阅读说明：本技术 用于有机电致发光器件的材料 (Material for organic electroluminescent device ) 是由 拉拉-伊莎贝尔·罗德里格斯 阿伦·莱克纳 克里斯托夫·普夫卢姆 阿梅尔·梅基奇 于 2019-09-09 设计创作，主要内容包括：本发明涉及包含空间位阻的荧光苝发光体化合物和敏化剂化合物的有机电致发光器件,以及涉及空间位阻的荧光苝发光体化合物。(The present invention relates to organic electroluminescent devices comprising sterically hindered fluorescent perylene emitter compounds and sensitizer compounds, and to sterically hindered fluorescent perylene emitter compounds.)

1. An electronic device comprising an anode, a cathode and at least one organic layer comprising a sterically hindered fluorescent perylene emitter compound, characterized in that the fluorescent perylene emitter compound is represented by formula (I) below and in that the organic layer or a layer adjacent to the organic layer at the anode or cathode side comprises a sensitizer compound selected from compounds exhibiting delayed fluorescence or phosphorescent compounds,

wherein

R¹To R¹²Each of which is selected, identically or differently, from H, straight-chain alkyl or alkoxy groups having from 3 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having from 3 to 20 carbon atoms, alkenyl or alkynyl groups having from 3 to 20 carbon atoms, preferably aralkyl groups having from 7 to 60 carbon atoms, where the abovementioned groups may each be substituted by one or more R²⁰Substituted by radicals and in which one or more CH groups of the above radicals are present₂The radical may be substituted by Si (R)²⁰)₂、Ge(R²⁰)₂、Sn(R²⁰)₂、C＝O、C＝S、C＝Se、C＝NR²⁰、P(＝O)(R²⁰)、SO、SO₂、NR²⁰-O-, -S-, -COO-or-CONR-²⁰-substituted, and wherein one or more H atoms in the above groups may be replaced by D, F, Cl, Br, I, CN or NO₂Alternatively, or as an aromatic ring system having from 5 to 60 aromatic ring atoms which may in each case be substituted by one or more R²⁰Substituted by groups;

R²⁰selected, identically or differently on each occurrence, from H, D, F or a straight-chain alkyl group having from 1 to 40 carbon atoms, or a branched or cyclic alkyl group having from 3 to 40 carbon atoms, or an alkenyl or alkynyl group having from 2 to 40 carbon atoms, or an aralkyl group having from 7 to 40 carbon atoms, where each of the above groups may be substituted by one or more R²¹Substituted by radicals, or an aromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted in each case by one or more R²¹Is substituted by radicals in which two or more R are²⁰The radicals can be linked to form an aromatic ring system or a (poly) cycloalkyl radical, which can be substituted in each case by one or more R²¹Substituted by groups;

R²¹selected, identically or differently on each occurrence, from H, D, F, or a straight-chain alkyl group having from 1 to 20 carbon atoms, or a branched or cyclic alkyl group having from 3 to 20 carbon atoms, or an alkenyl or alkynyl group having from 2 to 20 carbon atoms, or an aromatic ring system having from 5 to 30 aromatic ring atoms, wherein two or more R are²¹The groups may be linked to form an aromatic ring system or a (poly) cycloalkyl group;

provided that R is¹To R¹²At least two, preferably three, more preferably four of the groups that are not located on the same phenyl ring of the perylene backbone are not H.

2. Electronic device according to claim 1, characterised in that said compound of formula (I) represents a compound of general formula (II)

Wherein

R²、R⁵、R⁸、R¹¹Each identically or differently selected from linear alkyl or alkoxy groups having 3 to 20 carbon atoms, branched or cyclic alkyl or alkoxy groups having 3 to 20 carbon atoms, alkenyl or alkynyl groups having 3 to 20 carbon atoms, preferably aralkyl groups having 7 to 60 carbon atoms, where the above groups may each be substituted by one or more R²⁰Substituted by radicals and in which one or more CH groups of the above radicals are present₂The radical may be substituted by Si (R)²⁰)₂、Ge(R²⁰)₂、Sn(R²⁰)₂、C＝O、C＝S、C＝Se、C＝NR²⁰、P(＝O)(R²⁰)、SO、SO₂、NR²⁰-O-, -S-, -COO-or-CONR-²⁰-substituted, and wherein one or more H atoms in the above groups may be replaced by D, F, Cl, Br, I, CN or NO₂Alternatively, or as an aromatic ring system having from 5 to 60 aromatic ring atoms which may in each case be substituted by one or more R²⁰Substituted by groups;

R²⁰selected, identically or differently on each occurrence, from H, D, F, or a straight-chain alkyl group having from 1 to 40 carbon atoms, or a branched or cyclic alkyl group having from 3 to 40 carbon atoms, or an alkenyl or alkynyl group having from 2 to 40 carbon atoms, or an aralkyl group having from 7 to 40 carbon atoms, where each of the above-mentioned groups may be substituted by one or more R²¹Substituted by radicals, or an aromatic ring system having 5 to 40 aromatic ring atoms, which may be substituted in each case by one or more R²¹Is substituted by radicals in which two or more R are²⁰The radicals can be linked to form an aromatic ring system or a (poly) cycloalkyl radical, which can be substituted in each case by one or more R²¹Substituted by groups;

R²¹selected, identically or differently on each occurrence, from H, D, F, or a straight-chain alkyl group having from 1 to 20 carbon atoms, or a branched or cyclic alkyl group having from 3 to 20 carbon atoms, or an alkenyl or alkynyl group having from 2 to 20 carbon atoms, or an aromatic ring system having from 5 to 40 aromatic ring atoms, wherein two or more R are²¹The groups may be linked to form an aromatic ring system or a (poly) cycloalkyl group.

3. Electronic device according to claim 1 or 2, characterised in that R²、R⁵、R⁸、R¹¹Each of which is selected, identically or differently, from a linear, branched or cyclic alkyl radical having from 4 to 10 carbon atoms, a linear, branched or cyclic alkoxy radical having from 3 to 10 carbon atoms, an aralkyl radical having from 7 to 30 carbon atoms, where the abovementioned radicals may each be substituted by one or more R²⁰Substituted by radicals and in which one or more H atoms in the abovementioned radicals may be replaced by D, F, Cl or CN, or an aromatic ring system having from 6 to 30 aromatic ring atoms which may in each case be substituted by one or more R²⁰Substituted by groups;

R²⁰selected, identically or differently at each occurrence, from D, F, or a straight-chain alkyl group having from 1 to 20 carbon atoms, or a branched chain having from 3 to 20 carbon atomsOr a cyclic alkyl group, or an alkenyl or alkynyl group having 2 to 20 carbon atoms, wherein each of the foregoing groups may be substituted with one or more R²¹Substituted by radicals, or an aromatic ring system having 5 to 30 aromatic ring atoms, which may be substituted in each case by one or more R²¹Is substituted by radicals in which two or more R are²⁰The radicals can be linked to form an aromatic ring system or a (poly) cycloalkyl radical, which can be substituted in each case by one or more R²¹Substituted by groups;

R²¹selected, identically or differently on each occurrence, from H, D, F, or a straight-chain alkyl group having from 1 to 10 carbon atoms, or a branched or cyclic alkyl group having from 3 to 10 carbon atoms, or an alkenyl or alkynyl group having from 2 to 10 carbon atoms, or an aromatic ring system having from 5 to 30 aromatic ring atoms, wherein two or more R are²¹The groups may be linked to form an aromatic ring system or a (poly) cycloalkyl group.

4. Electronic device according to any of claims 1 to 3, characterised in that R²、R⁵、R⁸、R¹¹Each, identically or differently, is selected from

A branched or cyclic alkyl group represented by the following general formula (R-a)

Wherein

R²²、R²³、R²⁴Selected, identically or differently on each occurrence, from H, a straight-chain alkyl radical having from 1 to 10 carbon atoms, or a branched or cyclic alkyl radical having from 3 to 10 carbon atoms, where each of the abovementioned radicals may be substituted by one or more R²⁵Is substituted by radicals, and wherein R²²、R²³、R²⁴R of two or all of the radicals²²、R²³、R²⁴The groups may be linked to form a (poly) cycloalkyl groupMay be substituted by one or more R²⁵Substituted by groups;

R²⁵selected, identically or differently at each occurrence, from a linear alkyl group having from 1 to 10 carbon atoms or a branched or cyclic alkyl group having from 3 to 10 carbon atoms;

provided that R is present at each occurrence²²、R²³And R²⁴At least one of the radicals is not H, with the proviso that R is present at each occurrence²²、R²³And R²⁴Having a total of at least 4 carbon atoms in the group and with the proviso that if R is present at each occurrence²²、R²³、R²⁴Two of the groups are H, then the remaining groups are not straight chain;

or a branched or cyclic alkoxy group represented by the following general formula (R-b)

Wherein

R²⁶、R²⁷、R²⁸Selected, identically or differently on each occurrence, from H, a straight-chain alkyl radical having from 1 to 10 carbon atoms, or a branched or cyclic alkyl radical having from 3 to 10 carbon atoms, where each of the abovementioned radicals may be substituted by one or more R as defined above²⁵Is substituted by radicals, and wherein R²⁶、R²⁷、R²⁸R of two or all of the radicals²⁶、R²⁷、R²⁸The groups may be linked to form a (poly) cycloalkyl group which may be substituted by one or more R as defined above²⁵Substituted by groups;

provided that R is present at each occurrence²⁶、R²⁷And R²⁸Only one of the groups may be H;

or an aralkyl group represented by the following general formula (R-c)

Wherein

R²⁹、R³⁰、R³¹Selected, identically or differently on each occurrence, from H, a straight-chain alkyl radical having from 1 to 10 carbon atoms or a branched or cyclic alkyl radical having from 3 to 10 carbon atoms, where each of the abovementioned radicals may be substituted by one or more R³²Substituted by radicals, or an aromatic ring system having from 6 to 30 aromatic ring atoms, which may be substituted in each case by one or more R³²Is substituted by radicals, and wherein R²⁹、R³⁰、R³¹Two or all of the groups may be joined to form a (poly) cycloalkyl group or an aromatic ring system, each of which may be substituted with one or more R³²Substituted by groups;

R³²selected, identically or differently at each occurrence, from a straight-chain alkyl group having from 1 to 10 carbon atoms, or a branched or cyclic alkyl group having from 3 to 10 carbon atoms, or an aromatic ring system having from 6 to 24 aromatic ring atoms;

provided that R is present at each occurrence²⁹、R³⁰And R³¹At least one of the radicals is not H and R at each occurrence²⁹、R³⁰And R³¹At least one of the radicals is or comprises an aromatic ring system having at least 6 aromatic ring atoms;

or an aromatic ring system represented by the following general formula (R-d)

Wherein

R⁴⁰To R⁴⁴Selected, identically or differently on each occurrence, from H, a straight-chain alkyl radical having from 1 to 10 carbon atoms, or a branched or cyclic alkyl radical having from 3 to 10 carbon atoms, where each of the abovementioned radicals may be substituted by one or more R³²Substituted by radicals, or an aromatic ring system having from 6 to 30 aromatic ring atoms, which may be substituted in each case by one orPlural R³²Is substituted by radicals, and wherein R⁴⁰To R⁴⁴Two or more of the groups may be joined to form a (poly) cycloalkyl group or an aromatic ring system, each of which may be substituted by one or more R as defined above³²And (4) substituting the group.

5. Electronic device according to any of claims 1 to 4, characterised in that R²、R⁵、R⁸、R¹¹The same is true.

6. Electronic device according to any one of claims 1 to 5, characterised in that the compound of formula (I) represents a compound of general formula (III) or (IV)

Wherein

R⁴⁰、R⁴²、R⁴⁴Selected, identically or differently on each occurrence, from H, a straight-chain alkyl radical having from 1 to 10 carbon atoms, or a branched or cyclic alkyl radical having from 3 to 10 carbon atoms, where each of the abovementioned radicals may be substituted by one or more R³²Substituted by radicals, or an aromatic ring system having from 6 to 30 aromatic ring atoms, which may be substituted in each case by one or more R³²Substituted by groups; wherein R is³²The same as defined in claim 4;

provided that R is⁴⁰、R⁴²、R⁴⁴Is not H;

or

Wherein

R⁴¹、R⁴³Selected, identically or differently on each occurrence, from H, linear alkanes having 1 to 10 carbon atomsA radical group, or a branched or cyclic alkyl group having 3 to 10 carbon atoms, wherein each of the above groups may be substituted by one or more R³²Substituted by radicals, or an aromatic ring system having from 6 to 30 aromatic ring atoms, which may be substituted in each case by one or more R³²Substituted by groups; wherein R is³²The same as defined in claim 4;

provided that R is⁴¹、R⁴³Is not H.

7. Electronic device according to any of claims 1 to 6, characterised in that

R⁴²Selected, identically or differently on each occurrence, from H, a straight-chain alkyl radical having from 1 to 10 carbon atoms or a branched or cyclic alkyl radical having from 3 to 10 carbon atoms, where each of the abovementioned radicals may be substituted by one or more R³²Substituted by groups;

R⁴⁰、R⁴⁴selected, identically or differently on each occurrence, from aromatic ring systems having from 6 to 30 aromatic ring atoms which may in each case be substituted by one or more R³²Substituted by groups; wherein R is³²As defined in claim 4.

8. Electronic device according to any of claims 1 to 6, characterised in that

R⁴⁰、R⁴²、R⁴⁴Selected, identically or differently on each occurrence, from aromatic ring systems having from 6 to 30 aromatic ring atoms which may in each case be substituted by one or more R³²Substituted by groups; wherein R is³²As defined in claim 4.

9. Electronic device according to any one of claims 1 to 8, characterized in that the compound of formula (I) represents any one of the compounds of general formula (IIIa), (IIIb) or (IIIc)

Wherein

Wherein in each of formulae (IIIa), (IIIb) and (IIIc) with-R³²The indicated phenyl radicals being unsubstituted or substituted by one or more R³²Substituted by groups;

R⁴²and R⁴⁴Selected, identically or differently on each occurrence, from H, a straight-chain alkyl radical having from 1 to 10 carbon atoms or a branched or cyclic alkyl radical having from 3 to 10 carbon atoms, where each of the abovementioned radicals may be substituted by one or more R³²Substituted by groups; wherein R is³²As defined in claim 4.

10. Electronic device according to any of claims 1 to 6, characterised in that

R⁴²Selected, identically or differently on each occurrence, from H, a straight-chain alkyl radical having from 1 to 10 carbon atoms, or a branched or cyclic alkyl radical having from 3 to 10 carbon atoms, or an aromatic ring system having from 6 to 30 aromatic ring atoms, which radicals or aromatic ring systems may in each case be substituted by one or more R³²Substituted by groups;

R⁴⁰、R⁴⁴is identically selected on each occurrence from straight-chain alkyl groups having from 1 to 10 carbon atoms or branched or cyclic alkyl groups having from 3 to 10 carbon atoms, which groups may in each case be substituted by one or more R³²Substituted by groups; and R is³²As defined in claim 4.

11. Electronic device according to any of claims 1 to 10, characterized in that the organic layer comprises a sterically hindered fluorescent emitter compound and the sensitizer compound, preferably the light emitting layer.

12. Electronic device according to any of claims 1 to 11, characterized in that the organic layer comprises the sterically hindered fluorescent emitter compound, the sensitizer compound and at least one organic functional material selected from the group consisting of HTM, HIM, HBM, p-type dopant, ETM, EIM, EBM, n-type dopant, fluorescent emitter, phosphorescent emitter, delayed fluorescent material, host material, wide band gap material, quantum material (preferably quantum dots), preferably the light emitting layer.

13. A compound of formula (III) or (IV) as defined in claim 6, characterised in that R is⁴⁰、R⁴²、R⁴⁴And R⁴¹、R⁴³The radicals are defined as follows:

R⁴⁰to R⁴⁴Selected, identically or differently on each occurrence, from H, a straight-chain alkyl radical having from 1 to 10 carbon atoms, or a branched or cyclic alkyl radical having from 3 to 10 carbon atoms, where each of the abovementioned radicals may be substituted by one or more R³²Substituted by radicals, or an aromatic ring system having 6 to 24 aromatic ring atoms, which may be substituted in each case by one or more R³²Substituted by groups; and is

R³²Selected, identically or differently at each occurrence, from a straight-chain alkyl group having from 1 to 10 carbon atoms, or a branched or cyclic alkyl group having from 3 to 10 carbon atoms, or an aromatic ring system having from 6 to 24 aromatic ring atoms.

14. A compound according to claim 13, characterized in that R⁴⁰、R⁴²、R⁴⁴The radicals are defined as follows:

R⁴²selected, identically or differently at each occurrence, from H, a straight-chain alkyl group having from 1 to 10 carbon atoms or a branched-chain alkyl group having from 3 to 10 carbon atoms;

R⁴⁰、R⁴⁴selected identically or differently on each occurrence from aromatic ring systems having from 6 to 24 aromatic ring atoms,the aromatic ring system may in each case be substituted by one or more R³²Substituted by groups;

R³²selected, identically or differently at each occurrence, from a straight-chain alkyl group having from 1 to 6 carbon atoms or a branched-chain alkyl group having from 3 to 6 carbon atoms.

15. A compound according to claim 13, characterized in that R⁴⁰、R⁴²、R⁴⁴The radicals are defined as follows:

R⁴⁰、R⁴²、R⁴⁴selected, identically or differently on each occurrence, from aromatic ring systems having 6 to 24 aromatic ring atoms which may in each case be substituted by one or more R³²Substituted by groups;

R³²selected, identically or differently at each occurrence, from a straight-chain alkyl group having from 1 to 6 carbon atoms or a branched-chain alkyl group having from 3 to 6 carbon atoms.

16. Compound according to any one of claims 13 to 15, characterized in that the compound of formula (III) represents any one of the compounds of general formula (IIId), (IIIe) or (IIIf)

Wherein

In each of formulae (IIId), (IIIe) and (IIIf), with-R³²The indicated phenyl radicals being unsubstituted or substituted by one or more R³²Substituted by groups;

R⁴²and R⁴⁴Is selected, identically or differently on each occurrence, from H, a linear alkyl radical having from 1 to 10 carbon atoms or a branched alkyl radical having from 3 to 10 carbon atoms, where each of the abovementioned radicalsFrom one or more R³²Substituted by groups; and is

R³²Selected, identically or differently at each occurrence, from a straight-chain alkyl group having from 1 to 6 carbon atoms or a branched-chain alkyl group having from 3 to 6 carbon atoms.

17. A compound according to claim 13, characterized in that R⁴⁰、R⁴²、R⁴⁴The radicals are defined as follows:

R⁴²selected, identically or differently on each occurrence, from H, a straight-chain alkyl radical having from 1 to 10 carbon atoms, or a branched-chain alkyl radical having from 3 to 10 carbon atoms, or an aromatic ring system having from 6 to 24 aromatic ring atoms, which radicals or aromatic ring systems may in each case be substituted by one or more R³²Substituted by groups;

R⁴⁰、R⁴⁴selected, identically or differently on each occurrence, from straight-chain alkyl radicals having from 1 to 10 carbon atoms or branched-chain alkyl radicals having from 3 to 10 carbon atoms, which radicals may in each case be substituted by one or more R³²Substituted by groups; and is

R³²Selected, identically or differently at each occurrence, from a straight-chain alkyl group having from 1 to 6 carbon atoms or a branched-chain alkyl group having from 3 to 6 carbon atoms.

18. A compound according to claim 17, characterized in that R is⁴⁰、R⁴²、R⁴⁴The radicals are defined as follows:

R⁴²identically selected at each occurrence from H, a straight-chain alkyl group having from 1 to 10 carbon atoms or a branched-chain alkyl group having from 3 to 10 carbon atoms,

R⁴⁰、R⁴⁴identically selected at each occurrence from a straight chain alkyl group having from 1 to 10 carbon atoms or a branched alkyl group having from 3 to 10 carbon atoms.

19. Composition comprising a compound according to one or more of claims 13 to 18 and at least one organic or inorganic functional material selected from HTM, HIM, HBM, p-type dopant, ETM, EIM, EBM, n-type dopant, fluorescent emitter, phosphorescent emitter, delayed fluorescent material, matrix material, host material, wide band gap material, quantum material (preferably quantum dots).

20. A formulation comprising at least one compound according to any one of claims 13 to 18 or a composition according to claim 19 and at least one solvent.

21. A process for the preparation of a compound of formula (III) according to any one of claims 13 to 18, characterized in that at least the following step a) is carried out:

a) organometallic couplings under Suzuki conditions between the 1-C, 5-C, 8-C and 11-C atoms of the perylene basic skeleton and a substituted or unsubstituted aromatic group Ar having 6 to 24 aromatic ring atoms, which is used as starting material Ar-X, where X is any desired suitable leaving group, preferably selected from halogen, boronic acid, boronic ester, tosylate or triflate.

22. Use of a compound according to any one of claims 13 to 18, or a composition according to claim 19, or a formulation according to claim 20, in an electronic device, preferably in an organic electroluminescent device.

23. An electronic device comprising the composition of claim 19, or the formulation of claim 20, or the compound of any one of claims 13 to 18.

24. Electronic device according to any one of claims 1 to 12 or 23, preferably an organic electroluminescent device selected from the group consisting of Organic Integrated Circuits (OIC), Organic Field Effect Transistors (OFET), Organic Thin Film Transistors (OTFT), Organic Light Emitting Transistors (OLET), Organic Solar Cells (OSC), organic optical detectors, organic photoreceptors, Organic Field Quench Devices (OFQD), organic light emitting electrochemical cells (OLEC, LEC, LEEC), organic laser diodes (O-lasers) and Organic Light Emitting Diodes (OLED).