KR20140124816A - Deuterated compounds for luminescent applications - Google Patents

Abstract

The present invention relates to deuterated compounds useful in electroluminescent applications. The present invention also relates to electronic devices in which the active layer comprises such deuterated compounds.

Description

[0001] DEUTERATED COMPOUNDS FOR LUMINESCENT APPLICATIONS [0002]

Related Application Data

This application claims the benefit of 35 U.S.C. U.S. Provisional Patent Application No. 61 / 139,834, filed December 22, 2008, and U.S. Provisional Patent Application No. 61 / 176,141, filed May 7, 2009, under § 119 (e) Both of which are incorporated herein by reference in their entirety.

The present invention relates to at least partially deuterated electroactive compounds. The present invention also relates to electronic devices in which at least one active layer comprises such compounds.

BACKGROUND OF THE INVENTION Organic electronic devices that emit light, such as light emitting diodes that make up a display, exist in many different electronic devices. In both such devices, an organic active layer is interposed between the two electrical contact layers. At least one of the electrical contact layers is light transmissive so that light can pass through the electrical contact layer. The organic active layer emits light through the light-transmitting electrical contact layer when electricity is applied across the electrical contact layer.

The use of organic electroluminescent compounds as active ingredients in light emitting diodes is well known. It is known that simple organic molecules such as anthracene, thiadiazole derivatives, and coumarin derivatives exhibit electroluminescence. Semiconductor conjugated polymers have also been used as electroluminescent components, for example, as disclosed in U.S. Patent No. 5,247,190, U.S. Patent No. 5,408,109, and European Patent Application Publication No. 443 861.

However, an electroluminescent compound is continuously required.

(Diarylamino) anthracene and bis (diarylamino) chrysene, and at least one D is provided.

An electronic device comprising an active layer comprising said compound is also provided.

≪ RTI ID = 0.0 >

(I)

≪ RTI ID = 0.0 &

[In the above formula,

R ¹ is in each case the same or different and is selected from the group consisting of D, alkyl, alkoxy and aryl, wherein adjacent R ¹ groups may be joined together to form a 5- or 6-membered aliphatic ring;

Ar ¹ to Ar ⁴ are the same or different and are selected from the group consisting of aryl groups;

a is the same or different in each case and is an integer of 0 to 4;

b is the same or different in each case and is an integer of 0 to 5,

Compounds in which at least one D is present are also provided.

An electronic device comprising an active layer comprising a compound of formula (I) or (II) is also provided.

Embodiments are illustrated in the accompanying drawings to promote an understanding of the concepts presented herein.
≪ 1 >
Figure 1 includes an example of an example of an organic electronic device.
Those skilled in the art will recognize that the objects in the figures are illustrated for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some objects on the drawing may be exaggerated relative to other objects to help improve understanding of the embodiment.

Many aspects and embodiments are disclosed herein and are intended to be illustrative and not restrictive. Having read the present disclosure, those skilled in the art will recognize that other aspects and embodiments are possible without departing from the scope of the present invention.

Any one or more of the other features and advantages of the embodiments will become apparent from the detailed description and the claims that follow. The detailed description first reviews the definitions and explanations of terms, followed by electroactive compounds, electronic devices, and finally the examples.

1. Definition and Explanation of Terms

Before dealing with the details of the embodiments described below, some terms will be defined or clarified.

As used herein, the term "aliphatic ring" is intended to mean a cyclic group that does not have delocalized pi electrons. In some embodiments, the aliphatic ring does not have an unsaturation. In some embodiments, the ring has one double bond or triple bond.

The term "alkoxy" refers to the RO- group, wherein R is alkyl.

The term "alkyl" is intended to mean a group derived from an aliphatic hydrocarbon having one attachment point, including linear, branched or cyclic groups. The term is intended to include heteroalkyl and deuterated alkyl. The term is intended to include substituted and unsubstituted groups. The term "hydrocarbon alkyl" refers to an alkyl group that does not have a heteroatom. The term " deuterated alkyl "is a hydrocarbon alkyl substituted with at least one available H. In some embodiments, the alkyl group has from 1 to 20 carbon atoms.

The term "aryl" is intended to mean a group derived from an aromatic hydrocarbon having one attachment point. The term "aromatic" compound is intended to mean an organic compound comprising at least one unsaturated cyclic group having unpaired pi electrons. The term is intended to include heteroaryl and deuterated aryl. The term "hydrocarbon aryl" is intended to mean an aromatic compound that does not have a heteroatom in the ring. The term aryl includes groups with a single ring, and groups with multiple rings that can be joined by a single bond or fused together. The term " deuterated aryl "refers to an aryl group in which at least one available H atom directly bonded to the aryl is replaced by D. The term "arylene" is intended to mean a group derived from an aromatic hydrocarbon having two points of attachment. Any suitable ring position of the aryl moiety may be joined by a covalent bond to a defined chemical structure. In some embodiments, the hydrocarbon aryl group has from 3 to 60 carbon atoms, and in some embodiments, from 6 to 30 carbon atoms. The heteroaryl group may have from 3 to 50 carbon atoms, and in some embodiments, from 3 to 30 carbon atoms.

The term "branched alkyl" refers to an alkyl group having at least one secondary or tertiary carbon. The term "secondary alkyl" refers to a branched alkyl group having secondary carbon atoms. The term "tertiary alkyl" refers to a branched alkyl group having a tertiary carbon atom. In some embodiments, the branched alkyl group is attached through a secondary or tertiary carbon.

The term "charge transport" in relation to a layer, material, member, or structure means that such layer, material, member, or structure has a relatively low efficiency of charge and charge, To facilitate the movement of such charges. The hole transport material promotes positive charge; Electron transport material promotes negative charge. The term "charge, hole, or electron transport layer, material member, or structure" is not intended to include a layer, material, member, or structure whose primary function is the emission, although the light emitting material may also have some charge transport properties.

The term "compound" is intended to mean an electrically non-charged material consisting of a molecule in which the molecule is further constituted by an atom, wherein the atom can not be separated by physical means. When the phrase "adjacent" is used to refer to a layer in a device, it does not necessarily mean that one layer is next to another layer. On the other hand, the phrase "adjacent R groups" is used to refer to R groups adjacent to each other in the formula (i. E. R groups on atoms connected by a bond).

The term " dehydrated "is meant to mean that at least one available H has been replaced by D. X% The deuterated compound or group has been replaced by D where X% of the available H is. A deuterated compound or group is one in which deuterium is present at least 100 times the level of natural abundance.

When referring to a layer or material, the term "electroactive" is intended to denote a layer or material that electronically facilitates the operation of the device. Examples of the active material include a material that conducts, injects, transports, or blocks charges that may be electrons or holes, or a material that exhibits a change in concentration of electron-hole pairs when emitting radiation or receiving radiation, It is not limited. Examples of inactive materials include, but are not limited to, planarizing materials, insulating materials, and environmental barrier materials.

The prefix "Hetero" indicates that at least one carbon atom has been replaced with a different atom. In some embodiments, the different atoms are N, O, or S.

The term "layer" refers to a coating that is used interchangeably with the term "film " and covers the desired area. This term is not limited by size. The area may be as large as the entire device, as small as a certain functional area, such as a real visual display, or as small as a single sub-pixel. The layers and films may be formed by any conventional deposition technique, such as vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer have. Continuous deposition techniques include, but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot-die coating, spray coating, And continuous nozzle coatings. Discontinuous deposition techniques include, but are not limited to, ink jet printing, gravure printing, and screen printing.

The term "organic electronic device" or sometimes only "electronic device" is intended to mean an element comprising one or more organic semiconductor layers or materials.

The term "oxyalkyl" is intended to mean a heteroalkyl group in which one or more carbons is replaced by oxygen. The term includes groups linked through oxygen.

The term "silyl " refers to the group R ₃ Si-, where R is H, D, C1-20 alkyl, fluoroalkyl, or aryl. In some embodiments, at least one carbon in the R alkyl group is substituted with Si. In some embodiments, the silyl groups are (hexyl) ₂ Si (Me) CH ₂ CH ₂ Si (Me) ₂ - and [CF ₃ (CF ₂ ) ₆ CH ₂ CH ₂ ] ₂ SiMe-.

The term "siloxane" refers to the group (RO) ₃ Si-, wherein R is H, D, C1-20 alkyl or fluoroalkyl.

Unless otherwise indicated, all groups may be substituted or unsubstituted. In some embodiments, the substituent is selected from the group consisting of D, halide, alkyl, alkoxy, aryl, and cyano. Optionally substituted groups such as but not limited to alkyl or aryl may be substituted with one or more substituents which may be the same or different. Other suitable substituents include nitro, cyano, -N (R ') (R "), hydroxy, carboxy, alkenyl, alkynyl, aryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy, arylalkyl , silyl, siloxanes, _{thioalkoxy, -S (O) 2 -N (} R ') (R "), -C (= O) -N (R') (R"), (R ') (R ") (O) < RTI ID = 0.0 > _s -aryl < / RTI > wherein s is 0 to 2, Or -S (O) _s -heteroaryl wherein s is 0-2. Each R 'and R "is independently an optionally substituted alkyl, cycloalkyl, or aryl group. In certain embodiments, R' and R" together with the nitrogen atom to which they are attached form a ring system. can do. The substituent may also be a crosslinking group. As used herein, the terms "comprises,""comprises,""comprises,""includes,""having,""having," or any other variation thereof, I would like to. For example, a process, method, article, or apparatus that comprises elements of a given list need not necessarily be limited to those elements, and may include other elements not explicitly listed or inherent in such process, method, article, ≪ / RTI > Moreover, unless expressly stated to the contrary, "or" does not mean " comprehensive " or " exclusive " For example, a condition A or B is satisfied by any one of the following: A is true (or is present), B is false (or not present), A is false (Or present), and both A and B are true (or present).

In addition, the use of the indefinite article ("a" or "an") is employed to describe the elements and components described herein. This is done merely for convenience and to provide a general sense of the scope of the present invention. Such description should be understood to include one or at least one, and the singular also includes the plural, unless it is obvious that otherwise means.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods and embodiments are illustrative only and not intended to be limiting.

The IUPAC numbering system is used as a whole, wherein the families of the periodic table are numbered 1 to 18 from left to right (CRC Handbook of Chemistry and Physics, 81st Edition, 2000).

2. Electroactive compound

The compounds described herein are bis (diarylamino) anthracene or bis (diarylamino) crysene having at least one D, In some embodiments, the compound is deuterated at least 10%; In some embodiments, greater than 20% deuterated; In some embodiments, greater than 30% deuterated; In some embodiments, greater than 40% deuterated; In some embodiments, greater than 50% deuterated; In some embodiments, greater than 60% deuterated; In some embodiments, greater than 70% deuterated; In some embodiments, greater than 80% deuterated; In some embodiments, greater than 90% is deuterated.

In some embodiments, the electroactive compound is represented by Formula I or Formula II:

(I)

≪ RTI ID = 0.0 &

[In the above formula,

R ¹ is in each case the same or different and is selected from the group consisting of D, alkyl, alkoxy and aryl, wherein adjacent R ¹ groups may be joined together to form a 5- or 6-membered aliphatic ring;

Ar ¹ to Ar ⁴ are the same or different and are selected from the group consisting of aryl groups;

a is the same or different in each case and is an integer of 0 to 4;

b is the same or different in each case and is an integer of 0 to 5,

Wherein the compound has at least one D;

In some embodiments, the compound is capable of emitting red, green, or blue light.

In some embodiments of formulas I and II, the substituent group on the aryl ring is deuterated. The aryl group having a deuterated substituent group may be a core anthracene group of the formula (I) or a core crease group of the formula (II); Or aryl on nitrogen; Or a substituted aryl group. In some embodiments, the deuterated substituent group on the aryl ring is selected from alkyl, aryl, alkoxy, and aryloxy. In some embodiments, the substituent group is deuterated at least 10%; In some embodiments, greater than 20% deuterated; In some embodiments, greater than 30% deuterated; In some embodiments, greater than 40% deuterated; In some embodiments, greater than 50% deuterated; In some embodiments, greater than 60% deuterated; In some embodiments, greater than 70% deuterated; In some embodiments, greater than 80% deuterated; In some embodiments, greater than 90% is deuterated.

In some embodiments of formulas I and II, the aryl group is deuterated at any one or more of the aryl groups Ar ¹ to Ar ⁴ . In this case, at least one of Ar ¹ to Ar ⁴ is a deuterated aryl group. In some embodiments, Ar &^lt; ¹ > to Ar &^lt; ⁴ > This means that at least 10% of all available H bonded to aryl C in Ar &^lt; ¹ > to Ar &^lt; ⁴ > In some embodiments, each aryl ring will have a slight D. In some embodiments, some but not all of the aryl rings have Ds. In some embodiments, Ar ¹ to Ar ⁴ are deuterated at least 20%; In some embodiments, greater than 30% deuterated; In some embodiments, greater than 40% deuterated; In some embodiments, greater than 50% deuterated; In some embodiments, greater than 60% deuterated; In some embodiments, greater than 70% deuterated; In some embodiments, greater than 80% deuterated; In some embodiments, greater than 90% is deuterated.

In some embodiments of formulas I and II, both the substituent group and the aryl group are deuterated.

In some embodiments, the compounds of Formulas I and II are deuterated at least 10; In some embodiments, greater than 20% deuterated; In some embodiments, greater than 30% deuterated; In some embodiments, greater than 40% deuterated; In some embodiments, greater than 50% deuterated; In some embodiments, greater than 60% deuterated; In some embodiments, greater than 70% deuterated; In some embodiments, greater than 80% deuterated; In some embodiments, greater than 90% is deuterated.

In some embodiments of formula I, a is both 0.

In some embodiments of formula I, at least one a is greater than zero. In some embodiments, at least one R < ¹ > is a hydrocarbon alkyl. In some embodiments, R < ^{1 >} is deuterated alkyl. In some embodiments, R < ¹ > is selected from branched hydrocarbon alkyl and cyclic hydrocarbon alkyl.

In some embodiments of formula I, a is both 4 and R < ¹ >

In formula (II), the bond to (R < ¹ _> ) _a is intended to indicate that the R < ^{1 >} group may be present at any position on the two fused rings.

In some embodiments of formula II, b is 0 both.

In some embodiments of formula II, at least one b is greater than zero. In some embodiments, at least one R < ¹ > is a hydrocarbon alkyl. In some embodiments, R < ¹ > is selected from branched hydrocarbon alkyl and cyclic hydrocarbon alkyl.

In some embodiments of formula II, b is both 5 and R < ¹ >

In some embodiments, at least one of Ar &^lt; ¹ > to Ar &^lt; ^{4 &}

(III)

[here,

R ² is the same or different in each occurrence and is selected from the group consisting of D, alkyl, alkoxy, aryl, silyl, and siloxane, or adjacent R ² groups may be connected to form an aromatic ring;

c is the same or different in each occurrence and is an integer from 0 to 4;

d is the same or different in each occurrence and is an integer from 0 to 5;

m is the same or different in each case and is an integer of 0 to 6;

In some embodiments, at least one of Ar &^lt; ¹ > to Ar &^lt; ^{4 &}

(IV)

[here,

R ² is the same or different in each occurrence and is selected from the group consisting of D, alkyl, alkoxy, and aryl, or adjacent R ² groups may be connected to form an aromatic ring;

c is the same or different in each occurrence and is an integer from 0 to 4;

d is the same or different in each occurrence and is an integer from 0 to 5;

m is the same or different in each case and is an integer of 0 to 6].

In some embodiments, Ar ¹ to Ar ⁴ are selected from the group consisting of phenyl, biphenyl, terphenyl, naphthyl, phenylnaphthyl, naphthylphenyl, and binaphthyl.

In some embodiments, Ar ¹ to Ar ⁴ are perdeuterated.

In some embodiments, Ar &^lt; ¹ > to Ar &^lt; ⁴ > are hydrogenated over-hydrogen except for one alkyl group on the terminal aryl.

In some embodiments, the compound is symmetrical with respect to the diarylamino group. In this case, Ar ¹ = Ar ³ and Ar ² = Ar ⁴ .

In some embodiments, the compound is asymmetric with respect to the diarylamino group. In this case, Ar ¹ is different from both Ar ³ and Ar ⁴ . In some embodiments, Ar ² is also different from both Ar ³ and Ar ⁴ .

Some non-limiting examples of compounds having the formula I include the following compounds E1 and E2:

Compound E1:

Compound E2:

Some non-limiting examples of compounds having formula (II) include the following compounds E3 to E9:

Compound E3:

Compound E4:

Compound E5:

Compound E6:

Compound E7:

Compound E8:

E9:

Any of the techniques for producing CC or CN bonds can be used to produce non-hydrogenated analog compounds. A variety of such techniques are known, for example Suzuki, Yamamoto, Stille, and Pd- or Ni-catalyzed CN coupling. Then, in a similar manner using a deuterated precursor material, or more generally in the presence of a Lewis acid H / D exchange catalyst, such as aluminum trichloride or ethylaluminum chloride, in a deuterated solvent such as d6-benzene Lt; / RTI > can be used to prepare novel deuterated compounds. Exemplary manufacturing methods are given in the examples. The degree of deuteration can be determined by NMR analysis and mass spectrometry, for example, atmospheric solid analyte probe mass spectrometry ( ASAP - MS ).

The compounds described herein can be formed into films using liquid deposition techniques. Surprisingly, these compounds have greatly improved properties when compared to similar non-deuterated compounds. Electronic devices including active layers with the compounds described herein have a greatly improved lifetime. Additionally, the lifetime increase is achieved in combination with high quantum efficiency and good color saturation. In addition, the deuterated compounds described herein have greater air tolerance than non-deuterated analogs. This can lead to greater processing tolerance, both in the production and purification of the material and in the formation of electronic devices using the material.

The novel deuterated compounds described herein have utility as a hole transport material, as an electroluminescent material, and as a host for an electroluminescent material.

3. Electronic device

Organic electronic devices that can benefit from having one or more layers comprising the electroluminescent material described herein include (1) devices that convert electrical energy to radiation (e.g., light emitting diodes, light emitting diode displays, or diode lasers A photodetector, a photoconductive battery, a photoresistor, an optical switch, a phototransistor, a phototube, an IR detector), (3) a device that converts a radiation into electrical energy (E. G., Transistors or diodes) that include one or more electronic components including one or more organic semiconductor layers (e. G., Photovoltaic devices or solar cells), and (4) one or more organic semiconductor layers.

An example of an organic electronic device structure is shown in Fig. The device 100 has an anode layer 110 as a first electrical contact layer, a cathode layer 160 as a second electrical contact layer, and an electroactive layer 140 therebetween. There is a buffer layer 120 adjacent to the anode. Adjacent to the buffer layer, there is a hole transporting layer 130 including a hole transporting material. Adjacent to the cathode, there may be an electron transporting layer 150 comprising an electron transporting material. Optionally, the device may include at least one additional hole injection or hole transport layer (not shown) beside the anode 110 and / or at least one additional electron injection or electron transport layer (not shown) next to the cathode 160 Can be used.

The layers 120-150 are referred to individually and collectively as the active layer.

In one embodiment, the various layers have a thickness in the following ranges: the anode 110 is between 50 and 500 nm (500 to 5000 ANGSTROM), and in one embodiment between 100 and 200 ANGSTROM (1000 to 2000 ANGSTROM); The buffer layer 120 is between 5 and 200 nm (50 to 2000 ANGSTROM), and in one embodiment between 20 and 100 nm (200 to 1000 ANGSTROM); The hole transport layer 130 is between 5 and 200 nm (50 to 2000 ANGSTROM), and in one embodiment between 20 and 100 nm (200 to 1000 ANGSTROM); The electroactive layer 140 is between 1 and 200 nm (10 to 2000 Angstroms), and in one embodiment between 10 and 100 nm (100 to 1000 Angstroms); Layer 150 is between 5 and 200 nm (50 to 2000 Angstroms), in one embodiment between 10 and 100 nm (100 to 1000 Angstroms); The cathode 160 is 20 to 1000 nm (200 to 10000 angstroms), and in one embodiment is 30 to 500 nanometers (300 to 5000 angstroms). The location of the electron-hole recombination zone in the device, and thus the emission spectrum of the device, can be influenced by the relative thickness of each layer. The desired proportion of layer thickness will depend on the exact nature of the material used.

Depending on the application of the device 100, the electroactive layer 140 may be either a light emitting layer activated by an applied voltage (such as in a light emitting diode or a luminescent electrochemical cell), or in response to radiant energy ) Or a layer of material that generates a signal with or without an applied bias voltage. Examples of photodetectors include photoconductive cells, photoresistors, optical switches, phototransistors and phototubes, and photon cells, which terms are described in Markus, John, Electronics and Nucleonics Dictionary, 470 and 476 (McGraw-Hill, 1966).

In some embodiments, the novel deuterated compounds are useful as a hole transport material in layer 130. In some embodiments, at least one additional layer comprises a deuterated material. In some embodiments, the additional layer is buffer layer 120. In some embodiments, the additional layer is an electroactive layer 140. In some embodiments, the additional layer is an electron transport layer 150.

In some embodiments, the novel deuterated compounds are useful as host materials for the electroactive material in the electroactive layer 140. In some embodiments, the luminescent material is also deuterated. In some embodiments, at least one additional layer comprises a deuterated material. In some embodiments, the additional layer is buffer layer 120. In some embodiments, the additional layer is a hole transport layer 130. In some embodiments, the additional layer is an electron transport layer 150.

In some embodiments, the novel deuterated compounds are useful as electroactive materials in electroactive layer 140. In some embodiments, the host is also present in the electroactive layer. In some embodiments, the host material is also deuterated. In some embodiments, at least one additional layer comprises a deuterated material. In some embodiments, the additional layer is buffer layer 120. In some embodiments, the additional layer is a hole transport layer 130. In some embodiments, the additional layer is an electron transport layer 150.

In some embodiments, the novel deuterated compounds are useful as an electron transporting material in layer 150. In some embodiments, at least one additional layer comprises a deuterated material. In some embodiments, the additional layer is buffer layer 120. In some embodiments, the additional layer is a hole transport layer 130. In some embodiments, the additional layer is an electroactive layer 140.

In some embodiments, the electronic device has a deuterated material in any combination of layers selected from the group consisting of a buffer layer, a hole transport layer, an electroactive layer, and an electron transport layer.

In some embodiments, the device has additional layers to aid processing or improve functionality. All or any of these layers may comprise a deuterated material. In some embodiments, all organic device layers include deuterated materials. In some embodiments, all of the organic device layers consist essentially of a deuterated material.

a. Electroactive layer

The novel deuterated compounds described herein are useful as an electroactive material in layer (140). The compounds may be used alone or in combination with a host material.

In some embodiments, the electroactive layer consists essentially of a host material and the novel deuterated compounds described herein.

In some embodiments, the host is a bis-condensed cyclic aromatic compound.

In some embodiments, the host is an anthracene derivative compound. In some embodiments, the compound has the formula:

An-L-An

here,

An is an anthracene moiety;

L is a divalent linking group.

In some embodiments of this formula, L is a single bond, -O-, -S-, -N (R) -, or an aromatic group. In some embodiments, An is a mono- or diphenyl anthryl moiety.

In some embodiments, the host has the formula:

A - An - A

here,

An is an anthracene moiety;

A is the same or different in each case and is an aromatic group.

In some embodiments, group A is attached to the 9- and 10-positions of the anthracene moiety. In some embodiments, A is selected from the group consisting of naphthyl, naphthylphenylene, and naphthylnaphthylene. In some embodiments, the compound is symmetric and in some embodiments the compound is asymmetric.

In some embodiments, the host has the formula:

here,

A ¹ and A ² are the same or different in each case and are selected from the group consisting of H, an aromatic group, an alkyl group and an alkenyl group, or A may represent one or more fused aromatic rings;

p and q are the same or different and are an integer of 1 to 3;

In some embodiments, the anthracene derivative is asymmetric. In some embodiments, p is 2 and q is 1.

In some embodiments, at least one of A ¹ and A ² is a naphthyl group. In some embodiments, further substituents are present.

In some embodiments, the host

H1

H2

And combinations thereof.

The novel deuterated compounds described herein can also serve as charge transport hosts for other electroactive materials in the electroactive layer 140, in addition to being useful as electroactive materials in the electroactive layer. In some embodiments, the electroactive layer consists essentially of a novel deuterated material and one or more electroactive materials.

b. Other element layers

Other layers within the device can be made of any material known to be useful for such a layer.

The anode 110 is a particularly efficient electrode for injecting positive charge carriers. It may be made of materials including, for example, metals, mixed metals, alloys, metal oxides or mixed-metal oxides, or may be conductive polymers, or mixtures thereof. Suitable metals include Group 11 metals, metals within Groups 4-6, and Group 8-10 transition metals. If the anode is light transmissive, mixed-metal oxides of Group 12, 13 and Group 14 metals, such as indium-tin-oxide, are generally used. The anode 110 is described in "Flexible light-emitting diodes made from soluble conducting polymer ", Nature vol. 357, pp 477-479 (11 June 1992)]. At least one of the anode and the cathode is preferably at least partially transparent so that the generated light can be observed.

The buffer layer 120 includes a buffer material and is used to improve the planarization, charge transport and / or charge injection characteristics of the underlying layer in the organic electronic device, the removal of impurities such as oxygen or metal ions, Such as, but not limited to, < RTI ID = 0.0 > and / or < / RTI > The buffer material may be a polymer, an oligomer, or a small molecule. They may be deposited or deposited from a liquid which may be in the form of solutions, dispersions, suspensions, emulsions, colloidal mixtures or other compositions.

The buffer layer may be formed of a polymeric material that is often doped with a protic acid, for example, polyaniline (PANI) or polyethylenedioxythiophene (PEDOT). The protic acid may be, for example, poly (styrenesulfonic acid), poly (2-acrylamido-2-methyl-1-propanesulfonic acid) or the like.

The buffer layer may comprise a charge transport compound such as copper phthalocyanine and a tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) system.

In some embodiments, the buffer layer comprises at least one electrically conductive polymer and at least one fluorinated acid polymer. Such materials are described, for example, in published U.S. Patent Application Nos. 2004-0102577, 2004-0127637, and 2005/205860.

In some embodiments, the novel deuterated compounds described herein have utility as a hole transport material. Examples of porosity-transferring materials for layer 130 are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y. Wang. Both hole transport molecules and polymers can be used. Typically used hole transporting molecules include N, N'-diphenyl-N, N'-bis (3-methylphenyl) - [1,1'- biphenyl] -4,4'- diamine (TPD) (4-methylphenyl) - N, N'-bis (4-ethylphenyl) - [1,1 (3,3'-dimethyl) biphenyl] -4,4'-diamine (ETPD), tetrakis- (3-methylphenyl) -N, N, N ', N'- (PDA), a-phenyl-4-N, N-diphenylaminostyrene (TPS), p- (diethylamino) benzaldehyde diphenylhydrazone (DEH), triphenylamine Phenyl-3- [p- (diethylamino) styryl] -5- [p (methylphenyl) methane - (diethylamino) phenyl] pyrazoline (PPR or DEASP), 1,2-trans- bis (9H-carbazol-9-yl) cyclobutane (DCZB), N, N, N ' (4-methylphenyl) - (1,1'-biphenyl) -4,4'-diamine (TTB), N, N'-bis (naphthalen- ) Benzidine (? - NPB), and porphyrinic compounds, such as copper phthalocyanine. Commonly used hole transporting polymers are polyvinylcarbazole, (phenylmethyl) -polysilane, and polyaniline. A hole transporting polymer may also be obtained by doping hole transport molecules such as those mentioned above into a polymer such as polystyrene and polycarbonate. In some cases, triarylamine polymers, particularly triarylamine-fluorene copolymers, are used. In some cases, the polymers and copolymers are cross-linkable. Examples of crosslinkable hole transporting polymers can be found, for example, in U.S. Patent Application Publication No. 2005-0184287 and PCT Application Publication No. WO 2005/052027. In some embodiments, the hole transport layer comprises a p-dopant, such as tetrafluorotetracyanoquinodimethane and perylene-3,4,9,10-tetracarboxylic-3,4,9,10- 0.0 > dihydride. ≪ / RTI >

In some embodiments, the novel deuterated compounds described herein have utility as electron transporting materials. Examples of other electron transport materials that can be used in layer 150 include metal chelate oxinoid compounds such as tris (8-hydroxyquinolato) aluminum (Alq3); Bis (2-methyl-8-quinolinolato) (para-phenyl-phenolato) aluminum (III) (BAlQ); And azole compounds such as 2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole (PBD) and 3- (4-t-butylphenyl) -1,2,4-triazole (TAZ), and 1,3,5-tri (phenyl-2-benzimidazole) benzene (TPBI) ; Quinoxaline derivatives such as 2,3-bis (4-fluorophenyl) quinoxaline; Phenanthroline derivatives such as 9,10-diphenylphenanthroline (DPA) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); And mixtures thereof. The electron transporting layer may also be doped with an n-dopant, such as Cs or other alkali metal. The layer 150 may serve both as a confinement layer that not only promotes electron transport but also prevents buffering, or quenching of the exciton at the layer interface . Preferably, such a layer promotes electron mobility and reduces swelling.

The cathode 160 is a particularly efficient electrode for injecting electrons or negative charge carriers. The cathode may be any metal or non-metal having a lower work function than the anode. The material for the cathode may be selected from Group 1 alkali metals (e.g., Li, Cs), Group 2 (alkaline earth) metals, Group 12 metals (including rare earth elements and lanthanide and actinide elements). Aluminum, indium, calcium, barium, samarium, and magnesium may be used in combination with such materials. To lower the operating voltage, Li- or Cs- containing organometallic compounds, LiF, CsF, and Li ₂ O can also be deposited between the organic layer and the cathode layer.

It is known to have other layers in the organic electronic device. For example, a layer (not shown) that serves to control the amount of positive charge injected and / or to provide band-gap matching of the layer or to act as a passivation layer may be formed on the anode 110 and the buffer layer 120 ). ≪ / RTI > It is possible to use layers known in the art, for example, superfine layers of metals such as copper phthalocyanine, silicon oxy-nitride, fluorocarbon, silane, or Pt. Alternatively, some or all of the anode layer 110, the active layer 120, 130, 140, 150, or the cathode layer 160 may be surface treated to increase the charge carrier transport efficiency. The selection of the material of each component layer preferably determines the balance of positive and negative charges in the emitter layer to provide a device with high electroluminescent efficiency.

It is understood that each functional layer can consist of more than one layer.

The device may be manufactured by a variety of techniques including sequentially depositing individual layers on a suitable substrate. Materials such as glass, plastic and metal can be used. Conventional deposition techniques such as thermal evaporation, chemical vapor deposition and the like can be used. Alternatively, a solution or dispersion in a suitable solvent, such as, but not limited to, spin coating, dip coating, roll-to-roll technology, inkjet printing, screen printing, gravure printing, Layer can be applied.

In order to achieve a high efficiency LED, the HOMO (highest occupied molecular orbital) of the hole transport material is preferably aligned with the work function of the anode, and the LUMO (lowest unoccupied molecular orbital) of the electron transport material is preferably Lt; / RTI > Chemical compatibility and sublimation temperature of materials are also important considerations in selecting electron and hole transport materials.

It is understood that the efficiency of devices made with the chrysene compounds described herein can be further improved by optimizing other layers in the device. For example, a more efficient cathode such as Ca, Ba or LiF can be used. Shaped substrates and novel hole transporting materials which lead to a reduction in operating voltage or increase quantum efficiency are also applicable. Additional layers may also be added to tailor the energy levels of the various layers and promote electroluminescence.

The compounds of the present invention are often fluorescent and photoluminescent and may be useful in applications other than OLEDs, for example in oxygenation indicators and fluorescence indicators in bioassays.

Example

The following examples illustrate certain features and advantages of the present invention. The examples are intended to illustrate the invention and are not intended to be limiting. Unless otherwise indicated, all percentages are by weight.

Comparative Example A

This Comparative Example illustrates the preparation of Comparative Compound A, which is a non-hydrogenated electroluminescent material.

(a) Preparation of 1- (4-tert-butylstyryl) naphthalene.

The oven-dried 500 ml three-neck round bottom flask was equipped with a magnetic stirring bar, an addition funnel and a nitrogen inlet connector. To the flask was added (1-naphthylmethyl) triphenylphosphonium chloride (12.07 g, 27.5 mmol) and 200 ml of anhydrous THF. Sodium hydride (1.1 g, 25 mmol) was added in one portion. The mixture turned bright orange and allowed to stir at room temperature overnight. A solution of 4-tert-butyl-benzaldehyde (7.1 g, 25 mmol) in anhydrous THF (30 mL) was added to the addition funnel using a cannula. The aldehyde solution was added dropwise to the reaction mixture over 45 minutes. The reaction was allowed to stir at room temperature for 24 hours (orange color disappeared). Silica gel was added to the reaction mixture and the volatiles were removed under reduced pressure. The crude product was purified by column chromatography on silica gel using 5-10% dichloromethane in hexanes. The product was isolated as a mixture of cis- and trans-isomers (6.3 g, 89%) and used without isolation. ^The structure was confirmed by ¹ H NMR.

(b) Preparation of 3-tert-butylclycine.

1- (4-tert-butylstyryl) naphthalene (4.0 g, 14.0 mmol) was dissolved in dry toluene (1 L) in a 1-liter photochemical vessel equipped with a nitrogen inlet and stir bar. After cooling the bottle of dry propylene oxide in ice water, 100 ml of epoxide was withdrawn with a syringe and added to the reaction mixture. Iodine (3.61 g, 14.2 mmol) was added last. The condenser was attached to the top of the photochemical vessel and a halogen lamp (Hanovia, 450 W) was turned on. The color was confirmed to be gone and the reaction was stopped by turning off the lamp when no more iodine was left in the reaction mixture. The reaction was completed within 3.5 hours. Toluene and excess propylene oxide were removed under reduced pressure to give a dark yellow solid. The crude product was dissolved in a small amount of 25% dichloromethane in hexane, passed through a 4 "plug of neutral alumina and washed with 25% dichloromethane in hexane (approximately 1 liter). Removal of volatiles To give 3.6 g (91%) of 3-tert-butylclycene as a yellow solid. The structure was confirmed by ¹ H NMR.

(c) Preparation of 6,12-dibromo-3-tert-butylclycine

3-tert-butylclycene (4.0 g, 14.1 mmol) and trimethyl phosphate (110 mL) were mixed in a 500 mL round bottom flask. After addition of bromine (4.95 g, 31 mmol), a reflux condenser was attached to the flask and the reaction mixture was stirred in an oil bath at 105 ° C for 1 hour. A white precipitate formed almost immediately. The reaction mixture was worked up by pouring into a small volume of ice water (100 mL). The mixture was vacuum-filtered and washed well with water. The resulting tan solids were dried under vacuum. The crude product was boiled in methanol (100 mL), cooled to room temperature and filtered again to give 3.74 g (60%) of white solid. ^The structure was confirmed by ¹ H NMR.

(d) Preparation of 3-tert-butyl-N ⁶ , N ⁶ , N ¹² , N ¹² -tetraphenylcycline-6,12-diamine,

In a drybox, 6,12-dibromo-3-tert-butylclycene (0.8 g, 1.81 mmol) and diphenylamine (1.22 g, 7.2 mmol) were combined in a 500 mL round bottom flask and 10 mL of dry And dissolved in toluene. (0.036 g, 0.02 mmol) was dissolved in dry toluene (5 mL) and treated with 10 < RTI ID = 0.0 >Lt; / RTI > The catalyst solution was added to the reaction mixture and after stirring for 10 minutes sodium tert-butoxide (0.35 g, 3.62 mmol) and 5 mL of dry toluene were added. After an additional 10 minutes, the reaction flask was removed from the dry box, attached to a nitrogen line and stirred overnight at 110 占 폚. The next day, the reaction mixture was cooled to room temperature and filtered through a 5.08 cm (2 inch) plug of silica gel and Celite, washing with 500 mL of dichloromethane. The volatiles were removed under reduced pressure to give a dark brown oil. The crude product was further purified by flash chromatography on silica gel using an Isolera purification system from Biotage. The resulting solid was washed with methanol and then recrystallized from hot hexane to give 0.26 g (25%) of product. ^The structure was confirmed by ¹ H NMR.

Example 1

This example demonstrates the preparation of compound E3, which is a compound with formula II.

These compounds were prepared from 6,12-dibromo-3-tert-butylclycene and di (excess hydrogenated phenyl) amine using the procedure described above for Comparative Compound A. The yield was 0.37 g (36%). The structure of compound E3 was confirmed by ¹ H NMR.

Comparative Example B

This Comparative Example illustrates the preparation of Comparative Compound B, a non-hydrogenated electroluminescent material.

, U.; Adam, M.;

, K. Chem. Ber. 1994, 127, 437-444])을 질소 충전된 글러브 박스 내에서 둥근 바닥 플라스크에 넣고, 0.38 g (2.2 mM)의 다이페닐아민 및 0.2 g의 소듐 tert-부톡사이드 (2 mM)를 40 ㎖의 톨루엔과 함께 첨가하였다. 0.15 g의 Pd₂DBA₃ (0.15 mM) 및 0.07 g의 P(t-Bu)3 (0.3 mM)을 10 ㎖의 톨루엔에 용해시키고 교반하면서 첫 번째 용액에 첨가하였다. 모든 재료가 혼합되면, 용액이 천천히 발열하면서 황갈색이 된다. 글러브 박스 내에서 질소 하에 1시간 동안 용액을 80℃로 교반 및 가열하였다. 용액은 즉시는 어두운 자주색이 되나, 약 80℃에 도달하면 뚜렷한 녹색 발광을 동반하는 어두운 황록색이 된다. 실온으로 냉각시킨 후에 용액을 글러브 박스에서 꺼내고 톨루엔으로 용리하는 짧은 염기성-알루미나 플러그를 통해 여과하여 밝은 황록색 밴드를 수득한다. 증발시키고 톨루엔/메탄올로부터 재결정화하여, 1-H NMR로 확인된 바와 같이 예상 생성물을 0.55 g의 수율로 얻었다.0.45 g of 2,6-di-t-butyl-9,10-dibromoanthracene (1 mM)

, U .; Adam, M .;

, K. Chem. Ber. 1994, 127, 437-444) was placed in a round bottom flask in a nitrogen-filled glove box and 0.38 g (2.2 mM) of diphenylamine and 0.2 g of sodium tert-butoxide (2 mM) Was added with toluene. 0.15 g of Pd ₂ DBA ₃ (0.15 mM) and 0.07 g of P (t-Bu) 3 (0.3 mM) were dissolved in 10 ml of toluene and added to the first solution with stirring. When all the ingredients are mixed, the solution slowly turns yellow with a fever. The solution was stirred and heated to 80 < 0 > C under nitrogen for 1 hour in a glove box. The solution immediately becomes a dark purple color, but when it reaches about 80 ° C, it becomes a dark yellow green color accompanied by a pronounced green luminescence. After cooling to room temperature the solution is taken out of the glovebox and filtered through a short basic-alumina plug eluting with toluene to give a bright yellow-green band. Evaporation and recrystallization from toluene / methanol gave the expected product in 0.55 g yield as confirmed by 1-H NMR.

Example 2

This example demonstrates the preparation of compound E1, which is a compound having the formula (I).

These compounds were prepared from 9,10-dibromo-2,6-di-tert-butyl anthracene and di (excess hydrogenated phenyl) amine using the procedure described above for comparative compound B. The yield was 0.55 g. The structure of the compound E1 was confirmed by ¹ H NMR.

Example 3 and Comparative Example C

These examples illustrate the fabrication and performance of devices with blue emitters. The following materials were used:

P1

H1

The device had the following structure on the glass substrate:

Anode = indium tin oxide (ITO): 50 nm

Buffer layer = buffer (1) (50 nm), which is an aqueous dispersion of electrically conductive polymer and polymeric fluorinated sulfonic acid. Such materials are described, for example, in U.S. Patent Application Publication Nos. 2004/0102577, 2004/0127637, and 2005/0205860.

Hole transport layer = polymer P1 (20 nm)

Electroactive layer = 13: 1 host H1: dopant (40 nm)

Electron transport layer = metal quinolate derivative (10 nm)

Cathode = CsF / Al (0.7 / 100 nm)

OLED devices were fabricated by a combination of solution fabrication and thermal evaporation techniques. Patterned indium tin oxide (ITO) coated glass substrates from Thin Film Devices, Inc. were used. These ITO substrates are based on Corning 1737 glass coated with ITO having a sheet resistance of 30 ohms / square and a light transmittance of 80%. The patterned ITO substrate was ultrasonically cleaned in an aqueous detergent solution and rinsed with distilled water. The patterned ITO was then ultrasonically cleaned in acetone, rinsed with isopropanol and dried in a nitrogen stream.

Immediately prior to device fabrication, the cleaned and patterned ITO substrate was treated with UV ozone for 10 minutes. Immediately after cooling, the aqueous dispersion of Buffer 1 was spin-coated onto the ITO surface and heated to remove the solvent. After cooling, the substrate was then spin-coated with a solution of the hole transport material and then heated to remove the solvent. After cooling, the substrate was spin-coated with the light emitting layer solution and heated to remove the solvent. The substrate was masked and placed in a vacuum chamber. A layer of CsF was deposited subsequent to the electron transport layer by thermal evaporation. Subsequently, the mask was changed in a vacuum state and a layer of Al was deposited by thermal evaporation. The chamber was evacuated and the device encapsulated using a glass lid, a desiccant, and a UV curable epoxy.

OLED samples were characterized by measuring their (1) current-voltage (I-V) curves, (2) electroluminescence radiance vs voltage, and (3) electroluminescence spectral versus voltage. All three measurements were performed simultaneously and computer controlled. The current efficiency of a device at a given voltage is determined by dividing the electroluminescent emission luminance of the LED by the current density required to operate the device. The unit is cd / A. Power efficiency is the current efficiency divided by the operating voltage. The unit is lm / W. The device data is provided in Table 1.

The relative lifetime of a device made of a chrysene dopant having the formula (II) is significantly better than that of the device made with the comparative compound A.

Example 4 and Comparative Example D

These examples illustrate the fabrication and performance of devices with green emitters.

The device had the following structure on the glass substrate:

Anode = ITO (180 nm)

Buffer layer = Buffer 1 (50 nm)

Hole transport layer = polymer P1 (20 nm)

Electroactive layer = 13: 1 Host H1: dopant (60 nm)

Electron transport layer = metal quinolate derivative (10 nm)

Cathode = CsF / Al (1.0 / 100 nm)

An OLED device was prepared as described above for Example 3. The device data (average of three devices) is provided in Table 2.

The relative lifetime of a device made of an anthracene dopant having the formula I is significantly better than that of an anthracene dopant comparison compound B.

It is to be understood that not all of the acts described above in the general description or the examples are required, that some of the specified acts may not be required, and that one or more additional actions in addition to those described may be performed. Also, the order in which actions are listed is not necessarily the order in which they are performed.

In the foregoing specification, the concepts have been described with reference to specific embodiments. However, it will be understood by those skilled in the art that various changes and modifications may be made therein without departing from the scope of the invention as set forth in the claims below. Accordingly, the specification and drawings are to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present invention.

Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. It should be understood, however, that any feature (s) capable of generating or clarifying benefits, advantages, solutions to problems, and any benefit, advantage, or solution may be of particular importance to any or all of the claims , And should not be construed as required or essential features.

It is to be understood that certain features may be resorted to and described in connection with the separate embodiments for clarity and in combination with a single embodiment. Conversely, various features described in connection with a single embodiment for the sake of simplicity may also be provided separately or in any subcombination. In addition, references to ranges of values include all values within that range.

Claims (8)

Wherein the active layer comprises a compound of the formula (I) or (II), wherein the active layer comprises at least one D, wherein the first layer comprises a first electrical contact layer, a second electrical contact layer and at least one active layer therebetween. .
(I)

≪ RTI ID = 0.0 &

[In the above formula,
R ¹ is in each case the same or different and is selected from the group consisting of D, alkyl hydrocarbons and deuterated alkyl, wherein adjacent R ¹ groups may be joined together to form a 5- or 6-membered aliphatic ring, ;
Ar ¹ to Ar ⁴ are the same or different and are selected from the group consisting of an aryl group, the aryl group optionally having at least one substituent group on the aryl ring and containing heteroaryl, wherein the substituent group is selected from the group consisting of D, Alkyl, alkoxy, aryl, cyano, nitro, -N (R ') (R "), hydroxy, carboxy, alkenyl, alkynyl, aryloxy, alkoxycarbonyl, perfluoroalkyl, perfluoroalkoxy , aryl, silyl, siloxanes, _{thioalkoxy, -S (O) 2 -N (} R ') (R "), -C (= O) -N (R') (R"), (R ') ( (O) < / RTI > _s -aryl, wherein s is 0 to < RTI ID = 2, or -S (O) _s -heteroaryl where s is 0 to 2, and wherein each R 'and R "is independently selected from the group consisting of optionally substituted alkyl, cycloalkyl, Group, R 'and R "represent a nitrogen atom to which they are bonded and Together form a ring system, the substituent may also be a crosslinking group;
a is the same or different in each case and is an integer of 1 to 4;
b is the same or different in each case and is an integer of 1 to 5]. The organic electroluminescent device according to claim 1, wherein the compound of formula (I) or (II) is deuterated at 50% or more. The organic electronic device according to claim 1 or 2, wherein at least one of Ar ¹ to Ar ⁴ in the compound of formula (I) or (II) is deuterated arylene. 3. The compound according to claim 1 or 2, wherein the compound of formula (I) or (II) has at least one substituent group on at least one aryl ring of Ar ¹ to Ar ⁴ , and the at least one substituent group and at least one aryl ring ≪ / RTI > 3. The organic electronic device according to claim 1 or 2, wherein a in the compound of formula (I) is 4 and R < ¹ > 3. The organic electronic device according to claim 1 or 2, wherein b in the compound of formula (II) is 5 and R < ¹ > 3. A compound according to claim 1 or 2, wherein Ar ¹ to Ar ⁴ in the compounds of formula I or II are selected from the group consisting of naphthyl, phenylnaphthyl, naphthylphenyl, binaphthyl, Organic electroluminescent device.
(III)

[In the above formula,
R ² is the same or different in each occurrence and is selected from the group consisting of D, alkyl, alkoxy, aryl, silyl, and siloxane, or adjacent R ² groups may be connected to form an aromatic ring;
c is the same or different in each occurrence and is an integer from 0 to 4;
d is the same or different in each occurrence and is an integer from 0 to 5;
m is the same or different in each case and is an integer of 0 to 6]. The organic electronic device according to claim 1 or 2, wherein the active layer is an electroactive layer and further comprises a host material.

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