KR20070100949A - Material for doped and undoped hole and electron transport layer - Google Patents

Abstract

The present invention relates to materials useful as an electron or hole transport or injection layer in organic electrooptic devices. The material can form or be part of an electrically conductive organic layer, suitable for the transport of so-called positive charges or holes. The inventive HTL compounds are intrinsically doped HTLs which allows their deposition with greater homogeneity and reproducibility than matrix compositions consisting of a matrix material and an admixed p-dopant.

Description

Materials for doped and undoped hole and electron transport layers {MATERIAL FOR DOPED AND UNDOPED HOLE AND ELECTRON TRANSPORT LAYER}

The present invention relates to a material useful as an hole or electron transport layer or as a dopant for a hole or electron transport layer and a hole or electron injection layer in an organic electrical device, preferably an electro-optical device. Materials useful as hole or electron transport layers (HTL and ETL, respectively) or hole or electron injection layers can form or be part of an electrically conductive organic layer, suitable for the transport of so-called positive charges or holes. Electro-optical devices for the teachings of the present invention include organic light emitting diodes (OLEDs), organic field effect transistors (OFETs), lasers and photovoltaic devices suitable for photovoltaic solar energy conversion.

In general, the electro-optical device includes a plurality of electrically conductive organic compounds stacked in layers disposed between the electrodes.

The general structure of the EL device in which the material of the present invention for the hole transport layer can be used is schematically shown in Figs.

In the case of OLEDs, for example, adjacent to an anode made of ITO (Indium Tin Oxide), a hole transport layer (HTL) is optionally disposed along with the intermediate hole injection layer (HBL). A light emitting layer is disposed next to the HTL, and the compound generally emits visible light with energy derived from excitons generated by simultaneous localization of electrons and holes on the same molecule in the light emitting layer. The electron transport layer is disposed adjacent to the transport layer and the light emitting layer, followed by a cathode (for example, Mg, LiF / Al, Ca, Ba).

In some cases, electron transport beyond the light emitting layer toward the anode may be blocked by an electron blocking layer disposed between the hole transport layer and the light emitting layer. As another option, the movement of holes beyond the light emitting layer toward the cathode can be blocked by a hole blocking layer disposed between the light emitting layer and the electron transport layer.

An electron injection layer may be disposed between the electron transport layer and the cathode. In addition, the electron transport layer or electron injection layer can be separated from the cathode by an electron conductive protective layer, thereby enabling the processing steps necessary for the application of the cathode to the electron injection layer.

Materials for the hole transport layer (HTL) are known from WO 2004/016711 A1, for example intrinsic HTL doped with F ₄ -TCNQ or α-NPD as m-MTDATA.

Zhou et al., Applied Physics Letters, Vol. 78, No. 4, p. 410-412 discloses an OLED utilizing a p-type doped amorphous hole injection layer. Polycrystalline phthalocyanine and amorphous 4,4 ', 4'-tris- (N, N-diphenyl) p-doped by co-deposition with F ₄ -TCNQ (tetrafluoro-tetracyano-quinodimethane) It has been found that the hole transport layer of both amine) triphenylamine (TDATA) yields a conductivity greater than that of the undoped matrix material. The Zhou et al. Document suggests that p-type doping of matrix materials not only leads to higher current densities even at lower voltages, but also to maximum electroluminescence (EL) efficiency at lower drive voltages.

As a result, OLEDs containing p-type doped HTL exhibit very low operating voltages and improved EL efficiency due to controlled doping.

Purpose of the Invention

It is an object of the present invention to provide a substitute for p-type doped HTL material for use in organic electro-optic devices.

In a preferred embodiment of the present invention, the present invention seeks to provide HTL materials suitable for organic electro-optical devices that exhibit improved properties such as increased stability at high temperatures.

Another object of the present invention is to provide a method for synthesizing a novel HTL material.

Overall description of the invention

The present invention achieves the above object by providing a material suitable for the hole and electron transport layer and / or injection layer in an organic electro-optical device according to formula (I):

[Formula I]

In the above formula (I), the Y moiety conjugates with the accessory moieties A ¹ and A ² and optionally includes a hetero atom, and represents a central carbon-based structure having, for example, 5 to 14 atoms. Residues A ¹ and A ² are electron accepting residues having one or more π-bonds and are conjugated through the Y moiety to form a conjugated or aromatic system. In addition to the accessory residues A ¹ and A ² , further electron donor groups may be conjugated to the Y moiety. In addition to residues A ¹ and A ² , one hole transporting moiety (HTM) or a plurality of HTMs is covalently bonded to the Y moiety by an intermediate (intervening) X moiety. At least one HTM may hole transport by a mechanism known as hole transport. However, at least one HTM is not conjugated to the Y moiety. The intermediate X moiety can be any carbon atom and / or heteroatom or chemical bond that includes a moiety suitable for unconjugating one or more HTMs to Y.

The number of HTMs ranges from at least one to the maximum number of non-conjugated bonds of the Y moiety. Since the example for the Y moiety is a 5- or 6-membered carbon ring optionally substituted with a hetero atom, the number of HTMs can be 1, 2, 3 or 4. If the Y moiety consists of one, two or more condensed rings, for example comprising a total of 5 to 14 carbon atoms or heteroatoms, the number of residues X and HTM may increase.

Examples for the Y moiety may be represented by the following embodiments of Formula I, wherein the formulas represented herein represent the Y moieties derivatized with Xs, A ¹ and A ² :

Another embodiment of Formula I is represented by compounds of Formulas II-VI:

In the formulas embodying Formula (I), X is exemplified as X ¹ , X ² , X ³ , X ^{4 to} X ⁸ , each of which is independently an intervening group or atom or chemical bond, at least one of which is HTM Intervening (middle) moieties are substituted.

In Formulas I-VI, the central carbon-based conjugate or aromatic moiety Y may substitute one or more carbon atoms to include heteroatoms such as N, O, S, Si, Ge.

Residues A ¹ and A ² are electron acceptor residues having one or more π-electron rich bonds, which can increase the density of π-electrons in the Y moiety. In addition to the accessory residue residues A ¹ and A ^2, additional electron donor groups may be conjugated to the Y moiety. In addition to residues A ¹ and A ² , one hole transport moiety (HTM) or a plurality of HTMs is covalently linked to the Y moiety by the intermediate X moiety. At least one HTM is capable of hole or electron transport. However, at least one HTM is not conjugated to the Y moiety.

Embodiments of Formulas II-VI are preferred compounds wherein HRM is a moiety capable of hole transport, for example tris-[(N, N-diaryl) amino] -triphenylamine, such as 4,4 ', 4 "-Tris [(N- (1-naphthyl) -N-phenyl-amino-triphenylamine] (1-TNATA) and its derivatives, 4,4 ', 4" -tris [(N- (2-naph Tyl) -N-phenyl-amino) -triphenylamine] (2-TNATA) or 4,4 ', 4 "-tris [(N- (3-methylphenyl) -N-phenyl-amino) -triphenylamine] (m-TDATA) and its derivatives, 4,4 ', 4 "-tris (carbazol-9-yl) triphenylamine; N, N, N', N'-tetra arylbenzidine, such as N, N, N ', N'-tetraphenyl benzidine and its derivatives, N', N'-bis (1-naphthyl) -N, N'-diphenyl-benzidine (α-NPD), N, N'-di (naphthalene- 2-yl) -N, N'-diphenyl-benzidine (β-NPD), 4,4'-bis (carbazol-9-yl) biphenyl (CBP) and its derivatives and their heteroatomic substituted homologues (Eg, thienyl derivatives, selenyl derivatives, furanyl derivatives); 4,4'-bis (2,2'-diphenylvinyl) -1,1 '-Biphenyl (DPVBI) triarylamine and derivatives thereof, 4,4'-bis (N, N-diarylamino) -terphenyl, 4,4'-bis (N, N-diarylamino)- Selected from the group containing quarterphenyl and its homologues and derivatives,

A ¹ and A ² are independently an electron donor moiety selected from, for example, a cyano group, -C (CN) ₂ , -NCN;

At least one of X ^{1 to} X ⁸ is chemically bonded to the hole transport moiety (HTM). At least one of X ^{1 to} X ⁸ is -O-, -S-, R-, -SiR ¹ R ² , -CR ¹ R ² , -CR ¹ = R ² , -NR ¹ , -N = CR ¹ ,- N = N- and a chemical bond;

X ^{1 to} X ⁸ which are not bound to HTM are independently —H, —F, —CN, R—, —OR ¹ , —SR ¹ , —NR ¹ R ² , —SiR ¹ R ² R ³ , —CR ¹ R ² R ³ , -CR ¹ = CR ² R ³ , -N = NR ¹ and HTM;

R, R ¹ , R ² and R ³ are independently substituted or unsubstituted alkyl, vinyl, allyl and / or (hetero-) aryl and / or (hetero-) cyclic moieties, hydrogen or HTM as defined above Can be selected from.

If the X bond connecting one or more HTMs to Y is a chemical bond, the compound according to the invention is a dye.

A particular advantage of the HTL or ETL compounds according to the invention is that they are intrinsic p-type doped, and therefore co-deposition to form HTL of the matrix material with the dopant is no longer necessary. Therefore, using the HTL compound according to the present invention facilitates the manufacturing process of the organic EL device. As a further effect of the intrinsically doped HTL compounds according to the invention, HTL can be deposited more homogeneously and with higher reproducibility compared to matrix compositions composed of matrix materials and mixed p-type dopants.

Another advantage of the HTL and ETL compounds according to the invention is the higher glass transition temperature compared to the system of p-type doped matrix material. Higher glass transition temperatures are believed to result from steric effects in HTL compounds.

Another feature of the HTL and ETL compounds according to the invention is the generally reduced mobility in the electric field, which is a desirable property for producing stable organic electroluminescent (EL) devices, preferably leading to increased long-term stability. .

The compounds of the present invention are intrinsically doped HTL and ETL, respectively, which enable their deposition with greater homogeneity and reproducibility than matrix compositions composed of matrix material and mixed dopants.

In another aspect, the present invention provides a method for preparing an HTL compound, comprising the following main synthetic steps:

A) The disubstituted 1,4-cyclohexanedione moiety is reacted to form a stable diketal, for example a cyclic ketal on both ketone moieties. The two substituents of the 1,4-cyclohexanedione moiety are chemically reactive to form a chemical bond to the HTM. Preferred substituents are π-electron rich compounds, for example, it may be appropriate that the substituent is a halogenated aromatic moiety that is reactive with HTM comprising an aromatic moiety.

Bonding with one or more HTMs is obtained by reaction of chemically reactive substituents with residues of HTM, for example by reaction of halogenated phenyl groups with aromatic residues of HTM. This bond may be a direct bond between the 1,4-cyclohexanedione moiety and the HTM or a bond by an intermediate linker moiety. As a result, the cyclohexyl moiety substituted with two diketal groups is derivatized with HTM on its reactive substituent. In the subsequent oxidation reaction, two diketal groups are reoxidized to ketone groups.

It is essential that at least one HTM is conjugated with the 1,4-cyclohexanedione moiety.

B) After binding one or more HTMs to a carboxyl moiety substituted with two opposing ketone groups, the ketones are reacted to replace an electron acceptor moiety, such as a cyano imine group or dicyano methylene group. Subsequent oxidation reactions yield conjugated 1,4-cyclohexanedione groups at positions 2 and 5 of the two electron donor moieties. The 1,4-cyclohexanedione group is further substituted by nonconjugated bonds with one or more HTM.

In general, HTL compounds according to the invention are known, including vapor deposition (including PVD, CVD, OVPD) and coating from solution (spraying, rotating or knife coating) or sputtering, depending on the molecular weight and solubility of the compound. Coating by technique. In general, high molecular weight HTL compounds are difficult to deposit, and in such cases coating from solution is preferred. One skilled in the art can readily determine the appropriate method for coating the HTL compound. Methods of determining suitable solvents are also generally known. Preferred solvents are chlorobenzene, toluene and xylol.

Hereinafter, the present invention will be described through examples, but the scope of the present invention is not limited to these examples. The following description will be made with reference to the drawings of FIGS. 1 to 9.

1 schematically shows a cross section of an organic field effect transistor (OFET). Here, the layer marked as semiconductor represents the position of the HTL according to the invention.

2 schematically shows the cross section of an OLED in which HTL is formed of the compound according to the invention.

3 schematically shows the cross section of an inverse OLED in which HTL is formed of the compound according to the invention.

4 schematically shows a cross-sectional view of a solar cell in which a p-type layer semiconductor is formed of the compound according to the invention.

5 schematically depicts the steps for the synthesis of representative compounds according to the invention.

6 schematically depicts the steps for the synthesis of compound 19 of the invention.

7 schematically shows a structure comprising a compound of the invention as a charge transport layer.

8 shows the electrical behavior of 1-TNATA compared to 1-TNATA doped with compound 19 of the present invention.

9 illustrates the electrical behavior of compound 19 of the present invention.

Example 1 OLED Incorporating Inventive HTL, Vacuum Deposition

This embodiment describes the structure of the inverse OLED shown schematically in FIG. 3, but the non-inverse structure shown schematically in FIG. 2, for example, can also be implemented using the compounds according to the invention. For the non-reverse OLED structure, compound 14 and / or compound 19 obtained according to Example 3 was vacuum deposited onto an ITO coated glass substrate with a layer thickness of up to 10-500 nm. Subsequently, the electron blocking layer was vacuum deposited, and then the light emitting layer (Alq ₃ ), the hole blocking layer (BCP), and the electron transport layer (TAZ) were vacuum deposited. Cathode (LiF / Al) was deposited as the last layer.

)로도 알려진, 폴리(스티렌 설폰산)(PSS)과 함께 폴리(3,4-[에틸렌디옥시]-티오펜)(PEDT)을 증착한 뒤에, ITO를 캐소드로서 적용하였다.In the case of an inverse OLED structure, a cathode is deposited on the substrate, an electron transport layer is deposited, followed by the deposition of the selective hole blocking layer, the electroluminescent layer and the selective electron blocking layer, followed by deposition of the compound of the present invention to doping in 1-TNATA. The hole transport layer was formed as zero or as a pure material. Following the deposition of the hole transport layer, the protective layer (pentacene) is vacuum deposited, followed by PEDT: PSS (e.g. Baytron P

After depositing poly (3,4- [ethylenedioxy] -thiophene) (PEDT) with poly (styrene sulfonic acid) (PSS), also known as), ITO was applied as cathode.

As an alternative to the hole transport layer comprising the compound according to the invention as a dopant, the compounds of the invention can form the hole transport layer as the sole component of this layer.

Thus, in another embodiment, compound 14 and / or compound 19 may form an injection layer such that there is no need to use PEDT: PSS as the injection layer. As a result, the pentacene protective layer can be omitted. This is a particular advantage of the compounds according to the invention, since it is possible to apply the injection layer in a vacuum process substantially without interrupting, for example, the vacuum treatment for coating the final electrode layer. In addition, due to the particular advantages of the compounds according to the invention, which can eliminate the need for injection layers (e.g. PEDT: PSS) and protective layers (e.g. pentacene), the structure of the organic electrical device is further improved. Can be simplified. Prior to the present invention, a protective layer was needed to coat the stacked sensitive organic electrical compounds using wet-chemical treatments that could coat high conductivity compounds such as PEDT: PSS.

Example 2 OLED Including HTL of the Invention Deposited by Rotating Coating

Example 1 was repeated except that Compound 14 obtained according to Example 3, or alternatively Compound 19, was deposited to a final layer thickness of 10-500 nm by rotational coating from a solution (in solvent) Huh.

The electrical and EL properties were substantially consistent with those observed in Example 1.

Example 3: Electrical properties of 2,5-bis- (4-diphenylaminobenzyl) -1,4-bis- (dicyanomethylidene) -cyclohexa-2,5-diene (19)

The synthesis of compound (19) is schematically shown in FIG. The synthesis of compound (19) was substantially similar to the synthesis of compound (14) described in Example 4. Melting | fusing point of compound (19) is 252 degreeC.

As an example of a compound according to the invention, compound (19) shown in FIG. 6 is p-type in a 10 nm thick 1-TNATA layer at a concentration of 1.2 vol% and 2.5 vol%, respectively, compared to undoped 1-TNATA. Used as dopant. 1-TNATA doped with compound (19) was coated onto an ITO coated organic substrate and coated with an electrically conductive aluminum layer.

The structure of the measurement set-up and the structure of the simple semiconductor device are respectively shown in FIG. 7. As can be seen from Figure 7, the compounds of the present invention, when used as a dopant as a mixture with 1-TNATA or as a pure material, do not require an additional injection layer, i.e. do not require an additional matrix material, It is possible to form a layer in direct contact. This structure is sufficient for charge transport from one electrode to another.

The electrical properties of the charge transport layer comprising the material of the invention as a dopant of the matrix material (1-TNATA) are shown in FIG. 8, in which the increase in concentration of compound (19) responds to the increase in voltage (U [V]). That is, it demonstrates that when charge is injected from the ITO layer, it dramatically increases positive charge transport (I [A]). When the voltage was reversed to inject charge from the Al layer, the conductivity could not be measured.

As an alternative to using the compounds of the invention as p-type dopants, compounds 19 (pure films of p-type dopants) per se in the structure according to FIG. Electrical conductive layer was prepared. For the measurement, the polarity of the electrode was reversed as needed. Compound (19) was laminated on an ITO glass substrate and coated with aluminum as described above. When voltage was applied to inject charge from the ITO layer, a rapid increase in positive charge transport appeared as a reaction, while a rapid increase in negative charge transport appeared when the voltage was reversed for charge injection from the Al layer. This behavior shown in FIG. 9 is evidence that the compound of the present invention is suitable for forming an electrically conductive layer in a FET.

This example demonstrates that the compounds according to the invention can form a p-type dopant in the hole transport layer and, alternatively, that they can form a hole transport layer and an electron transport layer without adding additional matrix material. This is also evidence that the inventive material can be utilized as a hole and / or charge injection layer. The conductive layer formed of the compound according to the invention, as a particular advantage, yields a very homogeneous and evenly distributed phase.

Example 4: 2,5-bis {4-[(4'-diphenylamino-biphenyl-4-yl) -phenylamino] -benzyl} -1,4-bis (dicyanomethylidene) -cyclohexa Synthesis of -2,5-diene (14)

2,5-bis {4-[(4'-diphenylamino-biphenyl-4-yl) -phenylamino] -benzyl} -1,4-bis (dicyanomethylidene) -cyclohexa-2,5 The synthesis method of the diene 14 is schematically illustrated in FIG. 5. In this example, the 4'-bromobenzyl substituent represents two substituents of the 1,4-cyclohexanedione moiety that are chemically reactive such that a chemical bond to HTM is formed later.

2,5-bis (methoxycarbonyl) -cyclohexa-1,4-dione (1) as starting material and reacted with 4-bromobenzylbromide to give 2,5- via intermediate compound (2) Bis (methoxycarbonyl) -2,5-bis (4-bromobenzyl) -cyclohexa-1,4-dione (3) can be obtained. The result of the analysis for the compound (3) is as follows: MS (EI, 70 eV): m / z (%) = 566 (10) [M ⁺ ], EA: Theoretical C = 50.91, H = 3.91, Br = 28.22; Found C = 51.25, H = 3.95, Br = 28.07.

Compound (3) is heated in the presence of calcium bromide to remove two ester groups at positions 2 and 5. Specifically, 2,5-bis (methoxycarbonyl) -2,5-bis (4) in a 250 mL three-necked flask equipped with a reflux condenser in a mixture with 2.80 g of calcium bromide at 180 ° C. under an inert gas atmosphere. -Bromobenzyl) -cyclohexa-1,4-dione (3) 1.13 g (2 mmol) was stirred for 3 hours to give 2,5-bis (4-bromobenzyl) cyclohexa-1,4-dione ( 4) is obtained. Then 100 mL of 1 N HCl was added. The phases were separated and the aqueous phase was extracted four times with 15 mL of methylene chloride. The organic phase was dried over sodium sulphate and the solvent was removed on a rotary evaporator. The solid product was purified by Soxhlet extraction with diethyl ether. 0.72 g (1.6 mmol) of a white solid were obtained as an isomer mixture. The analytical result for the compound (4) is as follows: MS (EI, 70 eV): m / z (%) = 450 (40) [M ⁺ ] EA: Theoretical C = 53.36, H = 4.03, Br = 35.50 ; Found C = 53.74, H = 4.07, Br = 35.45, melting point mp = 158-160 ° C.

Conversion of compound (4) to 2,5-bis (4-bromobenzyl) -1,4,9,12-tetraoxa-disspiro [4.2.4.2] tetradecane (7) is described in Liebigs Ann. Chem. 186-190 (1982). MS (EI, 70 eV): m / z (%) = 538 (16) [M ⁺ ]. EA: Theoretical C = 53.55, H = 4.87, Br = 29.69; Found C = 55.33, H = 4.94, Br = 29.10, melting point mp = 200-202 ° C.

J. Am. Chem. Soc. 118, 7215-7216 (1996) and in J. Am. Chem. Soc. 62, 1568-1569 (1997) from N, N ', N-triphenyl-biphenyl-4,4 from compound (5) via Buchwald coupling using a reaction in toluene at 100 ° C. '-Diamine (6) can be obtained as a representative HTM. Compound (6) was purified by flash column chromatography (n-hexane: ethyl acetate (10: 1), Rf = 0.3).

2,5-bis {4- [4'-diphenylamino-biphenyl-4-yl) -phenyl-amino] -benzyl} -1,4 as a white solid from the reaction of compound (6) with compound (7) , 9,12-tetraoxa-disspiro [4.2.4.2] tetradecane (8) was isolated. Melting | fusing point of compound (8) was measured at 142-143 degreeC. ESI-MS (CH ₃ CN / Toluene): 1201 [M ⁺ ]. Elemental Analysis (EA): Theoretical C = 83.97, H = 6.04, N = 4.66; Found C = 83.87, H = 6.12, N = 4.42.

Alternatively, 2,5-bis (4-{[4 '-(naphthalen-1-yl-phenyl-amino) -biphenyl-4-yl] as a white solid from the reaction of compound (6A) with compound (7) -Amino} -benzyl) -1,4,9,12-tetraoxa-disspiro [4.2.4.2] tetradecane (9) was obtained. Melting point was measured at 130 ~ 132 ℃. ESI-MS (CH ₃ CN / toluene): m / z = 1301 [M ⁺ ] EA: Theoretical C = 84.88, H = 5.90, N = 4.30; Found C = 84.72, H = 6.24, N = 3.78.

2,5-bis (4-{[4'-diphenyl) was cooled by cooling 0.6 g (0.5 mmol) of compound (8) dissolved in 70 mL of dichloromethane in a 250 mL two-necked flask at 0 ° C. under an inert gas atmosphere. Amino-biphenyl-4-yl] -phenylamino] -benzyl} -cyclohexane-1,4-dione (10) was obtained slowly adding 0.5 mL of 70% HClO ₄ and stirring at 0 ° C. for 1 hour. After 3 hours, the reaction solution was neutralized with 100 mL of saturated NaHCO ₃ and stirred for 1 hour at room temperature The organic phase was dried over magnesium sulfate and the solvent was evaporated on a rotary evaporator The residue was methylene chloride: n- Hexane (5: 1) was purified by flash column chromatography using eluent, yielding 0.185 mg (1.6 mmol) of a white solid as an isomer mixture with melting points of 142 ° C. and 136 ° C., respectively.

Isomer 2: ¹ H NMR (200 MHz, CDCl ₃ ): δ = 7.36-6.87 (m, 54H, Har _. ), 3.18 (dd, J = 13.9 and 4.2 Hz, 2H, H _cyc. ), 3.09-2.71 (m, 2H, H _cyc. ), 2.62 (dd, J = 17.7 and 5.9 Hz, 2H, H _cyc. ), 2.49-2.21 (m, 4H, H _methylene ).

¹³ CNMR (50 MHz, CDCl ₃ ): δ = 209.3 (C _{C = O} ), 147.7-146.4 (C _ar. ), 134.8-122.8 (C _ar. ), 48.3 (C _{cyc., C H} ), 41.4 ( C _{cyc., C H2} ), 34.5 (C _methylene ).

ESI-MS (CH ₃ CN / Toluene): m / z = 1112 [M ⁺ ]

2,5-bis (4-{[4 '-(naphthalen-1-yl-phenylamino) by the same synthesis step as that of the compound (10) when the compound (9) is used as the starting material instead of the compound (8). ) -Biphenyl-4-yl] -phenylamino} -benzyl) -cyclohexa-1,4-dione (11) is obtained as an alternative to compound (10). Compound (11) is obtained as a white solid (isomer mixture).

In a 50 mL one-necked flask equipped with a reflux condenser, 0.9 mmol of compound (10) and compound (11) (0.99 g of compound (10)), respectively, 0.178 g (2.7 mmol) CH ₂ (CN) ₂ and catalyst amount Was stirred in a mixture with a beta-alanine, 10 mL alcoholic toluene solution (alcohol is preferably methanol, ethanol or propanol), and reacted with compound (10) and compound (11), respectively, to give 2,5-bis- { 4-[(4'-Diphenylamino-biphenyl-4-yl) -phenylamino] -benzyl} -1,4-bis- (dicyanomethylidene) -cyclohexane (12) and 2,5-bis -(4-{[4 '-(naphthalen-1-yl-phenylamino) -biphenyl-4-yl) -phenylamino} -benzyl) -1,4-bis- (dicyanomethylidene) -cyclohexane (13) was formed. After stirring at 80 ° C. for 72 hours, compound (12) and compound (13) were each collected by filtration and washed with ethanol. 0.85 g (0.7 mmol) of compound (12) were obtained as a pale yellow solid having a melting point of 278 to 280 ° C.

Compound 12: ¹ H NMR (200 MHz, CDCl ₃ ): δ = 7.48-7.01 (m, 54H, H _ar. ), 3.71 (dd, 2H, H _cyc. ), 3.22 (d, 2H, H _cyc. ) , 2.79-2.61 (m, 6H, H _{methylene and cyc.} ).

¹³ C NMR (50 MHz, CDCl ₃ ): δ = 176.9 (C _{C = C (CN)} ), 147.9-146.5 (C _ar. ), 135.5-123.0 (C _ar. ), 110.9 (C _{C N} ), 110.7 (C _{C N} ), 88.5 (C _{C = C (CN)} ), 45.6 (C _{cyc., C H} ), 39.9 (C _{cyc., C H2} ), 35.4 (C _methylene ), ESI-MS (CH ₃ CN / Toluene): m / z = 1208 [M ⁺ ]

EA: Theoretical C = 85.40, H = 5.33, N = 9.26; Found C = 84.92, H = 5.32, N = 8.90

Compound (13) was isolated as a yellow solid having a melting point of 156 to 158 캜.

Compound 13: ¹ H NMR (200 MHz, CDCl ₃ ): δ = 7.97-7.76 (m, 7H, H _naphthyl ); 7.52-6.90 (m, 53H, H _ar. ), 3.68 (dd, 2H, H _cyc. ), 3.21 (d, 2H, H _cyc. ), 2.84-2.70 (m, 6H, H _{methylene and cyc.} ).

¹³ C NMR (50 MHz, CDCl ₃ ): δ = 176.9 (C _{C = C (CN)} ), 148.5-1143.6 (C _ar. ), 135.6-122.0 (C _ar. ), 111.0 (C _{C N} ), 110.7 (C _{C N} ), 88.4 (C _{C = C (CN)} ), 45.6 (C _{cyc., C H} ), 40.0 (C _{cyc., C H2} ), 34.1 (C _methylene ). ESI-MS (CH ₃ CN / Toluene): m / z = 1309 [M ⁺ ].

EA: Theoretical C = 86.21, H = 5.23, N = 8.56; Found C = 86.10, H = 5.45, N = 7.80

2,5-bis {4-[(4'-diphenylamino-biphenyl-4-yl) phenylamino] -benzyl) -1,4-bis- (dicyanomethylidene) -cyclohexa-2,5 -Diene (14)

In a 250 mL two-necked flask, 0.2 g (0.2 mmol) of Compound (12) was dissolved in 50 mL of dichloromethane. To the solution formed, 0.55 g of active manganese dioxide was added. The mixture was stirred for 3 hours at room temperature under an inert gas atmosphere and then filtered over silica gel. The solvent was removed and the residue was recrystallized from a mixture of toluene and acetonitrile at -10 ° C. 0.12 g (0.1 mmol) of compound (14) were obtained as a green solid having a melting point of 177 to 179 ° C.

¹ H NMR (400 MHz, CDCl ₃ ): δ = 6.99-7.46 (m, 56H, H _{cyc. And ar.} ), 4.27 (s, br., 4H, H _methylene ), ¹³ C NMR (100 MHZ, CDCl) ₃ ): δ = 150.3 (C _{C = C (CN)} ), 147.7-122.8 (C _ar. ), 143.6 (C _{cyc., C = CH} ), 124 (C _{cyc., C = CH} ), 112.7 (C _{C N} ) 113.9 (C _CN ), 87.1 (C _{C = C (CN)} ), 38.4 (C _methylene ). ESI-MS (CH ₃ CN / Toluene): m / z = 1204 [M ⁺ ]. Elemental Analysis: Calculated: C = 85.69, H = 5.02, N = 9.30; Found: C = 85.54, H = 5.56, N = 8.54.

Claims (24)

Compounds useful in the electro-optical device, characterized by the formula (I): [Formula I]

Wherein the Y moiety represents a central carbon-based structure having accessory residues A ¹ and A ² conjugated to Y, respectively, and residues A ¹ and A ² are electron accepting moieties, and HTM is nonconjugated to the Y moiety. Hole transport moiety, X is an intervening group or chemical bond). The compound of claim 1, wherein X is a chemical bond. The compound of claim 1 or 2, wherein Y comprises a 5 or 6 membered ring conjugated with residues A ¹ and A ² . The compound of claim 3, wherein the 5- or 6-membered ring contains one or more heteroatoms. The compound according to any one of claims 1 to 4, wherein the formula I is one of the following formulas.

or

6. The method of claim 1, wherein 1 to ⁸ HTMs are included, each HTM being bonded to one of X ¹ , X ² , X ³ , X ^{4 to} X ⁸ . compound. The compound of any one of claims 1 to 6, wherein X ¹ , X ² , X ³ , X ^{4 to} X ⁸ substituted with HTM are -O-, -S-, -SiR ¹ R ² , -CR ^1. R ² , -CR ¹ = CR ² , -NR ¹ , -N = CR ¹ , -N = N- and a compound comprising a chemical bond. 8. X ¹ , X ² , X ³ , X ^{4 to} X ^{8 which} is not substituted with HTM is -H, -F, -CN, -OR ¹ , -SR ^1. , -NR ¹ R ² , -SiR ¹ R ² R ³ , -CR ¹ R ² R ³ , -CR ¹ = CR ² R ³ , -N = NR ¹ and HTM compound. 9. The HTM of claim 1, wherein the HTM is tris-[(N, N-diaryl) amino] -triphenylamine, 4,4 ′, 4 ″ -tris [(N- (1- Naphthyl) -N-phenyl-amino-triphenylamine] (1-TNATA) and its derivatives, 4,4 ', 4 "-tris [(N- (2-naphthyl) -N-phenyl-amino)- Triphenylamine] (2-TNATA); 4,4 ', 4 "-tris [(N- (3-methylphenyl) -N-phenyl-amino) -triphenylamine] (m-TDATA) and its derivatives, 4 , 4 ', 4 "-tris (carbazol-9-yl) triphenylamine; N, N, N', N'-tetra arylbenzidine, such as N, N, N ', N'-tetraphenyl benzidine and its Derivatives, N ', N'-bis (1-naphthyl) -N, N'-diphenyl-benzidine (α-NPD), N, N'-di (naphthalen-2-yl) -N, N'- Diphenyl-benzidine (β-NPD), 4,4'-bis (carbazol-9-yl) biphenyl (CBP) and derivatives thereof; 4,4'-bis (2,2'-diphenylvinyl)- 1,1'-biphenyl (DPVBI); triarylamine and derivatives thereof, 4,4'-bis (N, N-diarylamino) -terphenyl, 4,4'-bis (N, N-diaryl Amino) -quaterphenyl and its analogs and derivatives thereof The compound characterized in that the selected. 7. A compound according to claim 6, wherein HTM is a homologue thereof substituted with a hetero atom. 7. A compound according to claim 6, wherein the homologue substituted by a hetero atom is a thienyl derivative, selenyl derivative or furanyl derivative. 12. A compound according to any one of claims 1 to 11, wherein A ¹ and A ² are independently selected from the group comprising cyano groups, -C (CN) ₂ and -NCN. 2,5-bis {4-[(4'-diphenylamino-biphenyl-4-yl) -phenylamino] -benzyl) -1,4-bis- (dicyanomethylidene) -cyclohexa-2, 5-diene (14). 2,5-bis- (4-diphenylaminobenzyl) -1,4-bis- (dicyanomethylidene) -cyclohexa-2,5-diene (19). The compound according to claim 1, for use as a dopant in the hole or electron transport layer and / or in the hole or electron injection layer. The compound according to claim 1, for use as a hole or electron transport layer and / or a hole or electron injection layer without adding additional matrix material. A method for synthesizing a compound according to any one of claims 1 to 16, a) reacting a disubstituted 1,4-cyclohexanedione moiety to form a stable diketal, b) forming a non-conjugated chemical bond between the at least one HTM and the 1,4-cyclohexanedione moiety, c) chemically replacing the ketone group with an electron donor moiety to form a conjugated bond between the electron donor moiety and the cyclohexyl moiety, and d) oxidizing 1,4-bis (dicyanomethylidene) -cyclohexane to 1,4-bis (dicyanomethylidene) -1,4-cyclohexa-2,5-diene Method comprising a. An electrical device comprising a compound according to any one of claims 1 to 16. The electrical device of claim 18, wherein the electrical device is an OLED, OFET, laser or photovoltaic device. Method for producing an electro- or electro-optical device, characterized in that the compound according to any one of claims 1 to 16 is used. The method of claim 20, wherein the organic layer and the final contact electrode of the device are formed under vacuum. 21. The method of claim 20, wherein the vacuum process is a PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition) or OVPD (Organic Vapor Physical Deposition) process. The method of claim 20, wherein the compound according to claim 1 is applied by coating or sputtering from a solution. 24. The method of claim 23, wherein the coating is spray coating, rotary coating, dip coating or knife coating.

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