阅读说明：本技术 邻位取代热激活延迟荧光材料以及包括此的有机发光元件 (Ortho-substituted thermally activated delayed fluorescence material and organic light emitting device including the same ) 是由 李七源 孔明宣 车在领 于 2015-11-25 设计创作，主要内容包括：本发明提供一种热激活延迟荧光材料。热激活延迟荧光材料具有供电子基(Electron Donating Group)与吸电子基(Electron Withdrawing Group)连接于苯,且吸电子基相对于供电子基邻接(邻位)而连接的形状。(The invention provides a thermally activated delayed fluorescence material. The thermally activated delayed fluorescence material has a shape in which an Electron Donating Group (Electron Donating Group) and an Electron Withdrawing Group (Electron Withdrawing Group) are connected to benzene, and the Electron Withdrawing Group is connected adjacent to (ortho to) the Electron Donating Group.)

1. A luminescent material, characterized in that,

represented by any one of the following chemical formula 2 and chemical formula 3,

[ chemical formula 2]

[ chemical formula 3]

In the chemical formulas 2 and 3,

R₁to R₆Independently of one another, C1-C9 alkyl, C5-C30 cycloalkyl, C6-C30 aryl, C6-C30 alkylaryl, C6-C30 arylalkyl or C3-C30 heteroaryl; r₁And R₂、R₃And R₄、R₅And R₆Optionally taken together with the nitrogen to which they are attached to form a substituted or unsubstituted heterocyclyl or substituted or unsubstituted heteroaryl;

R₁₇to R₁₉Independently of one another, cyano, substituted or unsubstituted C1-C9 alkyl, substituted or unsubstituted C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 alkylaryl, substituted or unsubstituted C6-C30 arylalkyl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 aryloxy, C1-C9 alkylsilyl or substituted or unsubstituted-NR_aR_b；

The R is_aAnd R_bIndependently of one another, hydrogen, deuterium, substituted or unsubstituted C1-C9 alkyl, substituted or unsubstituted C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aralkyl or substituted or unsubstituted C3-C30 heteroaryl, R_aAnd R_bOptionally taken together with the nitrogen to which they are attached to form a substituted or unsubstituted heterocyclyl or substituted or unsubstituted heteroaryl;

R₂₂to R₃₃Independently of one another, hydrogen, deuterium, halogen, substituted or unsubstituted C4-C6 aryl or substituted or unsubstituted C1-C3 alkyl.

2. The luminescent material according to claim 1,

the compound represented by the chemical formula 2 is represented by the following chemical formula 5,

[ chemical formula 5]

In the chemical formula 5, R₁、R₂And R₂₂To R₂₅As defined in said chemical formula 2,

Sub₅and Sub₆Independently of one another, hydrogen, deuterium, halogen, cyano, C1-C9 alkyl, C6-Aryl of C30, heteroaryl of C3-C30, alkoxy of C1-C9, -NR_eR_fSilyl, phosphino, phosphinoxy, thiol, sulfoxide, sulfone, arylthio of C5-C30, aryloxy of C5-C30, arylamino of C5-C30, or aralkyl of C5-C30; sub₅And Sub₆Fused to a host to which they are bound, optionally and independently of one another, to form a substituted or unsubstituted cyclic group or a substituted or unsubstituted aryl group;

the R is_eAnd R_fIndependently of one another, C1-C9 alkyl, C5-C30 cycloalkyl, C6-C30 aryl, C6-C30 alkylaryl, C6-C30 arylalkyl or substituted or unsubstituted C3-C30 heteroaryl; the R is_eAnd R_fOptionally in combination with the nitrogen to which they are attached, to form a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heteroaryl group.

3. The luminescent material according to claim 2,

in the chemical formula 5, the first and second organic solvents,

the-NR₁R₂Is any one of structural formulas A6, A8, A9 and A10,

in the structural formula A6, A8, A9 or A10,

Sub₁and Sub₂Independently of one another, hydrogen, deuterium, halogen, cyano, alkyl of C1 to C9, cycloalkyl of C5 to C30, aryl of C6 to C30, alkylaryl of C6 to C30, heteroaryl of C3 to C30, alkoxy of C1 to C9, -NR_cR_dSilyl, phosphino, phosphinoxy, thiol, sulfoxide, sulfone, arylsilyl of C5-C30, arylthio of C5-C30, aryloxy of C5-C30, arylamino of C5-C30, or arylalkyl of C5-C30; sub₁To Sub₂Independently of each other and selectively fused to the body to which they are bound to form a substituted or unsubstituted cyclic group or to be substitutedAn aryl group which is substituted or unsubstituted,

the R is_cAnd R_dIndependently of one another, C1-C9 alkyl, C5-C30 cycloalkyl, C6-C30 aryl, C6-C30 aralkyl, or substituted or unsubstituted C3-C30 heteroaryl; r_cAnd R_dOptionally in combination with the nitrogen to which they are attached to form a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heteroaryl group,

R₁₁and R₁₂Independently of one another, hydrogen, deuterium, substituted or unsubstituted C1-C2 alkyl, or substituted or unsubstituted C6-C30 aryl.

4. The luminescent material according to claim 1,

the compound represented by the chemical formula 3 is represented by the following chemical formula 6,

[ chemical formula 6]

In the chemical formula 6, R₃、R₄、R₅、R₆、R₂₆To R₂₉And R₃₀To R₃₃As defined in said chemical formula 3,

Sub₅is hydrogen, deuterium, halogen, cyano, C1-C9 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, C1-C9 alkoxy, -NR_eR_fA silyl group, a phosphino group, a phosphinoxy group, a thiol group, a sulfoxide group, a sulfone group, an arylthio group of C5-C30, an aryloxy group of C5-C30, an arylamino group of C5-C30, or an aralkyl group of C5-C30; sub₅Optionally fused to a body to which they are bound to form a substituted or unsubstituted cyclic group or a substituted or unsubstituted aryl group;

the R is_eAnd R_fIndependently of one another, C1-C9 alkyl, C5-C30 cycloalkyl, substituted or unsubstitutedC6-C30 aryl, C6-C30 alkaryl, C6-C30 aralkyl, or substituted or unsubstituted C3-C30 heteroaryl; the R is_eAnd R_fOptionally in combination with the nitrogen to which they are attached, to form a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heteroaryl group.

5. The luminescent material according to claim 4,

in the chemical formula 6, the first and second organic solvents,

the NR is₃R₄And NR₅R₆Independently of one another, of the formulae A6, A8, A9 or A10,

in the structural formula A6, A8, A9 or A10,

Sub₁and Sub₂Independently of one another, hydrogen, deuterium, halogen, cyano, C1-C9 alkyl, substituted or unsubstituted C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, C6-C30 alkylaryl, substituted or unsubstituted C3-C30 heteroaryl, C1-C9 alkoxy, -NR 9_cR_dSilyl, phosphino, phosphinoxy, thiol, sulfoxide, sulfone, arylsilyl of C5-C30, arylthio of C5-C30, aryloxy of C5-C30, arylamino of C5-C30, or arylalkyl of C5-C30; sub₁And Sub₂Independently of each other and optionally fused to the body to which they are attached to form a substituted or unsubstituted cyclic group or a substituted or unsubstituted aryl group;

the R is_cAnd R_dIndependently of one another, is C1-C9 alkyl, C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, C6-C30 aralkyl, or substituted or unsubstituted C3-C30 heteroaryl; r_cAnd R_dOptionally combined with the nitrogen to which they are attached to form a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heterocyclic group(ii) a substituted heteroaryl group, wherein,

R₁₁and R₁₂Independently of one another, hydrogen, deuterium, substituted or unsubstituted C1-C2 alkyl, or substituted or unsubstituted C6-C30 aryl.

6. The luminescent material according to claim 1,

the compound represented by the chemical formula 2 is any one of the following chemical formulas 7 to 10,

[ chemical formula 7]

[ chemical formula 8]

[ chemical formula 9]

[ chemical formula 10]

In the chemical formulae 7 to 10,

R₁₇、R₁₈and R₂₂To R₂₅As defined in said chemical formula 2,

wherein R is₁₇And R₁₈At least one of structural formulae a6, A8, a9, a10, a20, a21, a24, or a 28:

in chemical formulas 7 to 10, structural formulas A6, A8, A9, A10, A20, A21, A24 and A28,

Sub₁and Sub₂Independently of one another, hydrogen, deuterium, halogen, cyano, C1-C9 alkyl, C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, C6-C30 alkylaryl, substituted or unsubstituted C3-C30 heteroaryl, C1-C9 alkoxy, -NR_cR_dSilyl, phosphino, phosphinoxy, thiol, sulfoxide, sulfone, arylsilyl of C5-C30, arylthio of C5-C30, aryloxy of C5-C30, arylamino of C5-C30, or arylalkyl of C5-C30; sub₁To Sub₂Independently of each other and optionally fused to the body to which they are attached to form a substituted or unsubstituted cyclic group or a substituted or unsubstituted aryl group,

the R is_cAnd R_dIndependently of one another, is C1-C9 alkyl, C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, C6-C30 aralkyl, or substituted or unsubstituted C3-C30 heteroaryl; r_cAnd R_dOptionally in combination with the nitrogen to which they are attached to form a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heteroaryl group,

Sub₃is hydrogen, deuterium, a halogen group, a cyano group, an alkyl group of C1-C9, a cycloalkyl group of C5-C30, a substituted or unsubstituted aryl group of C6-C30, an alkylaryl group of C6-C30, an arylalkyl group of C6-C30, a substituted or unsubstituted heteroaryl group of C3-C30, an alkoxy group of C1-C9, an aryloxy group of C6-C30, a silane group, a phosphine group, a phosphino group, a thiol group, a sulfoxide group, or a sulfone group,

R₁₁and R₁₂Independently of one another, hydrogen, deuterium, substituted or unsubstituted C1-C2 alkyl, or substituted or unsubstituted C6-C30 aryl.

7. The luminescent material according to claim 1,

the compound represented by said chemical formula 3 is represented by the following chemical formula 11,

[ chemical formula 11]

In the chemical formula 11, the first and second organic solvents,

R₁₉and R₂₆To R₃₃As defined in said chemical formula 3,

Sub₁and Sub₂Independently of one another, hydrogen, deuterium, halogen, cyano, C1-C9 alkyl, C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, C6-C30 alkylaryl, substituted or unsubstituted C3-C30 heteroaryl, C1-C9 alkoxy, -NR_cR_dSilyl, phosphino, phosphinoxy, thiol, sulfoxide, sulfone, arylsilyl of C5-C30, arylthio of C5-C30, aryloxy of C5-C30, arylamino of C5-C30, or arylalkyl of C5-C30; sub₁And Sub₂Independently of each other and optionally fused to the body to which they are attached to form a substituted or unsubstituted cyclic group or a substituted or unsubstituted aryl group,

the R is_cAnd R_dIndependently of one another, is C1-C9 alkyl, C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, C6-C30 aralkyl, or substituted or unsubstituted C3-C30 heteroaryl; r_cAnd R_dOptionally in combination with the nitrogen to which they are attached, to form a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heteroaryl group.

8. The luminescent material according to claim 1,

the luminescent material represented by the chemical formula 2 is any one of the following compounds 1 to 66,

9. the luminescent material according to claim 1,

the luminescent material represented by the chemical formula 3 is any one of the following compounds 67 to 82,

10. the luminescent material according to claim 1,

in the chemical formulas 2 and 3, -NR₁R₂、-NR₃R₄、-NR₅R₆Independently of one another, are any of the following formulae A1 to A45,

in the structural formulae a1 to a45,

R₁₁to R₁₄Independently of one another, hydrogen, deuterium, substituted or unsubstitutedA substituted C1-C2 alkyl group or a substituted or unsubstituted C6-C30 aryl group,

Sub₁to Sub₄Independently of one another, hydrogen, deuterium, halogen, cyano, C1-C9 alkyl, C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, C6-C30 alkylaryl, C6-C30 arylalkyl, substituted or unsubstituted C3-C30 heteroaryl, C1-C9 alkoxy, C6-C30 aryloxy, silyl, phosphino, phosphinoxy, thiol, sulfoxide, or sulfone.

11. The luminescent material according to claim 1,

in the chemical formula 2, the triazinyl group is any one of the following structural formulae B1 to B27,

in the structural formulae B1 to B27,

R₁₁and R₁₂Independently of one another, hydrogen, deuterium or a substituted or unsubstituted C1-C2 alkyl group,

Sub₅and Sub₆Independently of one another, hydrogen, deuterium, halogen, cyano, C1-C9 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, C1-C9 alkoxy, silyl, phosphino, phosphinyloxy, thiol, sulfoxide, sulfone, C5-C30 arylthio, C5-C30 aryloxy, C5-C30 arylamine, or C5-C30 aralkyl; sub₅And Sub₆Optionally fused independently of each other to the body to which they are attached to form a substituted or unsubstituted cyclic group or a substituted or unsubstituted aryl group.

12. The luminescent material according to claim 1,

in the chemical formula 3, the triazinyl group is any one of the following structural formulae B28 to B49,

in the structural formulae B28 to B49,

R₁₁and R₁₂Independently of one another, hydrogen, deuterium or a substituted or unsubstituted C1-C2 alkyl group.

13. An organic light emitting diode comprises an anode, a hole conduction layer, a light emitting layer, an electron conduction layer and a cathode which are sequentially laminated,

any one of the hole-conducting layer, the light-emitting layer and the electron-conducting layer comprises the compound according to claim 1.

14. The organic light-emitting diode of claim 13,

the light-emitting layer includes a host material and a dopant material,

the dopant species comprises the compound of claim 1.

15. The organic light-emitting diode of claim 14,

the doping substance is a delayed fluorescence emitting substance.

Technical Field

The present invention relates to a compound for an organic light emitting diode, and more particularly, to a thermally activated delayed fluorescence material as a compound for an organic light emitting diode.

Background

An organic light emitting diode (organic light emitting device) is a self-luminous element, and has advantages of wide viewing angle, excellent contrast, short response time, excellent characteristics such as luminance, driving voltage, and response speed, and multi-color.

A typical organic light emitting diode may include an anode and a cathode and an organic layer interposed between the anode and the cathode. The organic layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. When a voltage is applied between the anode and the cathode, holes injected from the anode move to the light-emitting layer via the hole transport layer, and electrons injected from the cathode move to the light-emitting layer via the electron transport layer. As described above, the hole and electron carriers recombine in the light emitting layer region to generate excitons (exiton), which generate light while changing to a ground state.

In general, excitons (exiton) generated when an organic light emitting diode is driven are generated with a probability of 25% of a singlet state and 75% of a triplet state, and in the case of a fluorescent light emitting material, light is generated only by 25% of the excitons in the singlet state, and thus the internal quantum efficiency is at a level of at most 25%. In order to improve such characteristics, it is widely known to use iridium or platinum complexes capable of utilizing triplet energy while retaining excellent quantum efficiency characteristics. However, the price of such materials is high, and especially, the application thereof is limited due to the instability of the blue light emitting material.

To solve such a problem, a thermally activated delayed fluorescence organic material has recently been developed. In such a thermally activated delayed fluorescence organic material, the difference between the singlet state and the triplet state of the exciton is 0.3eV or less, and in this case, the triplet state is transferred to the singlet state by heat corresponding to normal temperature or element driving temperature, and it is considered theoretically that the quantum efficiency of 100% can be expressed.

Disclosure of Invention

Technical problem

However, it is well known that the actual quantum efficiency of the thermally activated delayed fluorescence organic materials developed so far is very different from the theoretical quantum efficiency, and thus improvement is still required.

An object of the present invention is to provide a thermally activated delayed fluorescence material that can more efficiently transfer from a triplet state to a singlet state, and thus can improve the actual quantum efficiency, and an organic light-emitting element including the fluorescence material.

Technical scheme

To accomplish the above object, an aspect of the present invention provides a thermally activated delayed fluorescence material. The thermally activated delayed fluorescence material has a shape in which an Electron Donating Group (Electron Donating Group) and an Electron Withdrawing Group (Electron Withdrawing Group) are connected to benzene, and the Electron Withdrawing Group and the Electron Donating Group are connected adjacent to each other (ortho position).

The present invention provides a luminescent material represented by the following chemical formula 1:

[ chemical formula 1]

In the chemical formula 1, R_EDGIs an electron-donating group, R_EWGIs an electron-withdrawing group, R₅To R₈Independently of one another, hydrogen, deuterium, halogen, substituted or unsubstituted C4-C6 aryl or substituted or unsubstituted C1-C3 alkyl.

According to an embodiment of the present invention, the luminescent material represented by the chemical formula 1 is represented by any one of the following chemical formulas 2 to 4,

[ chemical formula 2]

[ chemical formula 3]

[ chemical formula 4]

In the chemical formulas 2 to 4, R₁To R₁₂Independently of one another, substituted or unsubstituted C1-C9 alkyl, substitutedOr unsubstituted C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 alkaryl, substituted or unsubstituted C6-C30 aralkyl, or substituted or unsubstituted C3-C30 heteroaryl; r₁And R₂、R₃And R₄、R₅And R₆、R₇And R₈、R₉And R₁₀Or R₁₁And R₁₂Optionally taken together with the nitrogen to which they are attached to form a substituted or unsubstituted heterocyclyl or substituted or unsubstituted heteroaryl; r₁₇To R₁₉Independently of one another, cyano, substituted or unsubstituted C1-C9 alkyl, substituted or unsubstituted C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 alkylaryl, substituted or unsubstituted C6-C30 arylalkyl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-C30 aryloxy, C1-C9 alkylsilyl or substituted or unsubstituted-NR_aR_b(ii) a The R is_aAnd R_bIndependently of one another, hydrogen, deuterium, substituted or unsubstituted C1-C9 alkyl, substituted or unsubstituted C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aralkyl or substituted or unsubstituted C3-C30 heteroaryl, R_aAnd R_bOptionally taken together with the nitrogen to which they are attached to form a substituted or unsubstituted heterocyclyl or substituted or unsubstituted heteroaryl; r₂₂To R₄₅Independently of one another, hydrogen, deuterium, halogen, substituted or unsubstituted C4-C6 aryl or substituted or unsubstituted C1-C3 alkyl.

According to an embodiment of the present invention, the compound represented by the chemical formula 2 is represented by the following chemical formula 5,

[ chemical formula 5]

In the chemical formula 5, R₁、R₂And R₂₂To R₂₅Same as defined in said chemical formula 2, Sub₅And Sub₆Independently of one another, hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl of C1-C9, substituted or unsubstituted aryl of C6-C30, substituted or unsubstituted heteroaryl of C3-C30, substituted or unsubstituted alkoxy of C1-C9, substituted or unsubstituted-NR_eR_fSubstituted or unsubstituted silyl, substituted or unsubstituted phosphino, substituted or unsubstituted phosphinoxy, substituted or unsubstituted thiol, substituted or unsubstituted sulfoxide, substituted or unsubstituted sulfone, substituted or unsubstituted arylthio of C5-C30, substituted or unsubstituted aryloxy of C5-C30, substituted or unsubstituted arylamino of C5-C30, or substituted or unsubstituted aralkyl of C5-C30; sub₅And Sub₆Fused to a host to which they are bound, optionally and independently of one another, to form a substituted or unsubstituted cyclic group or a substituted or unsubstituted aryl group; the R is_eAnd R_fIndependently of one another, is substituted or unsubstituted C1-C9 alkyl, substituted or unsubstituted C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 alkylaryl, substituted or unsubstituted C6-C30 arylalkyl or substituted or unsubstituted C3-C30 heteroaryl; the R is_eAnd R_fOptionally in combination with the nitrogen to which they are attached, to form a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heteroaryl group.

According to an embodiment of the present invention, in the chemical formula 5, the-NR₁R₂Is any one of structural formulas A6, A8, A9 and A10,

in the formulae A6, A8, A9 or A10, Sub₁And Sub₂Independently of one another, hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl of C1-C9, substituted or unsubstituted cycloalkyl of C5-C30, substituted or unsubstituted aryl of C6-C30, substituted or unsubstituted alkylaryl of C6-C30, substituted or unsubstituted heteroaryl of C3-C30, substituted or unsubstituted alkoxy of C1-C9, substituted or unsubstituted-NR_cR_dA substituted or unsubstituted silyl group, a substituted or unsubstituted phosphino group, a substituted or unsubstituted phosphinoxy group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide group, a substituted or unsubstituted sulfone group, a substituted or unsubstituted arylsilyl group of C5-C30, a substituted or unsubstituted arylthio group of C5-C30, a substituted or unsubstituted aryloxy group of C5-C30, a substituted or unsubstituted arylamino group of C5-C30, or a substituted or unsubstituted aralkyl group of C5-C30; sub₁To Sub₂Independently of each other and optionally fused to a body to which they are bound to form a substituted or unsubstituted cyclic group or a substituted or unsubstituted aryl group_cAnd R_dIndependently of one another, is a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C5-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aralkyl group, or a substituted or unsubstituted C3-C30 heteroaryl group; r_cAnd R_dOptionally in combination with the nitrogen to which they are attached, to form a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heteroaryl group.

According to an embodiment of the present invention, the compound represented by the chemical formula 3 is represented by the following chemical formula 6,

[ chemical formula 6]

In the chemical formula 6，R₃、R₄、R₅、R₆、R₂₆To R₂₉And R₃₀To R₃₃Same as defined in said chemical formula 3, Sub₅Is hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C9 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C1-C9 alkoxy, substituted or unsubstituted-NR_eR_fA substituted or unsubstituted silyl group, a substituted or unsubstituted phosphino group, a substituted or unsubstituted phosphinoxy group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide group, a substituted or unsubstituted sulfone group, a substituted or unsubstituted arylthio group of C5-C30, a substituted or unsubstituted aryloxy group of C5-C30, a substituted or unsubstituted arylamino group of C5-C30, or a substituted or unsubstituted aralkyl group of C5-C30; sub₅Optionally fused to a body to which they are bound to form a substituted or unsubstituted cyclic group or a substituted or unsubstituted aryl group; the R is_eAnd R_fIndependently of one another, is a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C5-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 alkylaryl group, a substituted or unsubstituted C6-C30 arylalkyl group, or a substituted or unsubstituted C3-C30 heteroaryl group; the R is_eAnd R_fOptionally in combination with the nitrogen to which they are attached, to form a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heteroaryl group.

According to an embodiment of the present invention, in the chemical formula 6, the NR₃R₄And NR₅R₆Independently of one another, of the formulae A6, A8, A9 or A10,

in the formulae A6, A8, A9 or A10, Sub₁And Sub₂Independently of one another, hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl of C1-C9, substituted or unsubstituted cycloalkyl of C5-C30, substituted or unsubstituted aryl of C6-C30, substituted or unsubstituted alkylaryl of C6-C30, substituted or unsubstituted heteroaryl of C3-C30, substituted or unsubstituted alkoxy of C1-C9, substituted or unsubstituted-NR_cR_dA substituted or unsubstituted silyl group, a substituted or unsubstituted phosphino group, a substituted or unsubstituted phosphinoxy group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide group, a substituted or unsubstituted sulfone group, a substituted or unsubstituted arylsilyl group of C5-C30, a substituted or unsubstituted arylthio group of C5-C30, a substituted or unsubstituted aryloxy group of C5-C30, a substituted or unsubstituted arylamino group of C5-C30, or a substituted or unsubstituted aralkyl group of C5-C30; sub₁And Sub₂Independently of each other and optionally fused to the body to which they are attached to form a substituted or unsubstituted cyclic group or a substituted or unsubstituted aryl group; the R is_cAnd R_dIndependently of one another, is a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C5-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aralkyl group, or a substituted or unsubstituted C3-C30 heteroaryl group; r_cAnd R_dOptionally in combination with the nitrogen to which they are attached, to form a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heteroaryl group.

According to an embodiment of the present invention, the compound represented by the chemical formula 2 is any one of the following chemical formulas 7 to 10,

[ chemical formula 7]

[ chemical formula 8]

[ chemical formula 9]

[ chemical formula 10]

In the chemical formulas 7 to 10, R₁₇、R₁₈And R₂₂To R₄₅Same as defined in said chemical formula 2, Sub₁And Sub₂Independently of one another, hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl of C1-C9, substituted or unsubstituted cycloalkyl of C5-C30, substituted or unsubstituted aryl of C6-C30, substituted or unsubstituted alkylaryl of C6-C30, substituted or unsubstituted heteroaryl of C3-C30, substituted or unsubstituted alkoxy of C1-C9, substituted or unsubstituted-NR_cR_dA substituted or unsubstituted silyl group, a substituted or unsubstituted phosphino group, a substituted or unsubstituted phosphinoxy group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide group, a substituted or unsubstituted sulfone group, a substituted or unsubstituted arylsilyl group of C5-C30, a substituted or unsubstituted arylthio group of C5-C30, a substituted or unsubstituted aryloxy group of C5-C30, a substituted or unsubstituted arylamino group of C5-C30, or a substituted or unsubstituted aralkyl group of C5-C30; sub₁To Sub₂Independently of each other and optionally fused to a body to which they are bound to form a substituted or unsubstituted cyclic group or a substituted or unsubstituted aryl group_cAnd R_dIndependently of one another, are substituted or unsubstituted C1-C9 alkyl, substituted or unsubstituted C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 arylA substituted or unsubstituted C6-C30 aralkyl group, or a substituted or unsubstituted C3-C30 heteroaryl group; r_cAnd R_dOptionally in combination with the nitrogen to which they are attached, to form a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heteroaryl group.

According to an embodiment of the present invention, the compound represented by the chemical formula 3 is represented by the following chemical formula 11,

[ chemical formula 11]

In the chemical formula 11, R₁₉And R₂₆To R₃₃Same as defined in said chemical formula 3, Sub₁And Sub₂Independently of one another, hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl of C1-C9, substituted or unsubstituted cycloalkyl of C5-C30, substituted or unsubstituted aryl of C6-C30, substituted or unsubstituted alkylaryl of C6-C30, substituted or unsubstituted heteroaryl of C3-C30, substituted or unsubstituted alkoxy of C1-C9, substituted or unsubstituted-NR_cR_dA substituted or unsubstituted silyl group, a substituted or unsubstituted phosphino group, a substituted or unsubstituted phosphinoxy group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide group, a substituted or unsubstituted sulfone group, a substituted or unsubstituted arylsilyl group of C5-C30, a substituted or unsubstituted arylthio group of C5-C30, a substituted or unsubstituted aryloxy group of C5-C30, a substituted or unsubstituted arylamino group of C5-C30, or a substituted or unsubstituted aralkyl group of C5-C30; sub₁And Sub₂Independently of each other and optionally fused to a body to which they are bound to form a substituted or unsubstituted cyclic group or a substituted or unsubstituted aryl group_cAnd R_dIndependently of one another, is substituted or unsubstituted C1-C9 alkyl, substituted or unsubstituted C5-C30 cycloalkyl, substitutedSubstituted or unsubstituted aryl of C6-C30, substituted or unsubstituted aralkyl of C6-C30, or substituted or unsubstituted heteroaryl of C3-C30; r_cAnd R_dOptionally in combination with the nitrogen to which they are attached, to form a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heteroaryl group.

According to an embodiment of the present invention, the compound represented by the chemical formula 4 is the following chemical formula 12,

[ chemical formula 12]

In the chemical formula 12, R₃₄To R₄₅Same as defined in said chemical formula 4, Sub₁And Sub₂Independently of one another, hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl of C1-C9, substituted or unsubstituted cycloalkyl of C5-C30, substituted or unsubstituted aryl of C6-C30, substituted or unsubstituted alkylaryl of C6-C30, substituted or unsubstituted heteroaryl of C3-C30, substituted or unsubstituted alkoxy of C1-C9, substituted or unsubstituted-NR_cR_dA substituted or unsubstituted silyl group, a substituted or unsubstituted phosphino group, a substituted or unsubstituted phosphinoxy group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide group, a substituted or unsubstituted sulfone group, a substituted or unsubstituted arylsilyl group of C5-C30, a substituted or unsubstituted arylthio group of C5-C30, a substituted or unsubstituted aryloxy group of C5-C30, a substituted or unsubstituted arylamino group of C5-C30, or a substituted or unsubstituted aralkyl group of C5-C30; sub₁To Sub₂Independently of each other and optionally fused to a body to which they are bound to form a substituted or unsubstituted cyclic group or a substituted or unsubstituted aryl group_cAnd R_dIndependently of one another, substituted or unsubstituted C1-C9 alkyl, substituted or unsubstituted C5-C30 cycloalkylSubstituted or unsubstituted aryl of C6-C30, substituted or unsubstituted aralkyl of C6-C30, or substituted or unsubstituted heteroaryl of C3-C30; r_cAnd R_dOptionally in combination with the nitrogen to which they are attached, to form a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heteroaryl group.

According to an embodiment of the present invention, the luminescent material represented by the chemical formula 2 is any one of the following compounds 1 to 66,

according to an embodiment of the present invention, the luminescent material represented by the chemical formula 3 is any one of the following compounds 67 to 82,

according to an embodiment of the present invention, the luminescent material represented by the chemical formula 4 is any one of the following compounds 83 to 92,

according to an embodiment of the present invention, -NR in the chemical formulas 2 to 4₁R₂、-NR₃R₄、-NR₅R₆、-NR₇R₈、-NR₉R₁₀and-NR₁₁R₁₂Independently of one another, are any of the following formulae A1 to A45,

in the structural formulae A1 to A45, R₁₁To R₁₄Independently of one another, hydrogen, deuterium, substituted or unsubstituted C1-C2 alkyl or substituted or unsubstituted C6-C30 aryl, Sub₁To Sub₄Independently of one another, hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C9 alkyl, substituted or unsubstituted C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 alkylaryl, substituted or unsubstituted C6-C30 arylalkyl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C1-C9 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted silane, substituted or unsubstituted phosphine, substituted or unsubstituted phosphino, substituted or unsubstituted phosphinoxy, substituted or unsubstituted thiol, substituted or unsubstituted sulfoxide, or substituted or unsubstituted sulfone.

According to an embodiment of the present invention, in the chemical formula 2, the triazinyl group is any one of the following structural formulae B1 to B27,

in the structural formulae B1 to B27, R₁₁And R₁₂Independently of one another, hydrogen, deuterium or a substituted or unsubstituted C1-C2 alkyl group, Sub₅And Sub₆Independently of one another, hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C9 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C1-C9 alkoxy, substituted or unsubstituted silane, substituted or unsubstituted phosphine, substituted or unsubstituted phosphinoxy, substituted or unsubstituted thiol, substituted or unsubstituted sulfoxide, substituted or unsubstituted sulfone, substituted or unsubstituted C5-C30 arylthio, substituted or unsubstituted C5-C30 aryloxy, substituted or unsubstituted C5-C30 arylamine, or substituted or unsubstituted C5-C30 aralkyl; sub₅And Sub₆Optionally fused independently of each other to the body to which they are attached to form a substituted or unsubstituted cyclic group or a substituted or unsubstituted aryl group.

According to an embodiment of the present invention, in the chemical formula 3, the triazinyl group is any one of the following structural formulae B28 to B49,

in the structural formulae B28 to B49, R₁₁And R₁₂Independently of one another, hydrogen, deuterium or a substituted or unsubstituted C1-C2 alkyl group.

According to another aspect of the present invention, there is provided an organic light emitting diode comprising an anode, a hole conducting layer, a light emitting layer, an electron conducting layer, a cathode, which are sequentially stacked, any one of the hole conducting layer, the light emitting layer, and the electron conducting layer comprising the compound as described above.

According to an embodiment of the present invention, the light emitting layer comprises a host material and a dopant material, the dopant material comprising a compound as described above.

According to an embodiment of the invention, the doping substance is a delayed fluorescence emitting substance.

Technical effects

According to the embodiment of the present invention, a compound in which an electron donating group and an electron withdrawing group are introduced to the ortho position of a benzene ring can exhibit delayed fluorescence because a triplet excited state can be relatively easily transferred to a singlet excited state by Reverse Intercross (RISC) due to heat at normal temperature or at a device operating temperature as the difference between singlet energy and triplet energy decreases.

Drawings

Fig. 1 is a cross-sectional view illustrating an organic light emitting diode according to an embodiment of the present invention.

Fig. 2 shows the molecular orbital function distribution for compound 1, comparative compound 2 and comparative compound 3 produced according to synthesis example 1.

Detailed Description

Hereinafter, in order to more specifically describe the present invention, preferred embodiments according to the present invention will be described in more detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein, and may be embodied in other forms. Throughout the specification, the same reference numerals denote the same constituent elements.

In the present specification, "alkyl" represents an aliphatic hydrocarbon group without any other limitation. An alkyl group may be a "saturated alkyl" group that does not include any double or triple bonds. Alternatively, the alkyl group may also be an "unsaturated alkyl" group comprising at least one double or triple bond. The alkyl groups, whether saturated or unsaturated, may be branched, straight-chain or cyclic. The alkyl group may be a C1 to C30 alkyl group. More specifically, the alkyl group may also be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, the alkyl group of C1 to C4 may be selected from the group consisting of methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.

In the present specification, "aryl" represents a polycyclic aromatic compound composed of a monocyclic aromatic compound or fused aromatic ring, and is a concept including heteroaryl, unless otherwise specified.

In the present specification, "heteroaryl" means, without any other limitation, a polycyclic aromatic compound composed of a monocyclic aromatic compound or a fused aromatic ring, which contains 1 or more heteroatoms selected from the group consisting of N, O, S, Se and P in at least one ring, and the remainder of which is carbon.

In the present specification, the "halogen group" is a concept representing a group 7 element, for example, F, Cl, Br or I, without any other limitation. For example, the halogen group may be F.

In the present specification, the term "Cx-Cy" is to be interpreted to include the number of carbon atoms corresponding to all integers between the number of carbon atoms x and the number of carbon atoms y.

Thermally activated delayed fluorescence material

The following chemical formula 1 represents a compound according to an embodiment of the present invention.

[ chemical formula 1]

In the chemical formula 1, the first and second organic solvents,

R_EDGis an Electron Donating Group (Electron Donating Group),

R_EWGis an Electron Withdrawing Group (Electron Withdrawing Group),

R₅to R₈Can be free of each otherThe aryl group is hydrogen atom, deuterium, substituted or unsubstituted C1-C9 alkyl group, substituted or unsubstituted C5-C30 cycloalkyl group, substituted or unsubstituted C6-C30 aryl group, substituted or unsubstituted C6-C30 alkylaryl group (alkylryl group), substituted or unsubstituted C6-C30 arylalkyl group (arylalkyl group), substituted or unsubstituted C3-C30 heteroaryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylamine group, substituted or unsubstituted fused arylamine group, substituted or unsubstituted phosphino or phosphinoxy group, substituted or unsubstituted thiol group, substituted or unsubstituted sulfoxide group or sulfone group.

The electron-donating group may be a substituted or unsubstituted amine group, and the electron-withdrawing group may be a substituted or unsubstituted triazinyl group.

The compound represented by the chemical formula 1 may be a light emitting material. Specifically, it may be a thermally activated delayed fluorescence material indicating thermally activated delayed fluorescence. More specifically, the organic light-emitting device can be used as a light-emitting dopant for an organic light-emitting element. However, the present invention is not limited to this, and may be used for any layer in an organic light emitting element, and may be used as a host material in a light emitting layer.

As described above, the compound represented by chemical formula 1 has a shape in which an electron-donating group and an electron-withdrawing group are bonded to a phenyl group, and the electron-withdrawing group is connected adjacent to (ortho to) the electron-donating group. As described above, an electron donating group and an electron withdrawing group are introduced into the ortho position of the phenyl group, and the overlap between the Highest Occupied Molecular Orbital (HOMO) and the Lowest Unoccupied Molecular Orbital (LUMO) can be adjusted by steric hindrance, and the difference between singlet energy (SI) and triplet energy (Tl) can be reduced. Specifically, by minimizing the difference between the singlet energy and the triplet energy (0.3eV or less) of a compound in which an electron-donating group and an electron-withdrawing group are introduced at the ortho-position of the benzene ring, the triplet excited state can be transferred to the singlet excited state relatively easily by the reverse system cross-over by heat (normal temperature or device operating temperature), and thus delayed fluorescence can be exhibited.

Specific examples of the compound represented by the chemical formula 1 may be represented by any one of the following chemical formulas 2 to 4.

[ chemical formula 2]

[ chemical formula 3]

[ chemical formula 4]

In the chemical formulas 2 to 4, R₁To R₁₂Independently of one another, is a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C5-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 alkylaryl group, a substituted or unsubstituted C6-C30 arylalkyl group, or a substituted or unsubstituted C3-C30 heteroaryl group; r₁And R₂、R₃And R₄、R₅And R₆、R₇And R₈、R₉And R₁₀Or R₁₁And R₁₂Optionally (optinally) taken together with the nitrogen to which they are attached, can form a substituted or unsubstituted heterocyclyl or substituted or unsubstituted heteroaryl.

In the chemical formulas 2 to 4, R₁₇To R₁₉Is a functional group linked to the triazine group by carbon, nitrogen, oxygen, silicon, sulfur or phosphorus, and may be, independently of one another, a cyano group, a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C5-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 alkylaryl group, a substituted or unsubstituted C6-C30 alkyl group,Substituted or unsubstituted aralkyl of C6-C30, substituted or unsubstituted heteroaryl of C3-C30, substituted or unsubstituted alkoxy of C1-C30, substituted or unsubstituted aryloxy of C3-C30, alkylsilyl of C1-C9, or substituted or unsubstituted-NR_aR_b. The R is_aAnd R_bMay be, independently of one another, hydrogen, deuterium, substituted or unsubstituted C1-C9 alkyl, substituted or unsubstituted C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 aralkyl, or substituted or unsubstituted C3-C30 heteroaryl. R_aAnd R_bOptionally (optinally) taken together with the nitrogen to which they are attached, can form a substituted or unsubstituted heterocyclyl or substituted or unsubstituted heteroaryl.

R₂₂To R₄₅May be reacted with R defined in the chemical formula 1₅To R₈Are the same, specifically, R₂₂To R₄₅May be, independently of one another, hydrogen, deuterium, halogen, substituted or unsubstituted C4-C6 aryl, or substituted or unsubstituted C1-C3 alkyl. At this time, the substituted C1-C3 alkyl group may be a halogenated C1-C3 alkyl group, and the halogen group may be F.

Electron donating group in the chemical formula 1 or-NR in the chemical formulae 2 to 4₁R₂、-NR₃R₄、-NR₅R₆、-NR₇R₈、-NR₉R₁₀and-NR₁₁R₁₂Any one of the following structural formulae a1 to a19 may be used independently of one another, and may be, for example, a6, A8, a9 or a 10.

In the structural formulae a1 to a19,

R₁and R in the chemical formula 2₁In the same way, the first and second,

R₁₁to R₁₄Independently of one another, hydrogen, deuterium, substituted or unsubstituted C1-C2 alkyl, or substituted or unsubstituted C6-C30 aryl,

Sub₁to Sub₂May be, independently of one another, hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C9 alkyl, substituted or unsubstituted C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 alkylaryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C1-C9 alkoxy, substituted or unsubstituted-NR_cR_dA substituted or unsubstituted silyl group, a substituted or unsubstituted phosphino group, a substituted or unsubstituted phosphinoxy group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide group, a substituted or unsubstituted sulfone group, a substituted or unsubstituted arylsilyl group of C5-C30, a substituted or unsubstituted arylthio group of C5-C30, a substituted or unsubstituted aryloxy group of C5-C30, a substituted or unsubstituted arylamino group of C5-C30, or a substituted or unsubstituted aralkyl group of C5-C30. The R is_cAnd R_dMay be, independently of one another, a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C5-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 aralkyl group or a substituted or unsubstituted C3-C30 heteroaryl group. R_cAnd R_dOptionally (optinally) taken together with the nitrogen to which they are attached, can form a substituted or unsubstituted heterocyclyl or substituted or unsubstituted heteroaryl. And, Sub₁To Sub₂Independently and selectively fused (fused) to the body to which they are bound, capable of forming a substituted or unsubstituted cyclic group or a substituted or unsubstituted aryl group. Especially, in Sub₁To Sub₂When at least any one of them is a substituted or unsubstituted arylsilyl group of C5-C30, a substituted or unsubstituted arylthio group of C5-C30, a substituted or unsubstituted aryloxy group of C5-C30, a substituted or unsubstituted arylamino group of C5-C30, or a substituted or unsubstituted aralkyl group of C5-C30, the aryl group contained therein may be fused (fused) to the main body to form a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heteroaryl group.

Electron donating group in the chemical formula 1 or-NR in the chemical formulae 2 to 4₁R₂、-NR₃R₄、-NR₅R₆、-NR₇R₈、-NR₉R₁₀and-NR₁₁R₁₂May be any one of the following structural formulae a20 to a38 independently of one another. In particular, the structural formula A9 can also be any one of the following structural formulas A20 to A38.

In the structural formulae a20 to a38,

R₁₁and R₁₂Independently of one another, hydrogen, deuterium, substituted or unsubstituted C1-C2 alkyl, or substituted or unsubstituted C6-C30 aryl,

Sub₁to Sub₄May be, independently of one another, hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C9 alkyl, substituted or unsubstituted C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 alkylaryl, substituted or unsubstituted C6-C30 arylalkyl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C1-C9 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted silane, substituted or unsubstituted phosphine, substituted or unsubstituted phosphino, substituted or unsubstituted phosphinoxy, substituted or unsubstituted thiol, substituted or unsubstituted sulfoxide, or substituted or unsubstituted sulfoxideAn unsubstituted sulfone group.

Electron donating group in the chemical formula 1 or-NR in the chemical formulae 2 to 4₁R₂、-NR₃R₄、-NR₅R₆、-NR₇R₈、-NR₉R₁₀and-NR₁₁R₁₂May be any one of the following structural formulae a39 to a45 independently of one another. In particular, the structural formula A10 can also be any one of the following structural formulas A39 to A45.

In the structural formulae a39 to a45,

R₁₁to R₁₄Independently of one another, hydrogen, deuterium, substituted or unsubstituted C1-C2 alkyl, or substituted or unsubstituted C6-C30 aryl,

Sub₁to Sub₄May be, independently of one another, hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C9 alkyl, substituted or unsubstituted C5-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 alkylaryl, substituted or unsubstituted C6-C30 arylalkyl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C1-C9 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted silane, substituted or unsubstituted phosphine, substituted or unsubstituted phosphino, substituted or unsubstituted phosphinoxy, substituted or unsubstituted thiol, substituted or unsubstituted sulfoxide, or substituted or unsubstituted sulfone.

Examples of the electron withdrawing group in chemical formula 1 or the triazine group in chemical formula 2 may be the same as the following structural formulae B1 to B14.

In the structural formulae B1 to B14,

R₁₁and R₁₂May be independently of one another hydrogen, deuterium, or a substituted or unsubstituted C1-C2 alkyl group,

Sub₅and Sub₆May be, independently of one another, hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C9 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C1-C9 alkoxy, substituted or unsubstituted-NR_eR_fA substituted or unsubstituted silyl group, a substituted or unsubstituted phosphino group, a substituted or unsubstituted phosphinoxy group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide group, a substituted or unsubstituted sulfone group, a substituted or unsubstituted arylthio group of C5-C30, a substituted or unsubstituted aryloxy group of C5-C30, a substituted or unsubstituted arylamino group of C5-C30, or a substituted or unsubstituted aralkyl group of C5-C30. In addition, Sub₅And Sub₆Fused (fused) to a body to which they are bonded, optionally (optics) and independently of one another, capable of forming a substituted or unsubstituted cyclic group or a substituted or unsubstituted aryl group. Especially when Sub₅Or Sub₆Is a substituted or unsubstituted arylthio group of C5-C30, a substituted or unsubstituted aryloxy group of C5-C30, a substituted or unsubstituted arylamino group of C5-C30, or a substituted or unsubstituted aralkyl group of C5-C30, the aryl group contained therein is fused (fused) to the main body to be able to form a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heteroaryl group.

The R is_eAnd R_fIndependently of one another, is a substituted or unsubstituted C1-C9 alkyl group, a substituted or unsubstituted C5-C30 cycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 alkylaryl group, a substituted or unsubstituted C6-C30 arylalkyl group, or a substituted or unsubstituted C3-C30 heteroaryl group; the R is_eAnd R_fSelectively (selectively) and attachingWith their nitrogens taken together to form a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted heteroaryl group.

An electron withdrawing group in the chemical formula 1 or R in the chemical formula 2₁₇And R₁₈Examples of the substituted triazinyl group may be the same as the following structural formulae B15 to B27. In particular, the structural formula B12 may be any one of the following structural formulae B15 to B27.

In the structural formulae B15 to B27,

R₁₁and R₁₂May be independently of one another hydrogen, deuterium, or a substituted or unsubstituted C1-C2 alkyl group,

in the chemical formula 3 at R₁₉Examples of the substituted triazinyl group may be the same as the following structural formulae B28 to B49.

In the structural formulae B28 to B49,

R₁₁and R₁₂May be independently of one another hydrogen, deuterium, or a substituted or unsubstituted C1-C2 alkyl group.

A specific example of the compound represented by the chemical formula 2 may be the following chemical formula 5, and a specific example of the compound represented by the chemical formula 3 may be the following chemical formula 6.

[ chemical formula 5]

In the chemical formula 5, R₁、R₂And R₂₂To R₂₅The same as defined in said chemical formula 2, specifically, said-NR₁R₂Is as followsAny one of the structural formulae a1 to a45 may be, for example, a6, A8, a9 or a 10.

In the chemical formula 5, Sub₅And Sub₆May be the same as defined in said structural formula B12. As an example, Sub₅And Sub₆At least any one of may be-NR_eR_f. Specifically, when Sub₅And Sub₆Only any one of them being-NR_eR_fAnd the-NR_eR_fWhen located at the ortho-position with respect to the triazine group, the compound of chemical formula 5 may be the same as the compound represented by chemical formula 6 below, when Sub₅And Sub₆Are all-NR_eR_fAnd the two-NR_eR_fWhen all are located at the ortho-position with respect to the triazine group, the compound of chemical formula 5 may be the same as the compound represented by chemical formula 4.

As an example, in the chemical formula 5, the triazine group may be exemplified by any one of the structural formulae B12 or B15 to B27.

[ chemical formula 6]

In the chemical formula 6, R₃、R₄、R₅、R₆、R₂₆To R₂₉And R₃₀To R₃₃The same as defined in said chemical formula 3. Specifically, the NR₃R₄And NR₅R₆Any one of the structural formulae a1 to a45 may be used independently of one another, and may be, for example, a6, A8, a9 or a 10.

In the chemical formula 6, Sub₅The same as defined in said structural formula B11. As an example, in the chemical formula 6, the triazine group may be exemplified by any one of the structural formulae B34 to B47.

Specific examples of the compound represented by the chemical formula 2 may be represented by any one of the following chemical formulas 7 to 10.

[ chemical formula 7]

[ chemical formula 8]

[ chemical formula 9]

[ chemical formula 10]

Specific examples of the compound represented by the above chemical formula 3 can be represented by the following chemical formula 11.

[ chemical formula 11]

Specific examples of the compound represented by the above chemical formula 4 may be represented by the following chemical formula 12.

[ chemical formula 12]

Sub in the chemical formulas 7, 11 and 12₁And Sub₂May be the same as defined in said structural formula a 9. As an example, the Sub in the chemical formulas 7, 11 and 12 are included₁And Sub₂The carbazolyl group of (a) may be any one of the structural formulae a20 to a 38. Sub in the chemical formula 8₁And Sub₂May be the same as defined in said structural formula A8. Sub in the chemical formula 9₁And Sub₂May be the same as defined in said structural formula a 6. Sub in the chemical formula 10₁And Sub₂May be the same as defined in said structural formula a 10. As an example, the compound includes Sub in the above chemical formula 10₁And Sub₂The acridine (acridane) group of (a) may also be any one of the structural formulae a39 to a 45.

In the chemical formulas 7 to 10, R₁₇And R₁₈May be the same as defined in said chemical formula 2. As an example, R is included₁₇To R₁₈The triazinyl group of (a) may be any one of the structural formulae B1 to B27. In particular, comprising R₁₇To R₁₈The triazinyl group (B) may be the structural formula B12, specifically, may be any one of the structural formulae B15 to B27. In the chemical formula 11, R₁₉May be the same as defined in said chemical formula 3. As another example, R is included₁₉The triazinyl group of (a) may be any one of the structural formulae B28 to B49.

In the chemical formulas 7 to 12, R₂₂To R₄₅May be reacted with R defined in the chemical formula 1₅To R₈Are the same, specifically, R₂₂To R₄₅May be, independently of one another, hydrogen, deuterium, halogen, substituted or unsubstituted C4-C6 aryl, or substituted or unsubstituted C1-C3 alkyl. At this time, the substituted C1-C3 alkyl group may be a halogenated C1-C3 alkyl group, and the halogen group may be F.

In the chemical formula 10, R₁₁And R₁₂May be independently of one another hydrogen, deuterium, or a substituted or unsubstituted C1-C2 alkyl group.

It has been confirmed that this thermally activated delayed fluorescent material can realize emission colors of red, green and blue by appropriately combining the introduction of electron-donating groups and electron-withdrawing groups, and can reduce the singlet energy and the triplet energy to 0.3eV or less.

Specific compounds of such a thermally activated delayed fluorescence material are represented by the following compounds 1 to 92, but are not limited thereto.

The compounds 1 to 21, 31 to 45, 52, 53, 55 to 60, 67 to 74 and 81 to 86 may be examples of the compound shown in the chemical formula 7, the compounds 22 to 30, 46 to 48, 75 to 78 and 89 to 92 may be examples of the compound shown in the chemical formula 8, the compounds 49, 50, 61 to 66, 87 and 88 may be examples of the compound shown in the chemical formula 9, the compounds 51, 54, 79 and 80 may be examples of the compound shown in the chemical formula 10, the compounds 67 to 74 may be examples of the compound shown in the chemical formula 11, and the compounds 83 to 86 may be examples of the compound shown in the chemical formula 12.

Organic light emitting diode

Fig. 1 is a cross-sectional view illustrating an organic light emitting diode according to an embodiment of the present invention.

Referring to fig. 1, the organic light emitting diode includes: an anode 10 and a cathode 70; a light-emitting layer 40 disposed between the two electrodes; a hole conducting layer 20 disposed between the anode 10 and the light emitting layer 40; and an electron conducting layer 50 disposed between the light emitting layer 40 and the cathode 70. The hole conducting layer 20 may have: a hole transport layer 25 for transporting holes; and a hole injection layer 23 for relatively easily injecting holes. The electron conductive layer 50 may include: an electron transport layer 55 for transporting electrons; an electron injection layer 53 for allowing electrons to be injected more easily. In addition, a hole blocking layer (not shown) may be disposed between the light-emitting layer 40 and the electron transport layer 55. An electron blocking layer (not shown) may be disposed between the light-emitting layer 40 and the hole transport layer 25. However, the electron transport layer 55 may function as a hole blocking layer, or the hole transport layer 25 may function as an electron blocking layer.

When a forward bias (forward bias) is applied to such an organic light emitting diode, holes flow into the light emitting layer 40 at the anode 10, and electrons flow into the light emitting layer 40 at the cathode 70. The electrons and holes flowing into the light emitting layer 40 combine to form excitons, and the excitons emit light while transferring to the ground state.

The light-emitting layer 40 may be composed of a single light-emitting material, or may contain a light-emitting host substance and a light-emitting dopant substance. The single light emitting material or the light emitting dopant substance may be a compound represented by any one of the aforementioned chemical formulas 1 to 12 and compounds 1 to 92, and particularly, may be a thermally activated delayed fluorescence material. In this case, the efficiency of the organic light emitting diode can be greatly improved. In this thermally activated delayed fluorescence material, an Electron Donating Group (Electron Donating Group) and an Electron Withdrawing Group (Electron Withdrawing Group) may be bonded to a phenyl Group, and the difference between singlet energy and triplet energy can be reduced to 0.3eV or less due to the shape in which the Electron Withdrawing Group is bonded adjacent to (ortho to) the Electron Donating Group. The thermally activated delayed fluorescence material can be more effectively transferred from a triplet excited state to a singlet excited state by heat (normal temperature or element operating temperature), thereby improving quantum efficiency. At the same time, by appropriately combining the introduction of electron-withdrawing groups and electron-donating groups, various emission colors of red, green and blue can be realized.

The luminescent host substance may be N, N-dicarbazolyl-3,5-benzene (mCP: N, N-dicarbazolyl-3, 5-benzone), 8-hydroxyquinoline aluminum (Alq3), 4-4 '-N, N' -dicarbazole-biphenyl (CBP), 9, 10-bis (naphthalen-2-yl) anthracene, 1,3, 5-tris (N-phenylbenzimidazol-2-yl) benzene (TPBI: l,3,5-tris (N-phenylbenzimidazamidazida-2-yl) benzone), 3-tert-butyl-9, 10-bis (naphthalen-2-yl) anthracene (TBADN), E3 (see the following chemical formula), or BeBq2 (see the following chemical formula).

The hole injection layer 23 and/or the hole transport layer 25 are layers having a HOMO level between the work function level of the anode 10 and the HOMO level of the light emitting layer 40, and function to improve the efficiency of hole injection or transport from the anode 10 to the light emitting layer 40. The electron injection layer 53 and/or the electron transport layer 55 have a LUMO level between the work function level of the cathode 70 and the LUMO level of the light-emitting layer 40, and function to improve the efficiency of electron injection or transport from the cathode 70 to the light-emitting layer 40.

The anode 10 may be a conductive metal oxide, metal alloy, or carbon material. The conductive metal oxide may be Indium Tin Oxide (ITO), Fluorine Tin Oxide (FTO), Antimony Tin Oxide (ATO), fluorine-doped tin oxide (FTO), SnO2, ZnO, or a combination thereof. Suitable metals or metal alloys for the anode 10 can be Au and CuI. The carbon material may be graphite, graphene or carbon nanotubes.

The hole injection layer 23 or the hole transport layer 25 may contain a material generally used as a hole transport material, and one layer may include different hole transport material layers from each other. The hole-transporting substance may be, for example, N' -dicarbazole-3, 5-benzene (mCP: N, N-dicarbazolyl-3, 5-bezene); poly (3, 4-ethylenedioxythiophene): polystyrene sulfonic acid (PEDOT: PSS (poly (3, 4-ethylenedioxythiophene): polystyrenesulfonate), N, N '-bis (1-naphthyl) -N, N' -diphenylbenzidine (NPD: N, N '-di (I-naphthyl) -N, N' -di- (diphenylbenzidine)); N, N '-biphenyl-N, N' -bis (3-methylphenyl) -4,4 '-diaminobiphenyl (TPD); N, N' -diphenyl-N, N '-dinaphthalene-4, 4' -diaminobiphenyl; N, N, N '-tetra-p-tolyl-4, 4' -diaminobiphenyl; N, N, N '-N-tetraphenyl-4, 4' -diaminobiphenyl; copper (II) 1,10,15, 20-tetraphenyl-21H, porphyrin (porphyrin) compound derivatives such as 23H-porphyrin; 1,1 ' -Bis [4- [ N, N ' -Di (p-tolyl) Amino ] benzene ] Cyclohexane (TAPC: l, l-Bis [4- [ N, N ' -Di (p-tolyl) Amino ] Phenyl ] Cyclohexane); n, N-tri (p-tolyl) amine; triarylamine derivatives such as 4, 4' -tris [ N- (3-methylphenyl) -N-phenylamino ] triphenylamine; carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole; phthalylated cyan derivatives such as metal-free phthalylated cyan and copper phthalylated cyan; a starburst amine derivative; derivatives of the enaminostilbene (enamine stilbene) series; derivatives of aromatic tertiary amines and styrylamine compounds; and polysilanes and the like. Such a hole-transporting substance can also function as an electron blocking layer.

The hole blocking layer plays a role of preventing diffusion of triplet excitons or holes in the direction of the cathode 70, and may be arbitrarily selected from well-known hole blocking materials. For example, oxadiazole derivatives or triazole derivatives, phenanthroline derivatives, and the like can be used.

The electron transport layer 55 may be diphenylphosphine oxide-4- (triphenylsilyl) benzene (TSPO 1: diphenylphosphinoxide-4- (triphenylsilylphenyl) phenyl), tris (8-hydroxyquinoline) aluminum (Alq3), 2, 5-diarylsilole derivative (PySPyPy), perfluoro compound (PF-6P), octasubstituted Cyclooctatetraene (COTs) (octaactual cyclooctanetetraene), TAZ (see the following chemical formula), 4, 7-diphenyl-1, 10-phenanthroLine (Bphen: 4, 7-diphenyll, 10-phenanthroLine), BCP (see the following chemical formula), or BALq (see the following chemical formula).

The electron injection layer 53 may be, for example, LiF, NaCl, CsF, Li2O, BaO, BaF2, or Liq (lithium quinolate).

The cathode 70 is a conductive film having a work function lower than that of the anode 70, and can be formed by using a metal such as aluminum, magnesium, calcium, sodium, potassium, indium, yttrium, lithium, silver, lead, cesium, or a combination of two or more of these metals, for example.

The anode 10 and the cathode 70 may be formed using a starburst (sputtering) method, a vapor deposition method, or an ion beam deposition method. The hole injection layer 23, the hole transport layer 25, the light emitting layer 40, the hole blocking layer, the electron transport layer 55, and the electron injection layer 53 may be formed independently of each other using a deposition method or a coating method, for example, spray coating, spin coating, dip coating, printing, a doctor blade method, or an electrophoresis method.

The organic light emitting diode may be disposed on a substrate (not shown), and the substrate may be disposed at a lower portion of the anode 10 or may be disposed at an upper portion of the cathode 70. In other words, the anode 10 may be formed earlier than the cathode 70 or the cathode 70 may be formed earlier than the anode 10 on the substrate.

The substrate as the flat plate-shaped member may be a light-transmitting substrate, in which case the substrate may be made of glass; a ceramic material; polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), Polyimide (PI), polypropylene (PP) and other high polymer materials. However, the present invention is not limited to this, and the substrate may be a metal substrate that can reflect light.

Hereinafter, preferred examples (examples) are provided to help understand the present invention. The following experimental examples are merely provided to facilitate understanding of the present invention, and the present invention is not limited to the following experimental examples.

[ Experimental Examples (EXAMPLES) ]

[ reaction formula 1]

In the reaction formula 1, in R₁And R₂In the case of both hydrogen is compound 1, in R₁Is methyl, R₂When it is hydrogen, is compound 2, in which R₁Is tert-butyl, R₂When it is hydrogen, is compound 3, in R₁Is hydrogen, R₂When it is methyl, is a compound37。

Synthesis example 1: synthesis of Compound 1

Step 1: carbazole (10.0g, 59.8mmol), 1,2 dibromobenzene (21.16g, 89.71mmol), potassium carbonate (16.53g, 119.61mmol) and copper iodide (CuI) (5.69g, 29.90mmol) were dissolved in 250ml of N, N-dimethylacetamide, and then oxygen in the solution was removed by a nitrogen bubbling method (nitrogen bubbling). After removal of oxygen, the loop was stirred for 24 hours. After the reaction solution was extracted with dichloromethane, column chromatography was performed using a dichloromethane/hexane mixed solvent as a developing solvent (eluent) to obtain 15.99g of 9- (2-bromophenyl) carbazole. 9- (2-bromophenyl) carbazole: mass analysis (El) M/z 322[ (M + H) +]

Step 2: after 9- (2-bromophenyl) carbazole (10g, 31.03mmol), 4,4,4 ', 5,5, 5' -octamethyl-2, 2 '-bis (1,2, 3-dioxaborolan) (11.82g, 46.55mmol), potassium acetate (9.14g, 93.11mmol), and 1, 1' -bis (diphenylphosphine) dipentairon-palladium (II) (0.76g, 0.93mmol) were dissolved in 180ml of 1, 4-dioxane, oxygen in the solution was removed by nitrogen bubbling. After removal of oxygen, the loop was stirred for 24 hours. After the reaction solution was extracted with methylene chloride, column chromatography was performed using a methylene chloride/hexane mixed solvent as a developing solvent to obtain 4.01g of 9- (2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan) -2-yl) benzene) carbazole. 9- (2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) benzene) carbazole: mass analysis (EI) M/z369[ (M + H) + ]

Step 3: 9- (2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) benzene) carbazole (3g, 8.12mmol), 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (2.61g, 9.75mmol), tetrakis (triphenylphosphine) palladium (0) (0.28g, 0.24mmol) were put in a mixed solvent of 60ml of tetrahydrofuran and 20ml of potassium phosphate 2M solution, and then circulated for 24 hours. After the reaction solution was extracted with dichloromethane, column chromatography was performed using a dichloromethane/hexane mixed solvent as a developing solvent, and finally sublimation was performed to obtain 3.31g of a pure white solid.

Compound 1: yield: 86% Mass analysis (EI) M/z 474[ (M + H)⁺]. Theoretical value of elemental analysis C₃₃H₂₂N₄: c (83.52%) H (4.67%) N (11.81%). Measurement value: c (83.52%) H (4.74%) N (11.69%).¹H NMR(500MHz，CDC1₃)：δ8.57(d，1H)，8.03(t，6H)，7.85(t，1H)，7.78(t，1H)，7.73(d，1H)，7.48(t，2H)，7.34(t，6H)，7.24～7.19(m，4H)。

Synthesis example 2: synthesis of Compound 2

Compound 2 was obtained in 83% yield in the same manner as in synthesis example 1, except that 3, 6-dimethylcarbazole was used instead of carbazole in step 1 of synthesis example 1.

Compound 2: mass analysis (FAB) M/z502[ (M + H)⁺]. Theoretical value of elemental analysis C₃₅H₂₆N₄: c (83.64%) H (5.21%) N (11.15%) found: c (83.69%) H (5.26%) N (11.09%).¹H NMR(500MHz，CDCl₃)：8.50(d，1H)，8.00(d，4H)，7.78(t，3H)，7.73(t，1H)，7.67(d，1H)，7.47(t，2H)，7.31(t，4H)，7.11(d，2H)，7.06(d，2H)，2.49(s，6H)。

Synthesis example 3: synthesis of Compound 3

Compound 3 was obtained in the same manner as in synthesis example 1, except that 3, 6-di-1-tert-butylcarbazole was used instead of carbazole in step 1 of synthesis example 1, and the yield was 81%.

Compound 3: mass analysis (EI) M/z586[ (M + H)⁺]. Theoretical value of elemental analysis C₄₁H₃₈N₄: c (83.92%) H (6.53%) N (9.55%) found: c (83.85%) H (6.61%) N (9.53%).¹H NMR(500MHz，CDCl₃)：8.56(d，1H)，8.09(d，4H)，8.02(d，2H)，7.81(t，1H)，7.74(t，1H)，7.68(d，1H)，7.49(t，2H)，7.34(t，6H)，7.11(d，2H)，1.42(s，18H)。

Synthesis example 4: synthesis of Compound 37

Compound 37 was obtained in 78% yield using the same method as in synthesis example 1, except that 2-chloro-4, 6-di-p-tolyl-1, 3, 5-triazine was used instead of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine in step 3 of synthesis example 1.

Compound 37: mass analysis (FAB) M/z502[ (M + H)⁺]. Theoretical value of elemental analysis C₃₅H₂₆N₄: c (83.64%) H (5.21%) N (11.15%) found: c (83.53%) H (5.27%) N (11.18%).

¹H NMR(500MHz，CDCl₃)：8.55(d，1H)，7.95(d，4H)，7.78～7.72(m，3H)，7.48(t，2H)，7.11(d，4H)，7.05～6.95(m，6H)，2.72(s，6H)。

Synthesis example 5: synthesis of Compound 22

[ reaction formula 2-1]

Step 1: diphenylamine (10.0g, 59.09mmol), 1, 2-dibromobenzene (27.88g, 118.19mmol), sodium tert-butoxide (6.814g, 70.908mmol), palladium acetate (0.663g, 2.95mmol) and tri-tert-butylphosphine (1.19g, 5.91mmol) were dissolved in 300ml of toluene, and then oxygen in the solution was removed by nitrogen bubbling. After removal of oxygen, the loop was stirred for 24 hours. After the reaction solution was extracted with dichloromethane, column chromatography was performed using a dichloromethane/hexane mixed solvent as a developing solvent to obtain 12.21g of intermediate 22-1.

Intermediate 22-1: mass analysis (El) M/z 324[ (M + H)⁺]。

[ reaction formula 2-2]

Step 2: after intermediate 22-1(10g, 30.84mmol), 4,4,4 ', 5,5, 5' -octamethyl-2, 2 '-bis (1,3, 2-dioxaborolan) (11.74g, 46.26mmol), potassium acetate (9.08g, 92.52mmol), 1' -bis (diphenylphosphino) dipentaferropalladium (2) dichloride dichloromethane complex (0.76g, 0.93mmol) were dissolved in 180ml of 1, 4-dioxane, the solution was purged by nitrogen bubblingOxygen of (2). After removal of oxygen, the loop was stirred for 24 hours. After the reaction solution was extracted with dichloromethane, column chromatography was performed using a dichloromethane/hexane mixed solvent as a developing solvent to obtain 4.58g of intermediate 22-2.

Intermediate 22-2:mass analysis (El) M/z 371[ (M + H)⁺]。

[ reaction formulae 2 to 3]

Step 3: intermediate 22-2(3g, 8.08mmol), 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (2.59g, 9.75mmol) and tetrakistriphenylphosphine palladium (0) (0.28g, 0.24mmol) were placed in a mixed solvent of 60ml of tetrahydrofuran and 20ml of potassium phosphate 2M solution, and then refluxed for 24 hours. After the reaction solution was extracted with dichloromethane, column chromatography was performed using a dichloromethane/hexane mixed solvent as a developing solvent, and finally sublimation was performed to obtain 3.08g of pure white solid compound 22.

Compound 22: yield: 86% Mass analysis (EI) M/z 476[ (M + H)⁺]. Theoretical value of elemental analysis C₃₃H₂₄N₄: c (83.17%) H (5.08%) N (11.76%). Measurement value: c (82.16%) H (5.12%) N (11.77%).¹H NMR(500MHz，CDC₁₃)：δ8.83(d，1H)，8.51(d，4H)，8.05(d，1H)，7.64～7.61(m，2H)，7.57～7.53(m，3H)，7.46(t，4H)，7.41(d，2H)，7.09～7.04(m，5H)，6.83～6.79(m，2H)。

Synthesis example 6: synthesis of Compound 23

[ reaction formula 3]

Compound 23 was obtained in 78% yield by the same method as in Synthesis example 5, except that di-p-tolylamine was used in place of diphenylamine in step 1 of Synthesis example 5, and 2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) -N, N-di-p-tolylaniline obtained in step 2 was used in step 3.

Compound 23: mass analysis (EI) M/z504[ (M + H)⁺]. Theoretical value of elemental analysis C₃₅H₂₈N₄: c (83.30%) H (5.59%) N (11.10%) found: c (83.32%) H (5.66%) N (11.05%).¹H NMR(500MHz，CDCl₃)：8.52(d，4H)，7.95(d，1H)，7.56(t，2H)，7.53～7.45(m，2H)，7.38～7.32(m，2H)，6.92(d，4H)，6.85(d，4H)。

Synthesis example 7: synthesis of Compound 36

[ reaction formula 4-1]

(2- (carbazol-9-yl) benzene) boronic acid (10g, 34.83mmol), 2, 4-dichloro-6-phenyl-1, 3, 5-triazine (7.87g, 34.83mmol), palladium tetrakistriphenylphosphine (0) (4.02g, 3.48mmol) and potassium phosphate (14.44g, 104.49mmol) were placed in 60ml of tetrahydrofuran and 20ml of distilled water, followed by stirring under reflux for 24 hours. After the reaction solution was extracted with dichloromethane, column chromatography was performed using a dichloromethane/hexane mixed solvent as a developing solvent to obtain 7.99g of intermediate 36-1.

Intermediate 36-1: mass analysis (El) M/z 432[ (M + H)⁺]。

[ reaction formula 4-2]

Intermediate 36-1(3g, 6.94mmol) and copper cyanide (2.18g, 24.31mmol) were dissolved in 50ml of N-methyl-2-pyrrolidone and the oxygen in the solution was removed by nitrogen bubbling. After removal of oxygen, the loop was stirred for 24 hours. After the reaction solution was extracted with dichloromethane, column chromatography was performed using a dichloromethane/hexane mixed solvent as a developing solvent to obtain 2.49g of compound 36.

Compound 36: mass analysis (EI) M/z423[ (M + H)⁺]. Theoretical value of elemental analysis C₂₈H₁₇N₅: c (79.42%) H (4.05%) N (16.54%) found: c (79.43%) H (4.07%) N (16.51%).¹H NMR(500MHz，CDCl₃)：8.41(d，1H)，8.02(d，2H)，7.85(t，1H)，7.75～7.70(m，2H)，7.36～7.29(m，5H)，7.22(t，2H)，7.51(d，2H)，7.10(t，2H)。

[ reaction formula 5]

In the reaction formula 5, in R₁And R₂In the case of both hydrogen is compound 61, in R₁Is hydrogen, R₂When methyl is present, it is compound 63.

Synthesis example 8: synthesis of Compound 61

Step 1: 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (5.0g, 18.67mmol), (2-fluorophenyl) boronic acid (3.92g, 28.01mmol), palladium (0) tetrakistriphenylphosphine (2.15g, 1.86mmol) and potassium carbonate (7.74g, 56.03mmol) were dissolved in 120ml of toluene, 60ml of ethanol and 90ml of distilled water (D.W), and then oxygen in the solution was removed by nitrogen bubbling. After removing oxygen, the mixture was stirred at room temperature for 1 hour and then stirred at 130 ℃ for 15 hours by circulation. Then, the reaction solution was subjected to solvent removal by a rotary evaporator (rota evaporator) and vacuum drying was performed. After the dried mixture was extracted with methylene chloride, column chromatography was performed using a methylene chloride/hexane mixed solvent as a developing solvent to obtain 5.4g of 2- (2-fluorophenyl) -4, 6-diphenyl-1, 3, 5-triazinyl.

2- (2-fluorophenyl) -4, 6-diphenyl-1, 3, 5-triazine: mass analysis (EI) M/z327[ (M + H)⁺]¹H NMR(500MHz，CDCl₃)：8.76(d，4H)，8.48(t，1H)，7.62(t，3H)，7.56(t，4H)，7.35(t，1H)，7.27(t，1H)。

Step 2: 2- (2-fluorophenyl) -4, 6-diphenyl-1, 3, 5-triazine (1.00g, 3.05mmol), indole (0.89g, 7.63mmol) and tert-butylAfter mixing the sodium alkoxide (0.73g, 7.63mmol) with 100ml of dimethylformamide solvent, the mixture was refluxed at 160 ℃ for 24 hours. After the reaction solution was extracted with dichloromethane, the reaction solution was purified by column chromatography using a dichloromethane/hexane mixed solvent as a developing solvent, and finally purified by sublimation to obtain 0.63g of a yellow solid compound 61.

Compound 61: yield: 49.5% mass analysis (EI) M/z 424[ (M + H)⁺]. Theoretical value of elemental analysis C₂₉H₂₀N₄: c (82.05%) H (4.75%) N (13.20%) found: c (81.98%) H (4.77%) N (13.11%).¹H NMR(500MHz，CDCl₃)：8.42(d，1H)，8.16(d，4H)，7.73(t，1H)，7.66(t，2H)，7.61(d，1H)，7.50(t，2H)，7.38(t，4H)，7.31(d，1H)，7.19～7.13(m，2H)，7.07(d，1H)，6.53(d，1H)。

Synthesis example 9: synthesis of Compound 63

In a similar manner to step 2 of Synthesis example 8 except that 2- (2-fluorophenyl) -4, 6-diphenyl-1, 3, 5-triazine (1.50g, 4.58mmol) obtained in step 1 of Synthesis example 8, 3-methylindole (1.50g, 11.45mmol) and sodium tert-butoxide (1.10g, 11.45mmol) were mixed with 100ml of a dimethylformamide solvent, 1.17g of compound 63 was obtained.

Compound 63: yield: 58.07%, Mass analysis (EI) M/z 438[ (M + H)⁺]. Theoretical value of elemental analysis C₃₀H₂₂N₄: c (82.17%) H (5.06%) N (12.78%), found: c (82.22%) H (4.97%) N (12.69%).¹H NMR(500MHz，CDCl₃)：8.43(d，1H)，8.20(d，4H)，7.71(t，1H)，7.62(t，2H)，7.52(t，3H)，7.39(t，4H)，7.19～7.17(m，1H)，7.10～6.94(m，2H)，6.94(s，1H)，2.26(s，3H)。

Synthesis example 10: synthesis of Compound 52

[ reaction formula 6]

2- (2-fluorophenyl) -4, 6-diphenyl-1, 3, 5-triazine (1.00g, 3.05mmol), 5H-benzofuran [3,2-c ] carbazole (0.98g, 3.82mmol) and sodium hydride (0.10g, 3.90mmol) were mixed with 100ml of a dimethylformamide solvent, and then circulated at 160 ℃ for 24 hours. After the reaction solution was extracted with dichloromethane, column chromatography was performed using a dichloromethane/hexane mixed solvent as a developing solvent, and finally sublimation was performed to obtain 1.35g of the solid compound 52.

Compound 52: yield: 78.4% Mass analysis (EI) M/z565[ (M + H)⁺]。¹H NMR(300MHz，DMSO)：7.16～7.26(m，6H)，7.34～7.51(m，6H)，7.82(d，1H)，7.88～7.99(m，6H)，8.03～8.31(m，3H)，8.30(d，lH)，8.60(d，lH)。

Synthesis example 11: synthesis of Compound 67

[ reaction formula 7]

9- (2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) benzene) carbazole (8.0g, 27.9mmol), 2, 4-dichloro-6-phenyl-1, 3, 5-triazine (3.0g, 13.3mmol), and tetrakistriphenylphosphine palladium (0) (1.53g, 1.33mmol) were put in a mixed solvent of 100ml of tetrahydrofuran and 40ml of potassium phosphate 2M solution, and then circulated for 24 hours. After the reaction solution was extracted with dichloromethane, column chromatography was performed using a dichloromethane/hexane mixed solvent as a developing solvent, and finally sublimation was performed to obtain a pure white solid compound with a yield of 71%.

Compound 67: mass analysis (EI) M/z639[ (M + H)⁺]. Theoretical value of elemental analysis C₄₅H₂₉N₅C (84.48%) H (4.57%) N (10.95%) found: c (84.48%) H (4.57%) N (10.86%).¹H NMR(500MHz，CDC1₃)：δδ6.79(d，2H，J＝8Hz)，6.895(t，2H，J＝15Hz)，6.965(d，4H，J＝8Hz)，7.163～7.217(m，5H)，7.263(t，4H，J＝15Hz)，7.478(t，2H，J＝15Hz)，7.563(d，2H，J＝8Hz)，7.659～7.708(m，4H)，7.986(d，4H，J＝8Hz)。

Synthesis example 12: synthesis of Compound 83

[ reaction formula 8]

9- (2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) benzene) carbazole (15.4g, 53.7mmol), cyanuric chloride (3.0g, 16.3mmol), tetrakistriphenylphosphine palladium (0) (2.82g, 2.44mmol) were placed in a mixed solvent of 100ml of tetrahydrofuran and 40ml of potassium phosphate 2M solution and then circulated for 24 hours. After the reaction solution was extracted with dichloromethane, column chromatography was performed using a dichloromethane/hexane mixed solvent as a developing solvent, and finally sublimation purification yielded a pure white solid with a yield of 37%.

Compound 83: mass analysis (EI) M/z803[ (M + H)⁺]. Theoretical value of elemental analysis C₅₇H₃₆N₆: c (85.05%) H (4.51%) N (10.44%) found: c (85.07%) H (4.49%) N (10.45%).¹H NMR(500MHz，CDC1₃)：δ6.238(d，3H，J＝8Hz)，6.558(d，6H，J＝8Hz)，6.968(t，3H，J＝15Hz)，7.216～7.261(m，12H)，7.341(d，3H，J＝8Hz)，7.485(t，3H，J＝15Hz)，8.10(d，6H，J＝7Hz)。

Production example 1: fabrication of delayed fluorescence organic light emitting diodes

(ITO/PEDOT: PSS/TAPC/mCP/mCP: Compound 1/TSPO1/TPBi/LiF/Al)

The glass substrate on which ITO was deposited as an anode was washed under ultrasonic waves using pure water and isopropyl alcohol for 30 minutes. The washed ITO was surface-treated using ultraviolet light of short wavelength and then treated to PEDOT: PSS (poly (3, 4-ethylenedioxythiophene): poly (styrene sulfonate)) is spin-coated to form a hole injection layer. Then, at 1X 10^-6TAPC (l, l-Bis [4- [ N, N' -Di (p-)) is treated at a rate of 0.1nm/s under the pressure of torrtolyl)Amino]phenyl]Cyclohexane) was deposited to form a20 nm hole transport layer. Then, at 1X 10^{- 6}mCP (N, N-dicarbazolyl-3, 5-bezene) was deposited at a rate of 0.1nm/s under torr pressure to form a10 nm exciton blocking layer. Then, at 1X 10^-6A light-emitting layer doped with 5% of a dopant in the host was formed by co-deposition of mCP as a host substance at a rate of 0.1nm/s and compound 1 as a delayed fluorescence dopant synthesized in synthesis example 1 at a rate of 0.005nm/s under a pressure of torr. At 1X 10^-6Under the pressure of an torr, TSPO1(diphenylphosphine oxide-4- (triphenylsilylyl) phenyl) and 1,3, 5-tri (N-benzimidazole-2-yl) benzene (TPBi) are sequentially deposited at the speed of 0.1nm/s to form an exciton blocking layer (exiton blocking layer) and an electron transport layer (electron transport layer) with the thickness of 5nm and 30nm respectively. Then, at 1X 10^-6LiF, an electron injection material, was deposited at a rate of 0.01nm/s under a pressure of torr to form an electron injection layer of 1 nm. Then, at 1X 10^-6Al is deposited at a rate of 0.5nm/sec under a pressure of torr to form a cathode of 100nm, thereby forming an organic light emitting diode. After forming the element, the element was sealed with a glass cover glass using a CaO moisture absorbent (CaO moisture).

The compound 1 was applied as a fluorescent dopant of an organic light-emitting element, and showed a quantum efficiency of 9.3%, a current efficiency of 14.6cd/a, and a power efficiency of 7.6lm/W at a voltage of 6V, and also showed x-0.15 and y-0.22 with respect to the chromaticity coordinates of CIE1931, thereby showing excellent blue emission characteristics. This result is far beyond the limit of the fluorescent material that is 5% (light extraction efficiency 20%) of the maximum external quantum efficiency that can be generated from a general fluorescent element, and thus can be a direct proof of the transition between triplet energy and singlet energy systems by thermal activation delayed fluorescence characteristics.

Production example 2: fabrication of delayed fluorescence organic light emitting diodes

(ITO/PEDOT: PSS/TAPC/mCP/mCP: Compound 2/TSPO1/TPBi/LiF/Al)

An organic light-emitting diode was produced in the same manner as in production example 1, except that the compound 2 synthesized in synthesis example 2 was used as a delayed fluorescence dopant.

The organic light emitting diode according to production example 2 showed excellent blue emission characteristics by applying compound 2 as a light emitting dopant of a fluorescent device, thereby showing a quantum efficiency of 14.7%, a current efficiency of 30.9cd/a, and a power efficiency of 14.9lm/W at a voltage of 6.5V, and further showing x of 0.17 and y of 0.34 based on the chromaticity coordinates of CIE 1931.

Production example 3: fabrication of delayed fluorescence organic light emitting diodes

(ITO/PEDOT: PSS/TAPC/mCP/mCP: Compound 3/TSPO1/TPBi/LiF/Al)

An organic light-emitting diode was produced in the same manner as in production example 1, except that the compound 3 synthesized in synthesis example 3 was used as a delayed fluorescence dopant.

The organic light emitting diode according to production example 3 showed excellent blue emission characteristics by applying compound 3 as a light emitting dopant of a fluorescent device, thereby showing a quantum efficiency of 12.3%, a current efficiency of 24.0cd/a, and a power efficiency of 12.6lm/W at a voltage of 6V, and further showing x of 0.16 and y of 0.30 based on the chromaticity coordinates of CIE 1931.

Production example 4: fabrication of delayed fluorescence organic light emitting diodes

(ITO/PEDOT: PSS/TAPC/mCP/mCP: Compound 37/TSPO1/TPBi/LiF/Al)

An organic light-emitting diode was produced by the same method as in production example 1, except that the compound 37 synthesized in synthesis example 4 was used as a delayed fluorescence dopant.

The organic light emitting diode according to production example 4, which used compound 37 as a light emitting dopant of a fluorescent device, showed 11.5% of quantum efficiency, 29.1cd/a of current efficiency, and 13.8lm/W of power efficiency at a voltage of 6V, and also showed excellent blue emission characteristics by showing x to 0.16 and y to 0.20 based on the chromaticity coordinates of CIE 1931.

Production example 5: fabrication of delayed fluorescence organic light emitting diodes

(ITO/PEDOT: PSS/TAPC/mCP/mCP: Compound 22/TSPO1/TPBi/LiF/Al)

An organic light-emitting diode was produced in the same manner as in production example 1, except that the compound 22 synthesized in synthesis example 5 was used as a delayed fluorescence dopant.

The organic light emitting diode according to production example 5, which used compound 22 as a light emitting dopant of a fluorescent device, showed a quantum efficiency of 17.2%, a current efficiency of 45.0cd/a, and a power efficiency of 31.4lm/W at a voltage of 9V, and also showed excellent blue-green emission characteristics by showing x of 0.21 and y of 0.45 on the basis of the chromaticity coordinates of CIE 1931.

Production example 6: fabrication of delayed fluorescence organic light emitting diodes

(ITO/PEDOT: PSS/TAPC/mCP/mCP: Compound 52/TSPO1/TPBi/LiF/Al)

An organic light-emitting diode was produced in the same manner as in production example 1, except that the compound 52 synthesized in synthesis example 10 was used as a delayed fluorescence dopant.

The organic light emitting diode according to production example 6 showed excellent blue emission characteristics by applying compound 52 as a light emitting dopant of a fluorescent device, thereby showing a quantum efficiency of 12.5%, a current efficiency of 19.8cd/a, and a power efficiency of 17.8lm/W at a voltage of 9V, and further showing x of 0.15 and y of 0.20 based on the chromaticity coordinates of CIE 1931.

Production example 7: fabrication of delayed fluorescence organic light emitting diodes

(ITO/PEDOT: PSS/TAPC/mCP/mCP: Compound 23/TSPO1/TPBi/LiF/Al)

An organic light-emitting diode was produced by the same method as in production example 1, except that the compound 23 synthesized in synthesis example 6 was used as a delayed fluorescence dopant.

The organic light emitting diode according to production example 7 showed excellent green emission characteristics by applying compound 23 as a light emitting dopant of a fluorescent device, showing a quantum efficiency of 16.3%, a current efficiency of 54.6cd/a, and a power efficiency of 38.2lm/W at a voltage of 9V, and further showing x of 0.35 and y of 0.58 based on the chromaticity coordinates of CIE 1931.

Production example 8: fabrication of delayed fluorescence organic light emitting diodes

(ITO/PEDOT: PSS/TAPC/mCP/mCP: Compound 36/TSPO1/TPBi/LiF/Al)

An organic light-emitting diode was manufactured by the same method as manufacturing example 1, except that the compound 36 synthesized by synthesis example 7 as a delayed fluorescence doping substance was used.

The organic light-emitting diode according to production example 8, which used compound 36 as a light-emitting dopant of a fluorescent device, showed 11.7% of quantum efficiency, 26.9cd/a of current efficiency, and 10.4lm/W of power efficiency at a voltage of 6V, and also showed excellent orange light-emitting characteristics, with x being 0.55 and y being 0.45, based on the chromaticity coordinates of CIE 1931.

Production example 9: fabrication of delayed fluorescence organic light emitting diodes

(ITO/PEDOT: PSS/TAPC/mCP/mCP: Compound 67/TSPO1/TPBi/LiF/Al)

An organic light-emitting diode was produced in the same manner as in production example 1, except that the compound 67 synthesized in synthesis example 11 was used as a delayed fluorescence dopant.

The organic light-emitting diode according to production example 9, which used compound 67 as a light-emitting dopant of a fluorescent device, exhibited a quantum efficiency of 12.2%, a current efficiency of 18.5cd/a, and a power efficiency of 6.47lm/W at a voltage of 8V, and also exhibited excellent blue emission characteristics, as x was 0.17 and y was 0.21 with respect to the chromaticity coordinates of CIE 1931.

Production example 10: delayed fluorescence organic emissionFabrication of photodiodes

(ITO/PEDOT: PSS/TAPC/mCP/mCP: Compound 83/TSPO1/TPBi/LiF/Al)

An organic light-emitting diode was produced in the same manner as in production example 1, except that the compound 83 synthesized in synthesis example 12 was used as a delayed fluorescence dopant.

The organic light-emitting diode according to production example 9, which used compound 83 as a light-emitting dopant of a fluorescent device, showed 14.9% of quantum efficiency, 23.0cd/a of current efficiency, and 9.57lm/W of power efficiency at a voltage of 8V, and also showed excellent blue emission characteristics by showing x to 0.15 and y to 0.22 based on the chromaticity coordinates of CIE 1931.

Comparative example 1: fabrication of delayed fluorescence organic light emitting diodes

(ITO/PEDOT：PSS/TAPC/mCP/mCP：CC2TA/TSPO1/TPBi/LiF/Al)

An organic light-emitting diode was produced by the same method as in production example 1, except that 2, 4-bis 3- (9H-carbazol-9-yl) -9H-carbazol-9-yl-6-phenyl-1, 3, 5-triazine (CC2TA) reported in the literature (letters of applied physics (APPLIED PHYSICS LETTERS)101, 093306(2012)) was used as a fluorescent dopant.

The organic light emitting diode according to the comparative example, in which CC2TA was used as a light emitting dopant of a fluorescent device, showed a quantum efficiency of 11.5%, a current efficiency of 29.1cd/a, and a power efficiency of 13.8lm/W at a voltage of 6V, and also showed x of 0.20 and y of 0.44 based on the chromaticity coordinates of CIE 1931.

Through the above production examples 1 to 10, the light-emitting layer was constituted using a thermally activated delayed fluorescence compound, thereby producing organic light-emitting diodes of blue (production examples 1 to 4,6, 9, 10), green (production examples 5 and 7), and red (production example 8). It is known that these organic light emitting diodes each show a quantum efficiency exceeding 5% (light extraction efficiency 20%) of the maximum external quantum efficiency that can be generated from a general fluorescent element, and this indicates that the compound according to the present embodiment used as a light emitting dopant enables efficient intersystem transition of triplet energy to singlet energy by thermally activating delayed fluorescence characteristics. Meanwhile, the organic light emitting diode according to comparative example 1 using CC2TA, which is well known as a conventional delayed fluorescence emitting material, showed a quantum efficiency of 11.5%, whereas the organic light emitting diodes according to the present manufacturing examples 2 to 10 showed the same or significantly high quantum efficiency. In particular, the green light-emitting element (production example 5) showed a high quantum efficiency of 17% or more, and thus showed very excellent light emission characteristics as compared with the conventional fluorescent element.

Table 1 below shows the values calculated by the molecular calculation method for compound 1, comparative compound a, and comparative compound B produced according to synthesis example 1. Molecular calculations were calculated using the B3LYP method of density functional theory (density functional) using the Gaussian 09 program with 6-31G bases set.

[ Table 1]

Referring to table 1, compounds a and B were compared in a form similar to compound 1, in which an electron-donating carbazole and an electron-withdrawing group-diphenyltriazinyl group were linked to the meta-and para-positions. As a result, the singlet energy gradually increases in the ortho-meta-para form, and the triplet energy gradually decreases in the ortho-meta-para form. As a result, the difference between the singlet energy and the triplet energy is minimized in the ortho-form. The smaller the difference between the singlet energy and the triplet energy, the easier Reverse Intersystem Crossing (RISC) becomes, and further excellent thermally activated delayed fluorescence characteristics can be obtained.

Fig. 2 shows the molecular orbital function distribution for compound 1, comparative compound a and comparative compound B produced according to synthesis example 1. The molecular orbital function distribution was calculated using 6-31G basis set using the B3LYP method of density functional theory using the Gaussian 09 program.

In order to effectively show the fluorescence emission characteristics, the overlap interval between HOMO and LUMO should be maintained at a predetermined level, but it is calculated that HOMO and LUMO of ortho-, meta-, and para-forms overlap with a phenyl group as a central linking unit, and therefore, the fluorescence emission characteristics of the ortho-form are expected to be similar to those of other materials. This result is a strong evidence that the ortho-position form can effectively shift triplet energy formed during electroluminescence to the singlet-reverse system, and singlet excitons shifted by the reverse system can exhibit effective fluorescence, as compared with the meta-position or para-position form.

The present invention has been described in detail with reference to the preferred embodiments, but the present invention is not limited to the embodiments, and various changes and modifications can be made by those skilled in the art within the technical spirit and scope of the present invention.