocyano [2,3-g] benzofuran (30 g, 109 mmol) and chloroform (540 mL) into the flask, the mixture was cooled to 0 ° C. Bromine (5.8 mL, 114 mmol) was slowly added dropwise to the mixture. The mixture was then stirred for 3 hours. After the reaction, the mixture was extracted with ethyl acetate, dried over magnesium sulfate and distilled under reduced pressure. The product was separated from the mixture by column chromatography to obtain compound 1-1 (23 g, yield: 60%).

Preparation of Compound 1-2 Compound 1-1 (18 g, 52.1 mmol), 2-chloroaniline (8.2 mL, 78.1 mmol), palladium acetate (1.1 g, 5.21 mmol), tri-tert-butylphosphine (5 mL) (50%), 10.4 mmol), sodium tert-butoxide (15 g, 156 mmol), and toluene (260 mL) were introduced into the flask and the mixture was stirred at reflux for 4 hours. After the reaction, the mixture was extracted with methylene chloride (MC), dried over magnesium sulfate, and distilled under reduced pressure. The product was separated from the mixture by column chromatography to obtain compound 1-2 (18 g, yield: 90%).

Preparation of Compound 1-3 Compound 1-2 (18 g, 47.0 mmol), palladium acetate (1.0 g, 4.70 mmol), tricyclohexylphosphonium tetrafluoroborate (3.4 g, 9.40 mmol), cesium carbonate ( 46 g, 141 mmol), and dimethylacetamide (240 mL) were introduced into the flask and the mixture was stirred at reflux for 4 hours. After the reaction, the mixture was extracted with methylene chloride (MC), dried over magnesium sulfate, and distilled under reduced pressure. The product was separated from the mixture by column chromatography to obtain compound 1-3 (6.7 g, yield: 40%).

Preparation of Compound C-15 Compound 1-3 (3 g, 8.25 mmol) and Compound B (3.4 g, 10.7 mmol) were dissolved in dimethylformamide (DMF) (40 mL) in a flask, and then NaH (1 g, 24.76 mmol, 60% in mineral oil) was added to the mixture. The mixture was then stirred at room temperature for 12 hours and methanol and distilled water were added thereto. The obtained solid was filtered under reduced pressure and purified by column chromatography to obtain compound C-15 (3.6 g, 67%).

[table]

  Example 4: Preparation of compound C-101

Preparation of Compound 1-1 After introducing benzo [b] [1benzocyano [2,3-g] benzofuran (30 g, 109 mmol) and chloroform (540 mL) to the flask, the mixture was cooled to 0 ° C. Bromine (5.8 mL, 114 mmol) was slowly added dropwise to the mixture. The mixture was then stirred for 3 hours. After the reaction, the mixture was extracted with ethyl acetate. The obtained organic layer was dried over magnesium sulfate and distilled under reduced pressure. The product was separated from the mixture by column chromatography to obtain compound 1-1 (23 g, yield: 60%).

Preparation of Compound 1-2 Compound 1-1 (18 g, 52.1 mmol), 2-chloroaniline (8.2 mL, 78.1 mmol), palladium acetate (1.1 g, 5.21 mmol), tri-tert-butylphosphine (5 mL) (50%), 10.4 mmol), sodium tert-butoxide (15 g, 156 mmol) and toluene (260 mL) were introduced into the flask and the mixture was stirred at reflux for 4 hours. After the reaction, the mixture was extracted with methylene chloride (MC), dried over magnesium sulfate, and distilled under reduced pressure. The product was separated from the mixture by column chromatography to obtain compound 1-2 (18 g, yield: 90%).

Preparation of Compound 1-3 Compound 1-2 (18 g, 47.0 mmol), palladium acetate (1.0 g, 4.70 mmol), tricyclohexylphosphonium tetrafluoroborate (3.4 g, 9.40 mmol), cesium carbonate ( 46 g, 141 mmol), and dimethylacetamide (240 mL) were introduced into the flask and the mixture was stirred at reflux for 4 hours. After the reaction, the mixture was extracted with methylene chloride (MC), dried over magnesium sulfate and then distilled under reduced pressure. The product was separated from the mixture by column chromatography to obtain compound 1-3 (6.7 g, yield: 40%).

Preparation of Compound C-101 Compound 1-3 (6.7 g, 18.4 mmol), 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine (7.8 g, 20.2 mmol) ), Tris (dibenzylindeneacetone) dipalladium (0.8 g, 0.92 mmol), tri-tert-butylphosphine (0.9 mL) (50%), 1.84 mmol), sodium tert-butoxide (4.4 g) 46.1 mmol), and toluene (100 mL) were introduced into the flask and the mixture was stirred at reflux for 3 hours. After the reaction, the mixture was extracted with methylene chloride (MC), dried over magnesium sulfate, and distilled under reduced pressure. The product was separated from the mixture by column chromatography to obtain compound C-101 (8.3 g, yield: 67%).

[table]

[Device Example 1] OLED using the compound of the present disclosure
An OLED was fabricated using the organic electroluminescent compound of the present disclosure as follows. Ultrasonic cleaning of indium tin oxide (ITO) thin film (15Ω / sq) (Geomatec) for transparent electrode on glass substrate of organic light emitting diode (OLED) using trichlorethylene, acetone, ethanol and distilled water sequentially And stored in isopropanol. Next, the ITO substrate was mounted on the substrate holder of the vacuum evaporation apparatus. ^{N 1, N 1 '- (} [1,1'- biphenyl] -4,4'-diyl) bis ^{(N 1} - ^{(naphthalen-1-yl)} -N ^{4, N} 4 - diphenyl-1,4 Diamine) was introduced into the cell of the vacuum deposition apparatus, and then the pressure in the chamber of the apparatus was adjusted to 10 ⁻⁶ Torr. Thereafter, an electric current was applied to the cell to deposit the introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. Next, N, N′-di (4-biphenyl) -N, N′-di (4-biphenyl) -4,4′-diaminobiphenyl is introduced into another cell of the vacuum deposition apparatus, and the current flows through the cell. To form a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, compound C-1 was introduced as a host into one cell of the vacuum deposition apparatus, and compound D-87 was introduced as a dopant into another cell. By depositing the two materials in different ratios, the dopant was deposited with a doping amount of 4 wt% based on the total amount of host and dopant, and a light emitting layer having a thickness of 30 nm was formed on the hole transport layer. Then, 2- (4- (9,10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole was introduced into one cell and lithium The quinolate was introduced into another cell. By depositing the two materials in the same ratio, they were each deposited with a doping amount of 50 wt%, and an electron transport layer having a thickness of 30 nm was formed on the light emitting layer. After doping lithium quinolate on the electron transport layer as an electron injection layer having a thickness of 2 nm, an Al cathode having a thickness of 150 nm was then deposited on the electron injection layer by another vacuum deposition apparatus. In this way, an OLED was produced. All materials used to make OLEDs were purified by vacuum sublimation at ^10-6 torr. The fabricated OLED showed red emission having a luminance of 1,050 cd / m ² and a current density of 8.1 mA / cm ² at a driving voltage of 3.6V. The shortest time required for the luminance of 5,000 nits to decrease to 90% was 200 hours.

[Comparative Example 1]
OLED using conventional organic electroluminescence compound

An OLED was produced in the same manner as in Example 1 of the device except that Compound A-1 and Compound D-88 shown below were used as a host and a dopant. The fabricated OLED showed red emission with a luminance of 980 cd / m ² and a current density of 16.4 mA / cm ² at a driving voltage of 3.8V. The shortest time taken for the brightness of 5,000 nits to drop to 90% was 12 hours.

[Comparative Example 2]
OLED using conventional organic electroluminescence compound

An OLED was produced in the same manner as in Example 1 of the device except that Compound A-2 and Compound D-88 shown below were used as a host and a dopant. The fabricated OLED showed red emission with a luminance of 1,020 cd / m ² and a current density of 13.1 mA / cm ² at a driving voltage of 4.1V. The shortest time required for the brightness of 5,000 nits to drop to 90% was 10 hours.

[Comparative Example 3]
OLED using conventional organic electroluminescence compound

An OLED was produced in the same manner as in Example 1 of the device except that Compound A-3 and Compound D-87 shown below were used as a host and a dopant. The fabricated OLED showed red emission with a luminance of 1,110 cd / m ² and a current density of 9.8 mA / cm ² at a driving voltage of 4.2V. The shortest time required for the brightness of 5,000 nits to drop to 90% was 10 hours.

  As confirmed above, the organic electroluminescent compounds of the present disclosure provide lower drive voltages, longer lifetimes, and better luminous efficiencies compared to conventional organic electroluminescent compounds. An organic electroluminescent device using the organic electroluminescent compound of the present disclosure exhibits superiority in driving voltage, lifetime, and emission characteristics, particularly current efficiency and power efficiency.

[Element Examples 1-1 to 1-7]
OLEDs made by using co-evaporation of a first host compound and a second host compound of the present disclosure

An OLED was fabricated using the light emitting material of the present disclosure as follows. Ultrasonic cleaning of indium tin oxide (ITO) thin film (10Ω / sq) (Geomatec) for transparent electrode on glass substrate of organic light emitting diode (OLED) using trichlorethylene, acetone, ethanol and distilled water sequentially And stored in isopropanol. Next, the ITO substrate was mounted on the substrate holder of the vacuum evaporation apparatus. N ⁴ , N ^{4 ′} -diphenyl-N ⁴ , N ^{4 ′} -bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl] -4,4′-diamine (HI-1 ) Was introduced into the cell of the vacuum deposition apparatus, and then the pressure in the chamber of the apparatus was adjusted to 10 ⁻⁶ Torr. Thereafter, an electric current was applied to the cell to deposit the introduced material, thereby forming a hole injection layer having a thickness of 80 nm on the ITO substrate. Then, 1,4,5,8,9,12-hexaazatriphenylene-hexacarbonitrile (HI-2) is introduced into another cell of the vacuum deposition apparatus and evaporated by applying an electric current to the cell, Thereby, a second hole injection layer having a thickness of 5 nm was formed on the first hole injection layer. N-([1,1′-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carbazole-3-yl) in one cell of the vacuum deposition apparatus Phenyl) -9H-fluoren-2-amine (HT-1) is introduced and deposited by applying a current to the cell, thereby having a first thickness of 10 nm on the second hole injection layer. A hole transport layer was formed. N, N-di ([1,1′-biphenyl] -4-yl) -4 ′-(9H-carbazol-9-yl)-[1,1′-biphenyl] -4-amine (HT—) 2) is introduced into another cell of the vacuum deposition apparatus and deposited by applying an electric current to the cell, whereby a second hole transport layer having a thickness of 60 nm on the first hole transport layer Formed. As host materials, the two compounds shown in Table 1 below were introduced into the two cells of the vacuum deposition apparatus as a first host compound and a second host compound, respectively. The dopant compounds shown in Table 1 were introduced into another cell. By depositing the two host compounds in the same ratio of 1: 1 while depositing the dopant in a different ratio than the host compound, the dopant is deposited in a doping amount of 3 wt% based on the total amount of the host and dopant, A light emitting layer having a thickness of 40 nm was formed on the hole transport layer. 2,4-bis (9,9-dimethyl-9H-fluorene-2-yl) -6- (naphthalene-2-yl) -1,3,5-triazine (ET-1) and lithium quinolate (EI- 1) was introduced into each of the two cells of the vacuum deposition apparatus and deposited at the same ratio of 1: 1, thereby forming an electron transport layer having a thickness of 30 nm on the light emitting layer. After doping lithium quinolate (EI-1) on the electron transport layer as an electron injection layer having a thickness of 2 nm, an Al cathode having a thickness of 80 nm is then deposited on the electron injection layer by another vacuum deposition apparatus. Vapor deposited.

[Comparative Examples 1-1 to 1-4]
OLED using a second host compound as a single host

  OLEDs were fabricated in the same manner as in Examples 1-1 to 1-7 of the device, except that only the second host compound shown in Table 1 below was used as the host of the light emitting layer.

[Comparative Examples 2-1 to 2-2]
OLED using the first host compound as a single host

  OLEDs were fabricated in the same manner as in Examples 1-1 to 1-7 of the device, except that only the first host compound shown in Table 1 below was used as the host of the light emitting layer.

  Table 1 below shows the characteristics of the organic electroluminescence elements prepared in Examples 1-1 to 1-7, Comparative Examples 1-1 to 1-4, and Comparative Examples 2-1 to 2-2. .

[table]

  When the devices of Comparative Examples 1-1 to 1-4 are compared with the devices of Comparative Examples 2-2 to 2-2, the organic electroluminescent device using one organic electroluminescent compound of the present disclosure as a host material has a driving voltage. Showed improvement in current efficiency, color purity, and lifetime. However, when Examples 1-1 to 1-7 of the device are compared with Comparative Examples 1-1 to 1-4, 2-1, and 2-2, the organic electroluminescent device is an organic electroluminescent compound of the present disclosure. By using a multi-component host material containing, it has shown superior performance, especially in the lifetime of the organic electroluminescent device. That is, an organic electroluminescence device using a multi-component host material can exhibit a longer lifetime than a device using one host compound.

Claims (9)

An organic electroluminescent compound represented by the following formula 1,

Wherein Ar ₁ represents substituted or unsubstituted (3 to 30 membered) heteroaryl, or substituted or unsubstituted (C6-C30) aryl;
L ₁ represents a single bond, substituted or unsubstituted (C6-C30) arylene, or substituted or unsubstituted (3 to 30 membered) heteroarylene;
Ring A is

Ring B is

Represents;
Y represents O, S, N (R ₆ ), or C (R ₄ ) (R ₅ ); X represents O, S, N (R ₆ ), or C (R ₇ ) (R ₈ ) Provided that X and Y cannot both be N (R ₆ ) at the same time;
R _{1 to} R ₃ are each independently hydrogen, deuterium, halogen, cyano, carboxy, nitro, hydroxy, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C3-C30) cyclo. Alkyl, substituted or unsubstituted (C3-C30) cycloalkenyl, substituted or unsubstituted (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3- 30 membered) representing a heteroaryl, -NR ₉ R ₁₀ , or -SiR ₁₁ R ₁₂ R ₁₃ , or bonded to adjacent substituent (s) to form a substituted or unsubstituted (C3-C30), May form monocyclic or polycyclic alicyclic or aromatic rings;
R _{4 to} R ₁₃ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3 ˜30 membered heteroaryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (5-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl (C1-C30) ) Represents alkyl, -NR < ₁₄ > R < ₁₅ >, -SiR < ₁₆ > R < ₁₇ > R < ₁₈ >, cyano, nitro, or hydroxy, or is combined with adjacent substituent (s) to give substituted or unsubstituted (C3-C30 ) May form monocyclic or polycyclic alicyclic or aromatic rings;
R _{14 to} R ₁₈ have the same definition as R _{4 to} R ₁₃ ;
The carbon atom (s) of the alicyclic or aromatic ring may be replaced with at least one heteroatom selected from nitrogen, oxygen, and sulfur;
Said heteroaryl (heteroarylene) and heterocycloalkyl contain at least one heteroatom selected from B, N, O, S, P (= O), Si, and P;
a, b, and c each independently represent an integer of 1 to 4; a, b, or c represents an integer of 2 or more, and each of R ₁ , R ₂ , or R ₃ is the same Or may be different;
However, the compound of the above formula 1 is represented by the following formula 2, and the ring that may be formed between any one of R _{1 to} R _{3 and} the adjacent substituent (s) is: The organic electroluminescent compound, which is not a substituted naphthalene ring.

The compound of formula 1 is represented by the following formulas

(Wherein Ar ₁ , L ₁ , X, Y, R _{1 to} R ₃ , a, b, and c are as defined in claim 1), Item 2. The organic electroluminescent compound according to Item 1. Ar ₁ represents substituted or unsubstituted (5-20 membered) heteroaryl or substituted or unsubstituted (C6-C20) aryl;
L ₁ represents a single bond, a substituted or unsubstituted (C6-C20) arylene, or a substituted or unsubstituted (5-20 membered) heteroarylene;
R _{1 to} R ₃ are each independently hydrogen, deuterium, substituted or unsubstituted (C1-C20) alkyl, substituted or unsubstituted (C3-C20) cycloalkyl, substituted or unsubstituted (C6- C30) represents aryl, substituted or unsubstituted (3-30 membered) heteroaryl, —NR ₉ R ₁₀ , or —SiR ₁₁ R ₁₂ R ₁₃ , or combined with adjacent substituent (s); The said organic electroluminescent compound of Claim 1 which may form the monocyclic or polycyclic alicyclic ring or aromatic ring of (C3-C20). The compound of formula 1 is

The organic electroluminescent compound according to claim 1, selected from the group consisting of:   The organic electroluminescent element containing the said organic electroluminescent compound of Claim 1.   An organic electroluminescent device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises one or more light emitting layers; at least one light emitting layer is 2. The organic electroluminescent compound represented by Formula 1 of claim 1, comprising one or more dopant compounds and two or more host compounds; wherein the first host compound of the two or more host compounds is The organic electroluminescence element. The first host compound of the two or more host compounds is the organic electroluminescent compound represented by Formula 1, and the second host compound is represented by the following Formulas 6 to 10:

(Where Cz represents the following structure:

L ₄ represents a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (5-30 membered) heteroarylene;
M represents substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (5-30 membered) heteroaryl;
Y ₁ and Y ₂ each independently represent —O—, —S—, —N (R ₃₁ ) —, or —C (R ₃₂ ) (R ₃₃ ) —, provided that Y ₁ and Y both ₂ and shall not be present at the same time;
X represents O or S;
R _{21 to} R ₂₄ are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted. of (C6-C30) aryl, substituted or unsubstituted (5-30 membered) heteroaryl, or _R 25 _R 26 _R 27 Si- or alkyl; bonded to or adjacent substituents (s), its A monocyclic or polycyclic alicyclic or aromatic ring of (C3-C30), wherein the carbon atom (s) may be replaced by at least one heteroatom selected from nitrogen, oxygen and sulfur However, when h of formula 6 or i of formula 7 is 1, R ₂₃ or R ₂₄ does not form a ring containing Y ₁ or Y ₂ of formulas 8 and 9 , R in formula 10 ₂₂ shall not form an indole ring linked to R ₂₁ of formulas 8 and 9;
R _{25 to} R ₂₇ each independently represent a substituted or unsubstituted (C1-C30) alkyl, or a substituted or unsubstituted (C6-C30) aryl;
R _{31 to} R ₃₃ are each independently hydrogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (5 to 30 members). Represents heteroaryl; or in combination with adjacent substituent (s), the carbon atom (s) may be replaced with at least one heteroatom selected from nitrogen, oxygen, and sulfur; May form a monocyclic or polycyclic alicyclic or aromatic ring of (C5-C30); R ₃₂ and R ₃₃ may be the same or different;
Said heteroaryl (heteroarylene) contains at least one heteroatom selected from B, N, O, S, P (= O), Si, and P;
h and i each independently represent an integer of 1 to 3; j, k, l, and m each independently represent an integer of 0 to 4; h, i, j, k, l Or each of (Cz-L ₄ ), each of (Cz), each of R ₂₁ , each of R ₂₂ , each of R ₂₃ , or each of R ₂₄ is the same when m is an integer of 2 or more The organic electroluminescent device according to claim 6, wherein the organic electroluminescent device is selected from compounds represented by: The second host compound has the following formula 11

Wherein A ₁ and A ₂ each independently represent a substituted or unsubstituted (C 6 -C 30) aryl; provided that the substituents of the substituted groups of A ₁ and A ₂ are nitrogen-containing Shall not be heteroaryl;
L ₂ represents a single bond or a substituted or unsubstituted (C6-C30) arylene;
Z _{1 to} Z ₁₆ are each independently hydrogen, deuterium, halogen, cyano, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted. (C2-C30) alkynyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C6-C60) aryl, substituted or unsubstituted (3-30 membered) heteroaryl, substituted or unsubstituted Of tri (C1-C30) alkylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl, substituted or unsubstituted ( C1-C30) alkyldi (C6-C30) arylsilyl, or substituted or unsubstituted mono or di C6-C30) represents arylamino; or substituted or unsubstituted (C3-C30) monocyclic or polycyclic alicyclic ring or aromatic in combination with adjacent substituent (s) The organic electroluminescence device according to claim 7, which may be formed by a ring. Said compounds represented by formulas 6-10 are:

The said organic electroluminescent element of Claim 7 selected from the group which consists of (In formula, TPS represents a triphenylsilyl).