KR20140088017A - Tetraphenylene ethylene based compound and oled device containing the same - Google Patents

Abstract

각각의 구조 (I) 및 (IA)에서, R₁, R₂, R₃ 및 R₄는 동일하거나 또는 상이하고,
R₁, R₂, R₃ 및 R₄는 각각 독립적으로 수소, 탄화수소, 치환된 탄화수소, 및 이들의 조합으로부터 선택된다.The present disclosure provides a composition, a film containing the composition, and an electronic device containing the composition. The composition comprises tetraphenylene ethylene having the structure of any one of Examples 1 to 25, tetraphenyleneethylene of structure (I), tetraphenyleneethylene of structure (IA), or combinations thereof.

In each of structures (I) and (IA), R ₁ , R ₂ , R ₃ and R ₄ are the same or different,
R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof.

Description

TECHNICAL FIELD [0001] The present invention relates to a tetraphenylene-based compound and an OLED device containing the same. BACKGROUND ART < RTI ID = 0.0 >

This disclosure claims priority from application PCT / CN2012 / 088034, filed December 31, 2012, the full text of which is incorporated herein by reference.

OLED (Organic Light Emitting Diode) is a light emitting diode (LED) that is a film of an organic compound in which a radioactive electroluminescent layer emits light in response to an electric current. A typical OLED has a multilayer structure, typically comprising an indium tin oxide (ITO) anode, and a metal cathode. A plurality of organic layers such as a hole injection layer (HIL), a hole transport layer (HTL), an emission material layer (EML), an electron transport layer (ETL), and an electron injection layer (EIL) are interposed between the ITO anode and the metal cathode. In order to facilitate hole injection and obtain a smooth surface, it is often desirable to locate a hole injection layer (HIL) between the ITO anode and the hole transport layer. The most commonly used HIL material is poly (3,4-ethylenedioxythiophene) / poly (styrenesulfonic acid) complex (PEDOT / PSS). However, OLEDs fabricated from PEDOT / PSS exhibit short lifetimes due to corrosion induced by the high acidity of PEDOT / PSS. In addition, PEDOT / PSS solutions are often aqueous solutions. When this is used in an OLED, a small amount of residual moisture in the film causes corrosion in the electric circuit, leading to element collapse. Thus, there is still a need for HIL materials for OLED applications, particularly non-aqueous HIL compositions.

Conventional multilayer OLED devices are produced by thermal deposition. However, thermal deposition has its disadvantages. Thermal deposition requires thermal evaporation under high vacuum, which increases fabrication complexity and makes the utilization of expensive OLED materials very inefficient (typically less than 20%). Also, pixelation using evaporation masks limits the scalability and resolution of OLED devices.

Solution processes such as ink-jet printing and nozzle printing have become viable alternatives to thermal deposition manufacturing techniques for OLED devices. (NPB) and 4,4 ', 4 ' -diamine < RTI ID = 0.0 > Conventional OLED materials such as 4'-tris [2-naphthyl (phenyl) amino] triphenylamine (2-TNATA) are not suitable for solution processing due to poor film morphology and crystallization after spin-casting.

Thus, there is a need for an OLED material that can be used in solution processes for the manufacture of OLED devices. There is also a need for an OLED material that can be used in both thermal deposition and solution processes for the manufacture of OLED devices.

The present invention provides a composition comprising tetraphenylene ethylene (TPE) having the structure of any one of Examples 1 to 25 of Table 2.

In one embodiment, this disclosure provides a composition comprising tetraphenylene ethylene of structure (I), tetraphenylene ethylene of structure (IA), or combinations thereof, as shown below.

In each of structures (I) and (IA), R ₁ , R ₂ , R ₃ And R < ₄ > are the same or different. R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof; or

R ₁ and R ₂ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof; R ₃ and R ₄ form a ring structure; or

R ₃ and R ₄ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof; R ₁ and R ₂ form a ring structure; or

R ₁ and R ₂ form a cyclic structure, and R ₃ and R ₄ form a cyclic structure.

The present disclosure also provides a film formed from the composition of the present invention comprising tetraphenylene ethylene of structure (I), tetraphenylene ethylene of structure (IA), or a combination thereof.

The present disclosure also provides an electronic device comprising at least one component formed from a composition of the present invention comprising tetraphenylene ethylene of structure (I), tetraphenylene ethylene of structure (IA), or a combination thereof.

An advantage of the composition of the present invention is that it can be used in both thermal evaporation and solution processes.

1 is a current-voltage curve of an OLED device according to an embodiment of the present disclosure;
2 is a graph illustrating the luminance efficiency of an OLED device according to an embodiment of the present disclosure;
3 is a graph illustrating the decay of intensity intensity over time of an OLED device according to an embodiment of the present disclosure;

1. Composition

The present disclosure provides a composition comprising tetraphenylene ethylene (TPE) having the structure of any one of Examples 1 to 25 of Table 2.

In one embodiment, this disclosure provides a composition comprising tetraphenylene ethylene of structure (I), tetraphenylene ethylene of structure (IA), or combinations thereof, as shown below.

In each of structures (I) and (IA), R ₁ , R ₂ , R ₃ and R ₄ are the same or different. R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, or combinations thereof; or

R ₁ and R ₂ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, or combinations thereof; R ₃ and R ₄ form a ring structure; or

R ₃ and R ₄ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, or combinations thereof; R ₁ and R ₂ form a ring structure; or

R ₁ and R ₂ form a cyclic structure, and R ₃ and R ₄ form a cyclic structure.

In one embodiment, R ₁ and R ₂ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, or combinations thereof; R ₃ and R ₄ form a ring structure.

In one embodiment, R ₃ and R ₄ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, or combinations thereof; R ₁ and R ₂ form a ring structure.

In one embodiment, R ₁ and R ₂ form a ring structure, and R ₃ and R ₄ form a ring structure.

Unidentified substituents of structure (I) and structure (IA) may be selected from hydrogen, hydrocarbons, substituted hydrocarbons, cyclic structures such as phenyl, naphthyl, anthracenyl and biphenyl, or combinations thereof. In one embodiment, the unidentified substituent of structure (I) and structure (IA) is hydrogen.

As used herein, "hydrocarbons" are compounds containing only hydrogen and carbon. Hydrocarbons contain from 1 to 50 carbon atoms. The hydrocarbons may be any combination of (i) branched or unbranched, (ii) saturated or unsaturated or aromatic, (iii) cyclic or acyclic, and (iv) (i) to (iii). The term "hydrocarbon" includes a "hydrocarbyl group" (or "hydrocarbyl group") which is a hydrocarbon substituent having a valency (typically a monovalent). In one embodiment, the hydrocarbon contains from 1 to 30 carbon atoms, or from 1 to 24 carbon atoms, or from 1 to 20 carbon atoms, or from 1 to 12 carbon atoms, or from 1 to 6 carbon atoms.

As used herein, "substituted hydrocarbons" are hydrocarbons containing one or more heteroatoms. "Heteroatom" refers to an atom that is not carbon or hydrogen. Non-limiting examples of heteroatoms include F, Cl, Br, N, O, P, B, S, Si, Sb, Al, Sn, As, Se and Ge.

"Substituted hydrocarbons" are hydrocarbons that do not contain heteroatoms.

As used herein, a "ring structure" is a ring composed of a hydrocarbon or a substituted hydrocarbon, the ring structure may be saturated or unsaturated, and the ring structure may contain one, or two, or more than two rings .

In one embodiment, the composition comprises tetraphenylene ethylene (TPE) having the structure (I) and isomers thereof. The structure (I) is as follows.

R ₁ , R ₂ , R ₃ and R ₄ are the same or different. R ₁ to R ₄ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof.

In one embodiment, R ₁ to R ₄ are each independently selected from hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and combinations thereof.

"Alkyl group" is a straight, branched or unbranched saturated hydrocarbon radical. Suitable alkyl radicals include, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl (or 2- methylpropyl), hexyl, In one embodiment, the alkyl group has 1 to 30, or 1 to 24, or 1 to 20, or 1 to 12, or 1 to 6 carbon atoms.

As used herein, the term "substituted alkyl group" refers to a hydrocarbon radical in the alkyl group just described, containing one or more heteroatoms.

Is an aromatic substituent which may be a single aromatic ring or multiple aromatic rings fused or covalently bonded together or bonded to a common group such as a methylene or ethylene moiety. The aromatic ring (s) may include, among others, phenyl, naphthyl, anthracenyl and biphenyl. In certain embodiments, the aryl group has 6 to 50, or 6 to 30, or 6 to 24, or 6 to 20, or 6 to 12 carbon atoms.

As used herein, the term "substituted aryl group" refers to an aryl group as just described, wherein the aromatic substituent comprises one or more heteroatoms.

In one embodiment, the compositions of the present invention comprise isomers of structure (I). The TPE of structure (I) includes Z-isomers, E-isomers, and combinations thereof.

The Z-isomer has the structure (I) shown below. In one embodiment, the composition comprises structure (I) wherein R ₁ , R ₂ , R ₃ and R ₄ are as defined above.

The E-isomer has the structure (IA) shown below. In one embodiment, the composition comprises structure (IA) wherein R ₁ , R ₂ , R ₃ and R ₄ are as defined above.

The composition of the present invention may comprise more than 0, or 1 to 99 wt% Z-isomer (structure I) and less than 100 wt%, or 99 wt% to 1 wt% E-isomer (structure IA) have.

In one embodiment, the composition comprises greater than 0, or greater than 1 weight percent, or greater than 10 weight percent, or greater than 25 weight percent, or greater than 50 weight percent, or greater than 75 weight percent, or greater than 90 weight percent, Excess Z-isomer; And less than 100 wt%, or less than 99 wt%, or less than 90 wt%, or less than 75 wt%, or less than 50 wt%, or less than 25 wt%, or less than 10 wt% Lt; / RTI > The weight percent is based on the total weight of the composition.

In one embodiment, one, some, or all of R ₁ to R ₄ comprises one or more aryl groups. In a further embodiment, R ₁ -R ₄ each comprise at least one aryl group.

In one embodiment, R ₁ and R ₂ form a ring structure. In a further embodiment, R ₁ and R ₂ each comprise an aryl group, and R ₁ and R ₂ form a ring structure.

In one embodiment, R ₃ and R ₄ form a ring structure. In a further embodiment, R ₃ and R ₄ each comprise an aryl group, and R ₃ and R ₄ form a cyclic structure.

In one embodiment, R ₁ and R ₂ form a ring structure, and R ₃ and R ₄ form another ring structure. In a further embodiment, R ₁ and R ₂ each contain an aryl group, R ₁ and R ₂ form a ring structure, R ₃ and R ₄ comprises an aryl group, respectively, and R ₃ and R ₄ is a ring structure .

In one embodiment, the TPE has a structure selected from structures 1 to 25 of Table 2.

In one embodiment, the TPE has a structure selected from structures 1 to 5, 7, 8, 10, 11, and 13 to 25 of Table 2.

In one embodiment, the TPE has a structure selected from structures 1, 2 and 3 of Table 2.

In one embodiment, the TPE has a structure selected from structures 1 to 3 and 6 to 25 of Table 2.

In one embodiment, the TPE has a structure selected from structures 1 to 3, 7, 8, 10, 11, and 13 to 25 of Table 2.

In one embodiment, each of R ₁ to R ₄ is a phenyl group. In a further embodiment, the TPE has the following structure (II).

In one embodiment, R ₁ to R ₄ of TPE are each a phenyl group. In a further embodiment, the TPE is a mixture of the Z-isomer (II) and the E-isomer (IIA) shown below.

In one embodiment, the TPE of structure (I), structure (IA), and combinations thereof is between -4.30 electron volts (eV) and -5.20 eV, or between -4.3 eV and -4.9 eV calculated highest level occupied molecular orbital (HOMO) level.

In one embodiment, the TPE of structure (I), structure (IA), or a combination thereof has a calculated HOMO level of -4.3 eV to -4.6 eV.

In one embodiment, the TPE of structure (I) has a molecular weight (MW) of 700 to 1300 g / mol. In a further embodiment, the TPE of structure (I) has a molecular weight of 800 to 1200 g / mole.

In one embodiment, the TPE containing structure (I), structure (IA), or a combination thereof has a weight average molecular weight (Mw) of 500 to 1500 g / mol.

In one embodiment, the composition is a solution. The solution comprises an aromatic solvent and the TPE composition of the present invention. TPE has structure (I), structure (IA), or a combination thereof. The TPE is dissolved in the solvent. In one embodiment, the aromatic solvent is selected from xylene, toluene, benzene, anisole, and combinations thereof.

Compositions of the present invention may include two or more embodiments disclosed herein.

2. The membrane

The present disclosure provides a film formed from a composition comprising a TPE having the structure of any one of Examples 1 to 25, a TPE of Structure (I), a TPE of Structure (IA), or a combination thereof. The TPE of structure (I) and the TPE of structure (IA) may be any of the TPEs described above.

In one embodiment, the membrane comprises a TPE of structure (I), a TPE of structure (IA), or a combination thereof, having the structure:

In each of structures (I) and (IA), R ₁ , R ₂ , R ₃ and R ₄ are the same or different. R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof; or

R ₁ and R ₂ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof; R ₃ and R ₄ form a ring structure; or

R ₃ and R ₄ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof; R ₁ and R ₂ form a ring structure; or

R ₁ and R ₂ form a cyclic structure, and R ₃ and R ₄ form a cyclic structure.

In one embodiment, R ₁ and R ₂ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof; R ₃ and R ₄ form a ring structure.

In one embodiment, R ₃ and R ₄ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof; R ₁ and R ₂ form a ring structure.

In one embodiment, R ₁ and R ₂ form a ring structure, and R ₃ and R ₄ form a ring structure.

In one embodiment, the membrane comprises at least two layers, namely layer A and layer B. Layer A comprises a TPE composition of the present invention or alternatively is formed from a composition containing a TPE of structure (I), a TPE of structure (IA), or a combination thereof. In a further embodiment, R ₁ to R ₄ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof.

In one embodiment, layer A is a hole injection layer. In a further embodiment, layer A is a hole injection layer formed from a composition comprising a TPE of structure (I), a TPE of structure (IA), or a combination thereof, wherein the HOMO level of the composition is between -4.3 eV and -4.6 eV to be.

In one embodiment, layer B is a hole transport layer.

In one embodiment, the thickness of layer A is 5 nm to 500 nm, or 5 nm to 100 nm, or 5 nm to 50 nm, and the thickness of layer B is 5 nm to 500 nm, or 5 nm to 100 nm, or 5 nm to 50 nm.

In one embodiment, layer A further comprises a p-type dopant. In a further embodiment, the p-type dopant is an organometallic compound or an organometallic salt.

In one embodiment, the p-type dopant is an organometallic salt comprising at least one phenyl group. In a further embodiment, the anion component of the salt comprises a boron atom. In a further embodiment, the organometallic salt has a structure selected from one of the following:

Or a combination thereof.

In one embodiment, the organometallic salt has the structure:

In one embodiment, the amount of dopant in layer A is from 1 wt% to 99 wt%, or from 1 wt% to 50 wt%, or from 1 wt% to 30 wt%, based on the weight of the composition.

The membrane of the present invention may comprise a combination of two or more embodiments disclosed herein.

3. Electronic devices

This disclosure relates to a process for the preparation of a composition comprising a composition comprising tetraphenylene ethylene having the structure of any one of Examples 1 to 25, tetraphenyleneethylene of structure (I), tetraphenyleneethylene of structure (IA) An electronic device comprising one or more components is provided. The TPE of structure (I) and the TPE of structure (IA) may be any of the TPEs described above.

In one embodiment, the electronic device comprises a TPE of structure (I), a TPE of structure (IA), or a combination thereof, having the structure:

In each of structures (I) and (IA), R ₁ , R ₂ , R ₃ and R ₄ are the same or different. R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof; or

R ₁ and R ₂ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof; R ₃ and R ₄ form a ring structure; or

R ₃ and R ₄ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof; R ₁ and R ₂ form a ring structure; or

R ₁ and R ₂ form a cyclic structure, and R ₃ and R ₄ form a cyclic structure.

In one embodiment, R ₁ and R ₂ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof; R ₃ and R ₄ form a ring structure.

In one embodiment, R ₃ and R ₄ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof; R ₁ and R ₂ form a ring structure.

In one embodiment, R ₁ and R ₂ form a ring structure, and R ₃ and R ₄ form a ring structure.

In one embodiment, the electronic device comprises at least one layer containing a composition of the present invention having a TPE of structure (I), a TPE of structure (IA), or a combination thereof.

In one embodiment, the electronic device comprises a first electrode.

In one embodiment, the electronic device includes a second electrode disposed over the first electrode.

In one embodiment, the electronic device comprises an organic layer disposed between the first electrode and the second electrode. The organic layer comprises a composition of the present invention comprising TPE of structure (I), TPE of structure (IA), or a combination thereof.

In one embodiment, the organic layer is layer A and layer A is a hole injection layer.

In one embodiment, the electronic device comprises a second layer B.

In one embodiment, layer B is a hole transport layer.

In one embodiment, layer A is in contact with layer B.

In one embodiment, the electronic device comprises an emissive layer.

In one embodiment, the thickness of layer A is from 1 nm to 1000 nm, or from 2 nm to 500 nm, or from 5 nm to 200 nm. The thickness of layer B is from 1 nm to 1000 nm, or from 2 nm to 500 nm, or from 5 nm to 200 nm.

In one embodiment, the electronic device is an OLED (organic light emitting device).

In one embodiment, the electronic device comprises a first electrode that is an ITO layer. The electronic device also includes a layer A comprising the TPE composition of the present invention having a TPE of structure (I), a TPE of structure (II), or a combination thereof, which is also a HIL layer. The electronic device also includes a layer B which is an HTL layer. The HOMO level of the TPE composition in layer A is between the HOMO level of the ITO layer and the HOMO level of the HTL material. In one embodiment, the TPE composition of layer A has a calculated HOMO level of -4.3 eV to -4.6 eV.

An electronic device of the present invention may comprise a combination of two or more of the embodiments disclosed herein.

Justice

All parts and percentages are by weight unless otherwise stated or implied by context, unless the context is customary in the art. The contents of any patent, patent application, or publication cited in the U.S. Patent Practice, particularly as regards the disclosure, definition (to the extent not inconsistent with all the definitions specifically provided herein) and the general knowledge in the art, Which is incorporated herein by reference (or its corresponding US version is incorporated by reference).

The terms " comprising, "" including," "having ", and derivatives thereof, are not intended to exclude the presence of any additional components, steps or procedures, whether or not they are specifically disclosed. To eliminate any doubt, all compositions claimed using the term "comprising " can include any additional additives, adjuvants, or polymers or other types of compounds, unless otherwise stated. In contrast, the term " consisting essentially of "excludes any other element, step or procedure other than that which is not essential to operability, from the following citation range. The term " consisting of "excludes any other ingredients, steps or procedures not specifically described or listed.

"Dopant" and like terms refer to an electron acceptor or donor that when added to an organic layer as an additive increases the conductivity of the organic layer of the organic electronic device. The electric conductivity of the organic semiconductor can also be affected by doping. Such an organic semiconducting matrix material may be composed of one of an electron donor characteristic or a compound having an electron acceptor characteristic.

"Emissive layer" and similar terms refer to a layer comprising a host and a dopant. The host material may be bipolar or unipolar, and may be used alone or in combination of two or more host materials. The photovoltaic properties of the host material may vary depending on what type of dopant (phosphorescent or fluorescent) is used. In the case of a fluorescent dopant, the auxiliary host material should have good spectral overlap between the adsorption of the dopant and the emission of the host to induce good Fouster transfer to the dopant. In the case of a phosphorescent dopant, the auxiliary host material must have a high triplet energy to limit the triplet of the dopant.

"HTL" and similar terms refer to a layer made from a material that transports holes. High hole mobility is recommended for OLED devices. The HTL is used to assist in blocking the passage of electrons transported by the emissive layer. Typically, low electron affinity is required to block electrons. Preferably, the HTL should have a larger triplet to block exciton movement from the adjacent EML layer. Examples of HTL compounds are di (p-tolyl) aminophenyl] cyclohexane (TPAC), N, N-diphenyl-N, Diamine (TPD), and N, N'-diphenyl-N, N'-bis (1-naphthyl) - (1,1'-biphenyl) -4,4'- diamine (NPB) But is not limited thereto.

Some embodiments of the present disclosure will now be described in detail in the following examples.

Example

1. Materials

The materials used in the following examples are shown in Table 1.

2. Analysis

Nuclear magnetic resonance ( ¹ H and ¹³ C NMR): The sample was dissolved in a suitable deuterated solvent at a concentration of 10 mg / ml. NMR spectra were recorded on a Varian Mercury Plus 400 MHz spectrometer. Chemical shifts were reported for tetramethylsilane.

Liquid chromatography / mass spectrometry (LC / MS):

Samples were dissolved at about 1 mg / ml in THF. One μl of the solution was injected for LC / MS analysis.

High Pressure Liquid Chromatography (HPLC): About 50 mg of sample was weighed and then diluted with 10 g of tetrahydrofuran. The sample solution was filtered through a 0.45 [mu] m syringe filter and 5 [mu] l of the filtrate was injected into the HPLC system.

Cyclic Voltammetry (CV): A scan rate of 10 mV / s on a CHI voltage-current analyzer in a 3-electrode cell with a Pt counter electrode, a Hg / Hg ₂ Cl ₂ reference electrode, M < / RTI > tetrabutylammonium hexafluorophosphate. Ferrocene was added as internal standard. The potential values were calculated according to the peak difference between the oxidation peak of the hole injection layer and the ferrocene standard.

Atomic Force Microscopy (AFM): Surface morphology was visualized by AFM and surface roughness and film thickness of spin-coated HIL films were measured. AFM measurements were performed in a tapping mode on a Dimension V instrument manufactured by Veeco.

The surface roughness was calculated using the amplitude (A) of the vertical deviation. The amplitude parameters R _a and R _q were used to describe the surface roughness. R _a is the arithmetic mean of the absolute amplitude values, R _q is the root mean square of the amplitude values, and is described as follows:

Here, A _i is the amplitude (height or depth) of a pixel i (meaning a point on the surface) in the AFM image, and n is the total number of pixels in the image.

To measure the thickness of the spin-coated film, a portion of the film was removed from the ITO substrate with a sharp blade and then scanned with a cantilever. The gap between the two sections represents the thickness of the membrane.

3. Tetraphenylene Ethylene type  Synthesis of materials

A. 1,2- Bis (4-bromophenyl) -1 ,2- Of the diphenylethene (1)  synthesis

<Reaction Scheme 1>

4-Bromobenzophenone (5 g, 19.2 mmol) and zinc dust (2.5 g, 38.2 mmol) were placed in a 250 mL 2-neck round bottom flask equipped with a reflux condenser. After vacuum evaporation and dry flushing three times with nitrogen, 100 mL of THF was added. The mixture was cooled in an ice water bath to 0 to 5 ℃, was added slowly using a TiCl ₄ 2.1 ㎖ (19.2 mmol) syringe. The mixture was slowly warmed to room temperature, stirred for 0.5 hours and then refluxed for 12 hours. After cooling to room temperature, the reaction mixture was poured into ice water and extracted three times with dichloromethane. The solvent was evaporated in vacuo and the residue was washed with ethanol to give a white powder (70% yield).

_{^{1 H-NMR (CDCl 3,}} 400 MHz): 7.19-7.25 (m, 3H), 7.06-7.13 (m, 7H), 6.96-7.03 (m, 5H), 6.85-6.90 (m, 3H).

B. 1,2-Bis [4- (N- Phenyl ) Aminophenyl ] -1,2- Of the diphenylethene (2)  synthesis

<Reaction Scheme 2>

(4.49 g, 10 mmol), Pd ₂ (dba) ₃ (0.549 g, 0.6 mmol), t- BuOK (4.49 g, 40 mmol) and BINAP 0.747 g, 1.2 mmol). Vacuum Evaporation and Drying After flushing three times with nitrogen, aniline (2.32 g, 25 mmol) and 60 mL of anhydrous toluene were added sequentially using a syringe. The mixture was heated to 80 &lt; 0 &gt; C overnight and cooled to room temperature. The mixture was centrifuged and the supernatant was concentrated and purified on a silica gel column using a mixture of petroleum ether and ethyl acetate (10: 1) as the eluent. The product (2) was a pale yellow powder (yield: 40%).

^{1 H-NMR (d 6 -DMSO} , 400 MHz), δ (TMS, ppm): 8.10-8.18 (d, 2H), 7.15-7.23 (m, 6 H), 7.05-7.15 (m, 4H), 6.95 -7.07 (m, 6H), 6.75-6.88 (m, 10H).

C. 1,2-bis (4- {N, N- [4- (N, N- Diphenylamino ) Phenyl ] Phenyl } Amino) -1,2- Of the diphenylethene (3)  synthesis

<Reaction Scheme 3>

(1.54 g, 3 mmol), Pd ₂ (dba) ₃ (0.137 g, 0.15 mmol) and t- BuOK (1.35 g, 12 mmol) were charged in a 250 mL 3-neck round bottom flask under nitrogen atmosphere . Vacuum Evaporation and Drying After flushing three times with nitrogen, P ( t- Bu) ₃ solution (100 mg / ml) in toluene (0.9 ml, 0.45 mmol) and 20 ml of anhydrous toluene were added sequentially using a syringe. The mixture was heated to 80 &lt; 0 &gt; C overnight and cooled to room temperature. The mixture was centrifuged and the supernatant was concentrated and purified on a silica gel column using a mixture of petroleum ether and dichloromethane (2: 1) as the eluent. The product (3) was a light yellow powder (60%). The yellow powder was purified by sublimation at 360 [deg.] C to give the pure product, which had an HPLC purity of 99.4% (Z isomer: 55.7%, E isomer: 46.7%).

¹ H-NMR (CD ₂ Cl ₂ , 400 MHz),? (TMS, ppm): 6.5-7.5 (m)

¹³ C-NMR (CD ₂ Cl ₂ , 100 MHz),? (Ppm): 122.27, 122.41, 123.78, 123.95, 125.34,125.46,126.34,127.62,129.20,131.46,132.21

HRMS (ESI, m / z ): 1001.45 (M + H ^& lt ^{; +} &

Non-limiting examples of TPE of structure (I), structure (IA) of the present invention are shown in Table 2 below.

4. HOMO  warrant officer

Calculation of HOMO

Density function calculations were performed using the Gaussian 09 set program. The basis state geometry of each molecule was optimized using the hybrid B3LYP function and the 6-31 g (d) basis set, and the HOMO molecular orbital value in electron volts (eV) was extracted therefrom.

The geometry of each molecule in the neutral and triplet states was optimized to the same method and basis system as in the ground state calculation and from this and the ground state calculation the triplet energy was calculated from the energy difference between the neutral triplet and the ground state energy.

J. Phys . Chem . A, 2003, 107, 5241-5251] was used to calculate the relocation energy of each molecule as a measure of electron and hole mobility.

Table 3 below compares the HOMO levels of Example 1 (from Table 2) with the HOMO levels of other tetraphenylene ethylene compounds (Inv - Inventive and Comp = Comparative).

5. The membrane

ITO glass (soda lime glass: 2 cm x 2 cm) was pretreated in turn by ultrasonic treatment in soapy water, acetone, ethanol and isopropane and completely dried in air. (3) prepared in Synthesis Example (above) was dissolved at a concentration of 5 mg / ml in anisole. The solution was then spin-coated onto clean ITO. The surface roughness of the film of spin-coated compound 3 on ITO was analyzed by atomic force microscopy (AFM) (shown in Table 4). Compared with the original ITO having a surface roughness of 5.3 nm, compound 3 was spin-coated thereon, and surface roughness ( _Rq ) was reduced to 0.5 nm after spin-coating compound 3 on ITO.

6. Device example

A. Device example  One

All organic materials were purified by sublimation prior to deposition. The OLED was fabricated on an ITO coated glass substrate that served as the anode, and an aluminum cathode was placed thereon. All organic layers were thermally deposited by chemical vapor deposition in a vacuum chamber with a base pressure of less than 1 x 10 &lt; ^-7 &gt; Torr. The aluminum cathode was deposited at 0.5 nm / s. The deposition rate of the organic layers was maintained at 0.1 to 0.05 nm / s. The active area of the OLED device was "3 mm x 3 mm" as defined by the cathode-worn shadow mask. The glass substrate (20 mm x 20 mm) was available from Samsung Corning and the ITO layer thickness was 1500 Angstroms.

ITO glass (2 cm x 2 cm) was cleaned as described in the film example and treated with oxygen plasma. Compound 3 prepared in Synthesis Example (above) was dissolved in anisole at a concentration of about 20 mg / ml. A solution of compound 3 was spin-coated as an HIL on an ITO glass substrate in a glove box. The film was annealed at 80 DEG C for 20 minutes. The membrane substrate was then transferred to a thermal evaporator at about 1 x ^10-7 Torr vacuum. HTL1, HTL2, in Fl blue EML, the aluminum 8-hydroxyquinolinato thickness of fun carbonate (Alq _3), and lithium quinol rate (Liq) and the layers successively with 5 nm, 25 nm, respectively, of 20 nm, 30 nm and 2 nm Lt; / RTI &gt; The deposition rate of the organic layers was maintained at 0.1 to 0.05 nm / s. The deposition rate of the organic layers was maintained at 0.1 to 0.05 nm / s. The aluminum cathode was deposited at 0.5 nm / s. The active area of the OLED was "3 mm x 3 mm" as defined by the cathode-worn shadow mask.

Finally, the device was tested after sealing with epoxy. The device structure was as follows:

Compound 3 (40 nm) / HTL1 ( 5 nm) / HTL2 (25 nm) / Fl Blue ML (20 nm) / Alq 3 (30 nm) / Liq (2 nm)

B. Device example  2

This procedure was the same as described in Example 1 except that composition (3) was vacuum deposited instead of spin-coating on ITO. The device structure was as follows:

Compound 3 (40 nm) / HTL1 (5 nm) / HTL2 (25 nm) / Fl Blue ML (20 nm) / Alq 3 (30 nm) / Liq (2 nm)

C. Comparative Example  3 - Device

This procedure was the same as described in Example 1 except that 2-TNATA was vacuum deposited as HIL instead of compound 3. [

D. Comparative Example  4 - Device

This procedure was the same as described in Apparatus Example 1 except that polythiophene (Plextronics Co.) was spin-coated instead of Compound 3 as HIL.

E. Testing

The current-voltage-luminance (J-V-L) analysis for the OLED was performed using a source measuring device (KEITHLY 238) luminometer (MINOLTA CS-100A). The EL spectra of the OLED devices were collected by an assay CCD spectrometer.

The current-voltage curves, the luminous efficiency curves, and the emission decay curves of the device examples 1 and 2 of the present invention and the comparative samples 3 and 4 are shown in FIGS. 1, 2 and 3, respectively. The data for the driving voltage (at 1000 Cd / m2), current efficiency (at 1000 Cd / m2) and lifetime (4000 Cd / m2, after 600 minutes) for these devices are collected in Table 5.

1 to 3 and Table 5 show that devices 1 and 2 of the present invention using the composition (3) of the present invention as a HIL (deposited by thermal evaporation or solution process) exhibited a driving voltage and efficiency equivalent to those of Comparative Examples 3 and 4 . However, Apparatus Examples 1 and 2 exhibit a better lifetime than the comparative sample. After 600 minutes at an initial luminance of 4000 Cd / m2, the brightness of the device remained the same (100%) as in the case of the device (Device Example 1) containing Compound 3 applied by the evaporation process, and Compound 3 (102.3%) in the case of the apparatus (apparatus example 2) including the &lt; / RTI &gt; However, for devices containing polythiophene (Comparative Example 3) and 2-TNATA (Comparative Example 4) as HIL, it decreased to 91.3% and 97.3% after the same period, respectively.

In this disclosure, Applicants have developed a hole injecting material formed from a composition comprising a TPE of structure (I), a TPE of structure (IA), or a combination thereof. The TPE compositions of the present invention are suitable for both thermal evaporation and solution processes. Devices incorporating such materials as HILs exhibit drive voltages and efficiencies comparable to those using polythiophenes and 2-TNATAs as HILs and longer lifetimes than devices using polythiophenes and 2-TNATAs as HILs.

This disclosure is not intended to be limited to the embodiments and examples described herein, but is intended to cover alternatives to those embodiments, including combinations of elements of the embodiments and portions of the embodiments, as falling within the scope of the following claims.

Claims (18)

Compositions comprising tetraphenylene ethylene of structure (I), tetraphenylene ethylene of structure (IA), or combinations thereof:

In each of structures (I) and (IA), R ₁ , R ₂ , R ₃ and R ₄ are the same or different,
R ₁ , R ₂ , R ₃ and R ₄ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof; or
R ₁ and R ₂ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof; R ₃ and R ₄ form a ring structure; or
R ₃ and R ₄ are each independently selected from hydrogen, hydrocarbons, substituted hydrocarbons, and combinations thereof; R ₁ and R ₂ form a ring structure; or
R ₁ and R ₂ form a cyclic structure, and R ₃ and R ₄ form a cyclic structure. The composition of claim 1 comprising an isomer of structure (I) selected from the group consisting of Z-isomers, E-isomers, and combinations thereof. The composition of claim 1, wherein R ₁ to R ₄ each comprise at least one aryl group. The composition of claim 1, wherein R ₁ to R ₄ are each a phenyl group. The composition of claim 1, wherein the tetraphenylene ethylene of structure (I), tetraphenylene ethylene of structure (IA), or combinations thereof has a calculated HOMO level of from -4.3 eV to -4.6 eV. The composition of claim 1, wherein the tetraphenylene ethylene of structure (I) has a molecular weight of from 700 g / mole to 1300 g / mole. The composition of claim 1, further comprising an aromatic solvent. 8. The composition of claim 7, wherein the aromatic solvent is selected from the group consisting of xylene, toluene, benzene, anisole, and combinations thereof. At least two layers, namely a layer A and a layer B, wherein the layer A is formed from the composition of claim 1. The film according to claim 9, wherein the layer A is a hole injection layer. 11. The membrane of claim 10, wherein the composition has a calculated HOMO level of from -4.3 eV to -4.6 eV. The film according to claim 9, wherein the layer B is a hole transport layer. An electronic device comprising at least one component formed from the composition of claim 1. 14. The electronic device of claim 13, further comprising a first electrode. 15. The electronic device of claim 13 or 14, further comprising a second electrode disposed over the first electrode. 14. The electronic device according to claim 13, wherein the component comprises the composition as an organic layer, and the organic layer is disposed between the first electrode and the second electrode. 14. The electronic device of claim 13, wherein the component is a hole injection layer comprising the composition. 18. The electronic device of claim 17, wherein the composition has a calculated HOMO level of from -4.3 eV to -4.6 eV.

Images