KR20150036725A - Deuterated compounds for electronic applications - Google Patents

Abstract

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

Description

[0001] DEUTERATED COMPOUNDS FOR ELECTRONIC APPLICATIONS [0002]

Related Application Data

This application claims the benefit of US Provisional Patent Application No. 61 / 156,181, filed February 27, 2009, US Provisional Patent Application No. 61 / 179,407, filed May 19, 2009, U.S. Provisional Patent Application No. 61 / 239,574, which claims priority under 35 USC § 119 (e), each of which is incorporated herein by reference in its entirety.

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

BACKGROUND ART [0002] Organic electronic devices that emit light, such as light emitting diodes that make up a display, exist in many different types of electronic equipment. In both such devices, an organic active layer is interposed between the two electrical contact layers. The at least one electrical contact layer is light transmissive so that light can pass through the electrical contact layer. The organic active layer emits light through the electrical contact layer when applying electricity across the optically transparent electrical contact layer.

The use of organic electroluminescent compounds as active ingredients in light emitting diodes is well known. Simple organic molecules such as anthracene, thiadiazole derivatives and coumarin derivatives are known to exhibit electroluminescence. Semiconducting conjugated polymers have also been used as electroluminescent compounds, 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. In many cases, the electroluminescent compound is present as a dopant in the host material.

There is a continuing need for new materials for electronic devices.

An aryl-substituted anthracene having at least one deuterium substituent is provided.

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

An electroactive composition comprising (a) an aryl-substituted anthracene having at least one deuterium substituent and (b) an electroluminescent capable electroactive dopant having an emission maximum between 380 and 750 nm is also provided.

Embodiments are illustrated in the accompanying drawings to facilitate an understanding of the concepts presented herein.
≪ 1 >
Figure 1 includes an illustration of one example of an organic electronic device.
2,
Figure 2 includes the < ¹ > H NMR spectrum of the comparative compound of Comparative Example A;
3,
Figure 3 includes a ¹ H NMR spectrum of the deuterated compound of Example 1.
<Fig. 4>
Figure 4 includes the mass spectrum of the deuterated compound of Example 1.
Skilled artisans appreciate that the subject matter of the drawings is illustrated for simplicity and clarity and is 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 suns 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 appreciate that other aspects and embodiments are possible without departing from the scope of the present invention.

Other features and advantages of any one or more of the embodiments will be apparent from the following detailed description and the claims. The detailed description first reviews the definition and commentary of terms, followed by deuterated 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 has no 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. 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 "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 a secondary carbon atom. The term "tertiary alkyl" refers to a branched alkyl group having a tertiary carbon atom. In some embodiments, the branched alkyl group is attached via secondary or tertiary carbon.

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. 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 bonded directly to an aryl is replaced by D. The term "arylene" is intended to mean a group derived from an aromatic hydrocarbon having two points of attachment. In some embodiments, the aryl group has from 3 to 60 carbon atoms.

The term "aryloxy" refers to the RO- group wherein R is aryl.

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. The phrase "adjacent " when used to refer to a layer in a device 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 adjacent R groups (i.e., R groups on atoms connected by a bond) in the formula.

The term "dehydrated" is intended to mean that at least one hydrogen (H) has been replaced by deuterium (D). Deuterium exists at least 100 times the level of natural abundance. A "deuterated derivative" of compound X has the same structure as compound X, but is accompanied by at least one D that replaces H.

The term "dopant" refers to a material in a layer comprising a host material, such that the radiation emission, acceptance or filtration of the layer in the absence of such material, as compared to the wavelength (s) Or to change the target wavelength (s) or electronic property (s) of filtration.

When referring to a layer or material, the term "electroactive" is intended to mean a layer or material that exhibits electronic or electron-emitting properties. In an electronic device, the electroactive material electronically promotes the operation of the device. Examples of electroactive materials include materials that conduct, inject, transport, or block charges that can be electrons or holes, and materials that exhibit a change in concentration of electron-hole pairs or emit radiation upon acceptance of radiation, It does not. 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 by a different atom. In some embodiments, the different atoms are N, O, or S.

The term "host material" is intended to mean a material to which a dopant is added. The host material may or may not have the ability to emit, accept, or filter the electronic property (s) or radiation. In some embodiments, the host material is present at a higher concentration.

The term "layer" is used interchangeably with the term "film " to refer to a coating that covers a desired area. This term is not limited by size. The area may be as large as the entire device, as small as a specific functional area, such as a real image 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 simply "electronic device" refers to an element comprising one or more organic semiconductor layers or materials. All groups may be substituted or unsubstituted, unless otherwise indicated. In some embodiments, the substituent is selected from the group consisting of D, halide, alkyl, alkoxy, aryl, aryloxy, cyano, and NR ₂ , wherein R is alkyl or aryl.

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 will depend on the definition. Also, 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. Deuterated compounds

The novel deuterated compound is an aryl-substituted anthracene compound having at least one D, In some embodiments, the compound is deuterated more than 10%. This means that at least 10% of H is replaced by D. In some embodiments, the compound is 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, the compound is 100% deuterated.

In one embodiment, the deuterated compound comprises a compound of formula &lt; RTI ID = 0.0 &gt;

(I)

(here,

R ¹ to R ⁸ are the same or different in each case and are selected from the group consisting of H, D, alkyl, alkoxy, aryl, aryloxy, siloxane, and silyl;

Ar ¹ and Ar ² are the same or different and are selected from the group consisting of an aryl group;

Ar ³ and Ar ⁴ are the same or different and are selected from the group consisting of H, D, and aryl groups,

And at least one D.

In some embodiments of formula I, at least one D is present in a substituent group on the aryl ring. In some embodiments, the substituent group is selected from alkyl and aryl.

In some embodiments of formula I, at least one of R &^lt; ¹ &gt; to R &^lt; ⁸ &gt; In some embodiments, at least two of R &^lt; ¹ &gt; to R &^lt; ⁸ &gt; In some embodiments, at least three are D; In some embodiments, at least four are D; In some embodiments, at least five are D; In some embodiments, at least six are D; In some embodiments, at least seven are D. In some embodiments, all of R &^lt; ¹ &gt; through R &^lt; ⁸ &gt;

In some embodiments, R ¹ to R ⁸ are selected from H and D. In some embodiments, one of R ¹ to R ⁸ is D and seven are H. In some embodiments, two of R ¹ through R ⁸ are D and six are H. In some embodiments, three of R ¹ to R ⁸ are D and five are H. In some embodiments, four of R ¹ to R ⁸ are D and four are H. In some embodiments, five of R ¹ to R ⁸ are D and three are H. In some embodiments, six of R ¹ through R ⁸ are D and two are H. In some embodiments, seven of R &^lt; ¹ &gt; to R &^lt; ⁸ &gt; In some embodiments, ^eight of R ¹ through R 8 are D;

In some embodiments, at least one of R ¹ to R ⁸ is selected from alkyl, alkoxy, aryl, aryloxy, siloxane, and silyl, and the remainder of R ¹ to R ⁸ is selected from H and D. In some embodiments, R ² is selected from alkyl, alkoxy, aryl, aryloxy, siloxane, and silyl. In some embodiments, R &lt; ² &gt; is selected from alkyl and aryl. In some embodiments, R &lt; ² &gt; is selected from deuterated alkyl and deuterated aryl. In some embodiments, R &lt; ² &gt; is selected from deuterated aryl, which is at least 10% deuterated. In some embodiments, R ² is deuterated at least 20%; In some embodiments, greater than 30% deuterated; In some embodiments, greater than 40% deuterated; In some embodiments, at least 50% deuterated; In some embodiments, at least 60% deuterated; In some embodiments, greater than 70% deuterated; In some embodiments, greater than 80% deuterated; In some embodiments, at least 90% deuterated is deuterated with deuterated allyl. In some embodiments, R &lt; ² &gt; is selected from 100% deuterated, deuterated aryl.

In some embodiments of formula I, at least one of Ar ¹ to Ar ⁴ is deuterated aryl. In some embodiments, Ar ³ and Ar ⁴ are selected from D and deuterated allyl.

In some embodiments of formula I, Ar &^lt; ¹ &gt; to Ar &^lt; ⁴ &gt; In some embodiments of formula I, 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% deuterated; In some embodiments, 100% deuterated.

In some embodiments, the compound of formula I 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 compound is 100% deuterated.

In some embodiments, Ar ¹ and Ar ² are selected from the group consisting of phenyl, naphthyl, phenanthryl, anthracenyl, and deuterated derivatives thereof. In some embodiments, Ar ¹ and Ar ² are selected from the group consisting of phenyl, naphthyl, and deuterated derivatives thereof.

In some embodiments, Ar ³ and Ar ⁴ are selected from the group consisting of phenyl, naphthyl, phenanthryl, anthracenyl, phenylnaphthylene, naphthylphenylene, deuterated derivatives thereof, and groups having the formula (II)

&Lt; RTI ID = 0.0 &

(here,

R ⁹ is the same or different in each case and is selected from the group consisting of H, D, alkyl, alkoxy, siloxane and silyl, or adjacent R ⁹ groups may be joined together to form an aromatic ring;

m is the same or different in each case and is an integer of 1 to 6).

In some embodiments, Ar ³ and Ar ⁴ are selected from the group consisting of phenyl, naphthyl, phenylnaphthylene, naphthylphenylene, a deuterated derivative thereof, and a group having the formula (III)

(III)

(Wherein R &lt; ⁹ &gt; and m are as defined above for formula II). In some embodiments, m is an integer from 1 to 3.

In some embodiments, at least one of Ar ¹ to Ar ⁴ is a heteroaryl group. In some embodiments, the heteroaryl group is deuterated. In some embodiments, the heteroaryl 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, the heteroaryl group is 100% deuterated. In some embodiments, the heteroaryl group is selected from carbazole, benzofuran, dibenzofuran, and deuterated derivatives thereof.

In some embodiments of formula I, at least one of R ¹ to R ⁸ is D and at least one of Ar ¹ to Ar ⁴ is deuterated aryl. In some embodiments, the compound is deuterated more than 10%. In some embodiments, the compound is 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, the compound is 100% deuterated.

Some non-limiting examples of compounds having the formula (I) include the following compounds H1 to H14:

Compound H1:

(Wherein x + y + z + n is 1 to 26)

Compound H2:

(Wherein x + y + z + p + n is 1 to 30)

Compound H3:

(Wherein x + y + z + p + n + r is 1 to 32)

Compound H4:

(Wherein x + y + z + p + n is 1 to 18)

Compound H5:

(Wherein x + y + z + p + n + q is 1 to 34)

Compound H6:

(Where x + y + z + n is 1 to 18)

Compound H7:

(Wherein x + y + z + p + n is 1 to 28)

Compound H8:

Compound H9:

Compound H10:

Compound H11:

Compound H12:

Compound H13:

Compound H14:

Non-deuterated analogs of the new compounds can be prepared by known coupling and substitution reactions. Subsequently, a Lewis acid H / D exchange catalyst, such as aluminum trichloride or ethylaluminum chloride, or an acid, such as CF ₃ COOD, is used in a similar manner using a deuterated precursor material, A new deuterated compound can be prepared by treating a compound that is non-deuterated with a deuterated solvent such as d6-benzene in the presence of DCl and the like. Exemplary preparations are provided 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). Intermediate hydrogenated or partially deuterated aromatic compounds or alkyl compounds can be obtained from commercial sources or obtained using known methods. Some examples of such methods can be found in the literature: a) "Efficient H / D Exchange Reactions of Alkyl-Substituted Benzene Derivatives by Means of the Pd / C-H2-D2O System" Hiroyoshi Esaki, Fumiyo Aoki, Miho Umemura, Masatsugu Kato, Tomohiro Maegawa, Yasunari Monguchi, and Hironao Sajiki Chem. Eur. J. 2007, 13, 4052-4063; b) Aromatic H / D Exchange Reaction Catalyzed by Groups 5 and 6 Metal Chlorides "GUO, Qiao-Xia, SHEN, Bao-Jian; GUO, Hai-Qing TAKAHASHI, Tamotsu Chinese Journal of Chemistry, 2005, 23, 341-344); c) a novel deuterium effect on dual charge-transfer and ligand-field emission of the cis-dichlorobis (2,2'-bipyridine) iridium (III) ion "Richard J. Watts, Shlomo Efrima, and Horia Metiu J Am. Chem. Soc., 1979, 101 (10), 2742-2743; d) Carmen Boix and Martyn Poliakoff Tetrahedron Letters 40 (1999) 4433-4436; "Efficient HD Exchange of Near-Critical D20 Catalysts by a Polymer-Supported Sulphonic Acid"; e) U.S. Pat. No. 3,849,458; f) "Efficient CH / CD Exchange Reaction on the Alkyl Side Chain of Aromatic Compounds Using Heterogeneous Pd / C in D2O" Hironao Sajiki, Fumio Aoki, Hiroyoshi Esaki, Tomohiro Maegawa, and Kosaku Hirota Org. Lett., 2004, 6 (9), 1485-1487].

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.

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. Hole injection layer 120 may be present adjacent to the anode. Adjacent to the hole injecting layer, there may be a hole transporting layer 130 including a hole transporting material. Adjacent the cathode, there may be an electron transporting layer 150 comprising an electron transporting material. The device may use one or more additional hole injection or hole transport layers (not shown) beside the anode 110 and / or one or more additional electron injection or electron transport layers (not shown) next to the cathode 160 have.

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 500 to 5000 A, in one embodiment 1000 to 2000 A; The hole injection layer 120 is 50 to 2000 A, in one embodiment 200 to 1000 A; The hole transporting layer 130 is between 50 and 2000 ANGSTROM, and in one embodiment between 200 and 1000 ANGSTROM; The electroactive layer 140 is between 10 and 2000 Angstroms, and in one embodiment between 100 and 1000 Angstroms; Layer 150 is between 50 and 2000 Angstroms, and in one embodiment between 100 and 1000 Angstroms; The cathode 160 is between 200 and 10000 angstroms, and in one embodiment between 300 and 5000 angstroms. The position of the electron-hole recombination zone in the device, i.e. the emission spectrum of the device, can be influenced by the relative thickness of each layer. The required ratio 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 photovoltaic cells, and these terms are described in Markus, John, Electronics and Nucleonics Dictionary, 470 and 476 (McGraw-Hill, Inc. 1966).

One or more new deuterated materials described herein may be present in one or more active layers of the device. Deuterated materials may be used alone or in combination with non-deuterated materials.

In some embodiments, a new deuterated compound is useful as a hole transport material in layer 130. In some embodiments, at least one additional layer comprises a new deuterated material. In some embodiments, the additional layer is a hole injection 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 compound is useful as a host material for an electroactive dopant 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 a hole injection 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, a new deuterated compound is 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 a hole injection 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 hole injection 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 of formula (I) are useful as host materials for electroactive dopant materials in layer (140). The compound may be used alone or in combination with the second host material. The new deuterated compound can be used as a host for dopants with emission of any color. In some embodiments, the new deuterated compound is used as a host for a green or blue light emitting material.

In some embodiments, the electroactive layer consists essentially of a host material having the formula I and at least one electroactive dopant. In some embodiments, the electroactive layer consists essentially of a first host material having the formula I, a second host material, and an electroactive dopant. Examples of the second host material include, but are not limited to, chrysene, phenanthrene, triphenylene, phenanthroline, naphthalene, anthracene, quinoline, isoquinoline, quinoxaline, phenylpyridine, benzodifuran, and metal quinolate complexes. It does not.

The amount of dopant present in the electroactive composition is generally from 3 to 20% by weight, based on the total weight of the composition; In some embodiments, in the range of 5 to 15 wt%. When a second host is present, the ratio of the first host to the second host having the formula I is generally from 1:20 to 20: 1; In some embodiments, in the range of 5:15 to 15: 5. In some embodiments, the first host material having the formula I comprises at least 50 wt% of the total host material; In some embodiments, it is at least 70% by weight.

In some embodiments, the second host material has the formula (IV)

(IV)

(here,

Ar ⁵ is the same or different in each case, and is an aryl group;

Q is a polyvalent aryl group and

&Lt; / RTI &gt;

T is _{(CR ') a, SiR 2} , S, SO 2, PR, PO, PO 2, is selected from the group consisting of BR, and R;

R is the same or different in each occurrence and is selected from the group consisting of alkyl, and aryl;

R 'is the same or different in each occurrence, and is selected from the group consisting of H and alkyl;

a is an integer of 1 to 6;

and n is an integer of 0 to 6).

n may have a value of from 0 to 6, but it will be understood that the value of n in some Q groups is limited by the chemical nature of the group. In some embodiments, n is 0 or 1.

In some embodiments of formula IV, adjacent Ar groups are linked together to form a carbazole-like ring. In formula IV, "adjacent" means that the Ar groups are attached to the same N.

In some embodiments, Ar ⁵ is independently selected from the group consisting of phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, naphthylphenyl, and phenanthrylphenyl. Analogs which are higher than quaterphenyl, having 5 to 10 phenyl rings, may also be used.

In some embodiments, at least one of Ar &lt; ⁵ &gt; has at least one substituent. The substituent groups may be present to alter the physical or electronic properties of the host material. In some embodiments, the substituent improves the processability of the host material. In some embodiments, the substituent increases the solubility and / or Tg of the host material. In some embodiments, the substituent is selected from the group consisting of D, an alkyl group, an alkoxy group, a silyl group, a siloxane, and combinations thereof.

In some embodiments, Q is an aryl group having at least two fused rings. In some embodiments, Q has from 3 to 5 fused aromatic rings. In some embodiments, Q is selected from the group consisting of klysene, phenanthrene, triphenylene, phenanthroline, naphthalene, anthracene, quinoline and isoquinoline.

The dopant is an electro-luminescent electroactive material having a maximum emission value between 380 and 750 nm. In some embodiments, the dopant emits red, green, or blue light.

Electroluminescent ("EL ") materials that can be used as dopants in electroactive layers include, but are not limited to, small molecule organic light emitting compounds, luminescent metal complexes, conjugated polymers, and mixtures thereof. Examples of small molecule luminescent compounds include, but are not limited to, chrysene, pyrene, perylene, rubrene, coumarin, anthracene, thiadiazole, derivatives thereof, and mixtures thereof. Examples of metal complexes include, but are not limited to, metal chelated oxinoid compounds. Examples of conjugated polymers include, but are not limited to, poly (phenylene vinylene), polyfluorene, poly (spirobifluorene), polythiophene, poly (p-phenylene), copolymers thereof, Do not.

Examples of the red light emitting material include, but are not limited to, peripher- tene, fluoranthene, and perylene. Red light emitting materials are disclosed, for example, in U.S. Patent No. 6,875,524 and U.S. Patent Application Publication No. 2005-0158577.

Examples of the green light emitting material include, but are not limited to, diaminoanthracene, and polyphenylene vinylene polymer. The green light emitting material is disclosed, for example, in International Patent Publication No. WO 2007/021117.

Examples of blue light emitting materials include, but are not limited to, diaryl anthracene, diaminocrysene, diaminopyrene, and polyfluorene polymers. Blue light emitting materials are disclosed, for example, in U.S. Patent No. 6,875,524 and U.S. Patent Application Publication Nos. 2007-0292713 and 2007-0063638.

In some embodiments, the dopant is an organic compound. In some embodiments, the dopant is selected from the group consisting of non-polymeric spirobifluorene compounds and fluoranthene compounds.

In some embodiments, the dopant is a compound having an arylamine group. In some embodiments, the electroactive dopant is selected from the following formulas:

here,

A is in each case the same or different and is an aromatic group having from 3 to 60 carbon atoms;

Q 'is a single bond or an aromatic group having 3 to 60 carbon atoms;

p and q are independently an integer of 1 to 6;

In some embodiments of the above formulas, at least one of A and Q 'in each formula has at least three condensed rings. In some embodiments, p and q are equal to one.

In some embodiments, Q 'is a styryl or styryl phenyl group.

In some embodiments, Q 'is an aromatic group having at least two condensed rings. In some embodiments, Q 'is selected from the group consisting of naphthalene, anthracene, klycene, pyrene, tetracene, xanthene, perylene, coumarin, rhodamine, quinacridone, and rubrene.

In some embodiments, A is selected from the group consisting of phenyl, biphenyl, tolyl, naphthyl, naphthylphenyl, and anthracenyl groups.

In some embodiments, the dopant has the formula:

(here,

Y is in each case the same or different and is an aromatic group having from 3 to 60 carbon atoms;

Quot; Q "is an aromatic group, a divalent triphenylamine residue, or a single bond.

In some embodiments, the dopant is arylacene. In some embodiments, the dopant is a non-symmetrical arylacene.

In some embodiments, the dopant is an anthracene derivative having the formula V:

(V)

(here,

R ¹⁰ is the same or different in each occurrence and is selected from the group consisting of D, alkyl, alkoxy and aryl, wherein adjacent R ¹⁰ groups may be joined together to form a 5- or 6-membered aliphatic ring;

Ar ⁶ to Ar ⁹ are the same or different and are selected from the group consisting of an aryl group;

d is the same or different in each case and is an integer of 0 to 4).

In some embodiments, the dopant of formula V is minimized. In some embodiments, the aryl group is deuterated. In some embodiments, the alkyl group is deuterated. In some embodiments, the dopant is deuterated by 50% or more; 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% deuterated; In some embodiments, 100% deuterated.

In some embodiments, the dopant is a chrysene derivative having the formula &lt; RTI ID = 0.0 &gt; VI &

(VI)

(here,

R ¹¹ is in each case the same or different and is selected from the group consisting of D, alkyl, alkoxyaryl, fluoro, cyano, nitro, -SO ₂ R ¹² wherein R ¹² is alkyl or perfluoroalkyl , Wherein adjacent R &lt; ¹¹ &gt; groups may be joined together to form a 5- or 6-membered aliphatic ring;

Ar ⁶ to Ar ⁹ are the same or different and are selected from the group consisting of an aryl group;

e is the same or different in each case and is an integer of 0 to 5).

In some embodiments, the dopant of formula (VI) is deuterated. In some embodiments, the aryl group is deuterated. In some embodiments, the alkyl group is deuterated. In some embodiments, the dopant is deuterated by 50% or more; 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% deuterated; In some embodiments, 100% deuterated.

Some non-limiting examples of green dopants are compounds D1 to D8 shown below.

D1:

D2:

D3:

D4:

D5:

D6:

D7:

D8:

Some non-limiting examples of blue dopants are compounds D9 to D16 shown below.

D9:

D10:

D11:

D12:

D13:

D14:

D15:

D16:

In some embodiments, the electroactive dopant is selected from the group consisting of amino-substituted chrysene and amino-substituted anthracene.

In some embodiments, the novel deuterated compounds described herein are electroluminescent materials and are present as 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 a positive charge carrier. It may be made of, for example, a material containing a metal, a mixed metal, an alloy, a metal oxide or a mixed-metal oxide, or it may be a conducting polymer, or a mixture thereof. Suitable metals include Group 11 metals, Groups 4 to 6 metals, and Group 8 to Group 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 also referred to as "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 enough to allow the generated light to be observed.

The hole injecting layer 120 includes a hole injecting material, and improves the performance of the organic electronic device in planarization, charge transport and / or charge injection characteristics of the base layer, removal of impurities such as oxygen or metal ions, Or &lt; / RTI &gt; other aspects, including but not limited to other aspects. The hole injecting material may be a polymer, an oligomer, or a small molecule. The hole injecting material may be deposited or deposited from a liquid that may be in the form of a solution, dispersion, suspension, emulsion, colloidal mixture or other composition.

The hole injection layer may be formed of a polymeric material such as polyaniline (PANI) or polyethylene dioxythiophene (PEDOT), which is often doped with a protonic acid. The protic acid may be, for example, poly (styrenesulfonic acid), poly (2-acrylamido-2-methyl-1-propanesulfonic acid) or the like.

The hole injection layer may comprise a charge transfer compound, such as copper phthalocyanine and a tetra thiafulene-tetracyanoquinodimethane system (TTF-TCNQ).

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

In some embodiments, the hole transport layer 130 comprises a novel deuterated compound of formula (I). Examples of other hole transport materials for layer 130 are described in, for example, 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, (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- [2-methylphenyl] N, N ', N ' -dicyclohexylcarbodiimide (DCZB), p- (diethylamino) phenyl] pyrazoline (PPR or DEASP) (TTB), N, N'-bis (naphthalen-1-yl) -N, N'-bis- (Phenyl) benzidine (-NPB), and A le porphyrin-based 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, polymers and copolymers are cross-linkable. Examples of crosslinkable hole transport polymers can be found, for example, in U.S. Patent Application Publication No. 2005-0184287 and International Patent 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 &gt; dihydride. &Lt; / RTI &gt;

In some embodiments, the electron transport layer 150 comprises a novel deuterated compound of formula (I). Examples of other electron transport materials that can be used in layer 150 include metal chelated 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-biphenylyl) -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. Layer 150 can serve both as a confinement layer that not only facilitates electron transport but also prevents buffering or quenching of the exciton at the layer interface have. 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 can 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 and lanthanide), and Actinide. Aluminum, indium, calcium, barium, samarium and magnesium, as well as combinations thereof. A, Li- or Cs- containing organometallic compounds, LiF, CsF, Li ₂ O, and to lower the operation voltage can also be deposited between the organic layer and the cathode layer.

It is known to have other layers in organic electronic devices. 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 protective layer, may be deposited on the anode 110 and the hole injection layer 120). It is possible to use a layer known in the art, for example a superfine layer of metal such as copper phthalocyanine, silicon oxy-nitride, fluorocarbon, silane, or Pt. Alternatively, some or all of the anode layer 110, the active layers 120, 130, 140, and 150, or the cathode layer 160 may be surface treated to increase the charge carrier transport efficiency. The choice of material for each component layer is preferably determined to provide a device with a high electroluminescent efficiency by balancing positive and negative charges in the emitter layer.

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

The device may be fabricated by a variety of techniques, including sequential deposition of discrete layers on a suitable substrate. Substrates 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, the organic layer may be formed into a solution or dispersion in a suitable solvent using conventional coating or printing techniques, including but not limited to spin coating, dip coating, roll-to-roll technology, inkjet printing, screen printing, gravure printing, Can be applied.

The present invention also relates to an electronic device comprising at least one active layer located between two electrical contact layers, wherein at least one active layer of the device comprises an anthracene compound of formula (I). Devices often have additional hole transport and electron transport layers.

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 &gt; 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 an element made of an anthracene compound 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 transport materials that lead to a reduction in operating voltage or increase quantum efficiency are also applicable. An additional layer may also be added to match the energy levels of the various layers and facilitate electroluminescence.

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

Example

The following examples illustrate certain features and advantages of the present invention. The examples are intended to illustrate the invention but not to limit it. All percentages are by weight unless otherwise indicated.

Synthesis of dopant materials

(1) The dopant D6 was prepared as follows.

Synthesis of intermediate (a):

35 g (300 mM) of 2-methyl-2-hexanol and 17.8 g of anthracene (100 mM) were added to 50 ml of trifluoroacetic acid and refluxed under nitrogen overnight. The solution rapidly darkened to a brown, heterogeneous material. It was cooled to room temperature, evaporated under a stream of nitrogen and extracted with methylene chloride. Separated, the organic layer was dried over magnesium sulfate and evaporated to dryness. The resulting solid was extracted with hexane through a silica column and the pale yellow solution was recovered. Evaporation gave a deep yellow oil which was recrystallized from acetone / methanol by slow cooling and recrystallization from methanol. The structure was confirmed by NMR analysis.

Synthesis of intermediate (b):

6.0 g (16 mM) of intermediate (a) (pure 2,6 isomer) was added to 100 mL of dichloroethane and 2.10 mL bromine (40 mM) was added dropwise with stirring at room temperature for 4 hours. This was poured into water and sodium sulfate was added to consume the residual bromine. This was then extracted with methylene chloride and the organic layer was dried over magnesium sulfate. The resulting material was passed through an alumina column using methylene chloride eluent, then evaporated, and methanol was added to precipitate a light yellow solid. About 7.2 g was obtained.

Synthesis of intermediate (c):

18.9 g (155 mM) boronic acid was added to 25 g of bromo-carbazole (77.7 mM) in a glove box. 1.0 g of Pd2DBA3 (1.0 mM), 0.5 g of P (t-Bu) 3 (2.1 mM) and 20 g of sodium carbonate (200 mM) were added thereto and all dissolved in 200 ml of dioxane and 50 ml of water. In the glove box, it was mixed and heated at 50 ° C for 1 hour in the mantle and then warmed gently (minimum variable resistor setting) under nitrogen overnight. The solution was immediately dark purple and dark brown at about 50 &lt; 0 &gt; C. Water was added to the brown solution outside the glove box and the oily yellow layer was separated. DCM was added and the organic layer was separated. The filtrate was dried over magnesium sulfate to give a light orange solution which produced a bright solid upon evaporation. After evaporation to a small volume and addition of hexane, the white solid was filtered off. The solid was washed well with methanol until the washings became colorless, rinsed with ether and dried by suction to give 21 g of a white solid. The structure was confirmed by NMR analysis.

Synthesis of intermediate (d):

In a glove box, 0.4 g of Pd2DBA3, 0.4 g of 1,1'-bis (diphenylphosphine) ferrocene (DPPF) and 4.3 g of sodium t-butoxide were mixed together and dissolved in 200 ml of xylene. After stirring for 15 minutes, 25 g of 3-iodo-bromobenzene was added. After stirring for 15 minutes, 10 g carbazole was added and the mixture was refluxed. Was refluxed overnight using an air condenser. The solution was immediately dark purple / brown, but dark reddish brown and turbid when it reached about 80 ° C. After heating to near reflux overnight, the solution was dark brown and clear. Evaporation in a nitrogen stream outside the glovebox followed by dissolution in DCM and extraction through (slaughter) via bed of silica and basic alumina (laminated to the slaughter) using DCM / hexane. The dark orange solution was collected and evaporated to dryness. Dark orange oil remained. This was washed with methanol, then dissolved in ether and re-precipitated with methanol. The orange-brown oil was evaporated to a small volume in ether and then acetone / methanol was added to precipitate an off-white solid to give about 6.4 g. This was collected by filtration, washed with a small amount of acetone and dried by suction. The structure was confirmed by NMR analysis.

Synthesis of intermediate (e)

1.7 g of amine (0.01 M) was added to 4.8 g of intermediate (d) (0.01 M) in a glove box. To this was added 0.10 g Pd2DBA3 (0.11 mM), 0.045 g P (t-Bu) 3 (0.22 mM) and 1.1 g t-BuONa and all dissolved in 25 ml toluene. When the catalyst material was added, there was a slight exotherm. This was heated in a mantle in a glove box at 80 [deg.] C for 2 hours under nitrogen as dark brown solution (darkness). After cooling, the solution was worked up by? -Alumina chromatography eluting with DCM. A dark yellow solution with light purple / blue light emission was collected. This was evaporated to a small volume in nitrogen to form a viscous orange oil which solidified to a dark yellow glass upon cooling. This was stirred in methanol / DCM and crystallized as a pale yellow / white solid and ca. 5 g was obtained. The structure was confirmed by NMR analysis.

Synthesis of dopant D6:

2.81 g (5 mM) of intermediate (e) and 0.5 g of t-BuONa (5 mM) were added to 1.32 g of intermediate (b) (2.5 mM) with 50 ml of toluene in a glove box. To this was added 0.2 g of Pd2DBA3 (0.2 mM) and 0.08 g of P (t-Bu) 3 (0.4 mM) dissolved in 10 ml of toluene. After mixing, the solution slowly heated and became yellowish brown. In the glove box, it was mixed and heated in a mantle at about 100 DEG C for 1 hour under nitrogen. The solution was immediately dark purple, but when it reached about 80 ° C it was a dark yellowish green with pronounced green luminescence. The mixture was stirred overnight at the minimum variable resistor setting. After cooling, the material was taken out from the glovebox and filtered through an acidic alumina plug eluting with toluene and methylene chloride. The dark orange solution was evaporated to low volume. This was passed through a silica column (using 60:40 toluene: hexane). A yellow-orange solution was collected which showed a blue leading spot on TLC. This was redissolved in hexane: toluene (80:20) and eluted with 80% hexane / toluene to pass through acidic alumina. The faster blue bands (anthracene and monoaminated anthracene) were discarded. The resulting yellow band was evaporated to low volume and crystallized from toluene / acetone / methanol. This was washed with methanol and hexane and dried by suction to obtain a free flowing microcrystalline yellow powder. The structure was confirmed by NMR analysis.

(2 &apos; -isoproparylphenyl-4-yl) cydecene-6,12-diamine was prepared by reacting the dopant D12, N6, N12-bis (2,4-dimethylphenyl) -N6, N12- .

In a drybox, 6,12-dibromocyclohexane (0.54 g, 1.38 mmol), N- (2,4-dimethylphenyl) -N- (4'- g (0.082 g, 0.069 mmol) and tris (dibenzylideneacetone) dipalladium (0) were combined in a round bottom flask and 20 mL Of dry toluene. The solution was stirred for 1 minute and then sodium tert-butoxide (0.29 g, 3.03 mmol) and 10 mL of dry toluene were added. A heating mantle was added and the reaction was heated to &lt; RTI ID = 0.0 &gt; 60 C &lt; / RTI &gt; The reaction mixture was then cooled to room temperature and filtered through a 1-inch plug of 1-inch celite and silica gel, washing with toluene (500 mL). The volatiles were removed under reduced pressure to give a yellow solid. The crude product was further purified by silica gel column chromatography using a gradient of chloroform in hexane (0% to 40%). Recrystallization from DCM and acetonitrile gave 0.540 g (40%) of the product as a yellow solid. ¹ H NMR (CDCl ₃ ) was consistent with the structural formula.

(3) dopant D13, N6, N12-bis (2,4-dimethylphenyl) -N6, N12-bis (4 " Lt; RTI ID = 0.0 &gt; D12. &Lt; / RTI &gt;

Comparative Example A

This Comparative Example illustrates the preparation of Comparative Compound A, which is a non-deuterated compound.

This compound can be prepared according to the following reaction scheme:

Synthesis of Compound 2:

To a 3 L flask equipped with a mechanical stirrer, dropping funnel, thermometer and N ₂ bubbler was added 54 g (275.2 mmol) of anthrone in 1.5 L dry methylene chloride. The flask was cooled in an ice bath and 1,8-diazabicyclo [5.4.0] undec-7-ene ("DBU"), 83.7 ml (559.7 mmol) was added via a dropping funnel over 1.5 h. The solution turned orange, became opaque, then turned dark red. To the still cold solution, 58 ml (345.0 mmol) of triflic anhydride was added via syringe over a period of 1.5 hours while maintaining the temperature of the solution below 5 ° C. After allowing the reaction to proceed at room temperature for 3 hours, an additional 1 mL of triflic anhydride was added and stirring was continued at RT for 30 minutes. 500 ml of water was slowly added and the layers were separated. The aqueous layer was extracted with 3 x 200 mL dichloromethane ("DCM") and the combined organic layers were dried with magnesium sulfate, filtered and concentrated by rotary evaporation to give a red oil. Column chromatography on silica gel followed by recrystallization from hexane afforded 43.1 g (43%) of tan powder.

Synthesis of Compound 3:

9-yl trifluoromethanesulfonate (6.0 g, 18.40 mmol), naphthalene-2-yl-boronic acid (prepared according to the method described in Example 1) in a 200 ml Kjeldahl reaction flask equipped with a magnetic stir bar in a nitrogen- (17.0 g, 82.0 mmol), palladium (II) acetate (0.41 g, 1.8 mmol), tricyclohexylphosphine (0.52 g, 1.8 mmol) and THF (100 mL) . After removal from the dry box, the reaction mixture was purged with nitrogen and degassed (50 mL) was added via syringe. The condenser was then added and the reaction mixture was refluxed overnight. The reaction was monitored by TLC. When complete, the reaction mixture was cooled to room temperature. The organic layer was separated and the aqueous layer was extracted with DCM. The organic fractions were combined, washed with brine and dried with magnesium sulfate. The solvent was removed under reduced pressure. The resulting solid was washed with acetone and hexane and filtered. Purification by column chromatography on silica gel gave 4.03 g (72%) of the product as pale yellow crystalline material.

Synthesis of Compound 4:

11.17 g (36.7 mmol) of 9- (naphthalen-2-yl) anthracene were suspended in 100 mL of DCM. 6.86 g (38.5 mmol) of N-bromosuccinimide was added and the mixture was stirred under illumination of a 100 W lamp. After the yellow transparent solution was formed, precipitation occurred. The reaction was monitored by TLC. After 1.5 h, the reaction mixture was partially concentrated to remove methylene chloride and then crystallized from acetonitrile to give 12.2 g of pale yellow crystals (87%).

Synthesis of Compound 7:

In a nitrogen-filled glove box, naphthalen-1-yl-1-boronic acid (14.2 g, 82.6 mmol), 1-bromo-2-iodobenzene (25.8 g, 91.2 mmol), tetrakis (triphenylphosphine) palladium (0) (1.2 g, 1.4 mmol), sodium carbonate (25.4 g, 240 mmol) and toluene (120 mL). After removal from the dry box, the reaction mixture was purged with nitrogen and degassed (120 mL) was added via syringe. The condenser was then placed in the reaction flask and the reaction mixture was refluxed for 15 hours. The reaction was monitored by TLC. The reaction mixture was cooled to room temperature. The organic layer was separated and the aqueous layer was extracted with DCM. The organic fractions were combined and the solvent removed under reduced pressure to give a yellow oil. Purification by column chromatography using silica gel gave 13.6 g of clear oil (58%).

Synthesis of Compound 6:

(28.4 g, 10.0 mmol) and bis (pinacolate) diboron (40.8 g, 16.0 mmol) were added to a 1-liter flask equipped with a magnetic stir bar, a reflux condenser connected to a nitrogen line and an oil bath ), Pd (dppf) ₂ Cl ₂ (1.64 g, 2.0 mmol) _, potassium acetate (19.7 g, 200 mmol) and DMSO (350 mL). The mixture was bubbled with nitrogen for 15 minutes and then Pd (dppf) ₂ Cl ₂ (1.64 g, 0.002 mol) was added. During the process the mixture gradually turned dark brown. The reaction mixture was stirred under nitrogen at 120 &lt; 0 &gt; C (oil bath) for 18 h. After cooling, the mixture was poured into ice water and extracted with chloroform (3x). The organic layer was washed with water (3x) and saturated brine (1x) and dried over MgSO4. After filtration and solvent removal, the residue was purified by chromatography on a silica gel column. The fractions containing the product were pooled and the solvent removed with a rotary evaporator. The resulting white solid was crystallized from hexane / chloroform and dried in a vacuum oven at 40 &lt; 0 &gt; C to yield the product as a white crystalline flake (15.0 g in 45% yield). 1H and &lt; 13 &gt; C-NMR spectra are consistent with the expected structure.

Synthesis of Comparative Compound A

To a 250 mL flask in a glove box (2.00 g, 5.23 mmol), 4,4,5,5-tetramethyl-2- (4- (naphthalen-4-yl) phenyl) (1.90 g, 5.74 mmol), tris (dibenzylideneacetone) dipalladium (0) (0.24 g, 0.26 mmol) And toluene (50 mL). The reaction flask was removed from the dry box and a condenser and a nitrogen inlet were installed. Degassed aqueous sodium carbonate (2 M, 20 mL) was added via syringe. The reaction mixture was stirred and heated to 90 &lt; 0 &gt; C overnight. The reaction was monitored by HPLC. After cooling to room temperature, the organic layer was separated. The aqueous layer was washed twice with DCM, the organic layers were combined and concentrated with a rotary evaporator to give a gray powder. Filtration on neutral alumina, hexane precipitation, and column chromatography on silica gel gave 2.28 g of a white powder (86%).

The product was further purified as described in U.S. Patent Application Publication No. 2008-0138655 to achieve an HPLC purity of 99.9% or greater and an impurity absorbance of 0.01 or less.

The ¹ H NMR spectrum of Compound A is provided in FIG.

Example 1

This example demonstrates the preparation of compound H14, which is a compound having the formula (I).

AlCl ₃ (0.48 g, 3.6 mmol) was added to a hydrogenated benzene or benzene-D6 (C ₆ D ₆ ) solution (100 mL) of Comparative Compound A (5 g, 9.87 mmol) from Comparative Example A under a nitrogen atmosphere Respectively. The resulting mixture was stirred at room temperature for 6 hours before D ₂ O (50 mL) was added. After separating the layers, the aqueous layer was washed with CH ₂ Cl ₂ (2 × 30 mL). The organic layers were combined, dried over magnesium sulfate, and the volatile components were removed using a rotary evaporator. The crude product was purified by column chromatography. The dehydrated product H1 (x + y + n + m = 21-23) was obtained as a white powder (4.5 g).

The product was further purified as described in U.S. Patent Application Publication No. 2008-0138655 to achieve an HPLC purity of 99.9% or greater and an impurity absorbance of 0.01 or less. From the above, it was determined that the substance had the same level of purity as the comparative compound A.

¹ H NMR (CD ₂ Cl ₂ ) and ASAP-MS are shown in FIG. 3 and FIG. 4, respectively. The compound had the structure provided below: &lt; RTI ID = 0.0 &gt;

Here, "D / H" indicates that the probability of H or D at this atomic position is approximately the same. ^The structure was confirmed by ¹ H NMR, ¹³ C NMR, ² D NMR and ¹ H- ¹³ C HSQC (Heteronuclear Single Quantum Coherence).

Examples 2 and 3 and Comparative Example B and Comparative Example C

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

The device had the following structure on a glass substrate:

Anode = indium tin oxide (ITO): 50 nm

Hole injection layer = HIJ1 (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, 2005/0205860, and International Patent Publication WO 2009/018009.

Hole transport layer = polymer P1 (20 nm), a non-cross-linked arylamine polymer,

Electroactive layer = 13: 1 host: dopant (40 nm) (as shown in Table 1)

Electron transport layer = ET1 (metal quinolate derivative (10 nm))

Cathode = CsF / Al (1.0 / 100 nm)

[Table 1]

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

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 HIJ1 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 the solvent was removed by heating. 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. The mask was then changed in vacuum and the layer of Al was deposited by thermal evaporation. The chamber was vented 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 the device at a given voltage is determined by dividing the electroluminescent emission luminance of the LED by the current required to operate the device. The unit is cd / A. Power efficiency is the current efficiency multiplied by pi and divided by the operating voltage. The unit is lm / W. The device data is given in Table 2.

[Table 2]

It can be seen that with the deuterated host of the present invention, the lifetime of the device is greatly increased while maintaining other device characteristics. In the case of using the emitter D12, the average expected T50 of the comparative devices having the non-deuterated host (Comparative Example B-1 to Comparative Example B-4) was 10,649 hours. When deuterated analog host H14 was used (Examples 2-1 to 2-4), the average expected T50 of the device was 20,379 hours. When the emitter D13 was used, the average expected T50 of the comparative elements C-1 and C-2 was 15,637 hours. When deuterated analogue host H14 was used (3-1 and 3-2), the mean expected T50 was 24,807 hours.

Example 4

This example illustrates the preparation of some deuterated intermediate compounds that can be used to synthesize compounds having formula (I) with controlled deuteration levels.

Intermediate 4A:

To a solution of anthracene-dlO (18.8 g, 0.10 mol) in CCl4 (500 mL) was added copper anhydrous bromide (45 g, 0.202 mol) in one portion. The reaction mixture was stirred and heated at reflux for 12 hours. The brown cupric chloride is slowly converted to white copper bromide, and hydrogen bromide is slowly formed (bound to the base bath absorber). At the end of the reaction, the cuprous bromide was removed by filtration, and a carbon tetrachloride solution was passed through a 35 mm chromatography column packed with 200 g of alumina. The column is eluted with 200 mL of CH2Cl2. The combined eluates were evaporated to dryness to give 24 g (87%) of 9-bromoanthracene-d9 as a lemon-yellow solid. It contains impurities of about 2% of the raw materials and about 2% of the dibromo-by-products. This material was used directly for further coupling reactions without purification. The intermediate can be further purified by recrystallization using hexane or cyclohexane to give the pure compound.

Intermediate 4B:

d5-bromobenzene (MW 162, 100 g, 0.617 mol) was added at room temperature 93 ml of a mixed solvent of 50% H ₂ SO ₄ and 494 ml of HOAc. The finely divided I ₂ (MW 254, 61.7 g, 0.243 mol) was then added followed by the addition of finely divided NaIO ₄ (MW 214, 26.4 g, 0.123 mol). The mixture was vigorously stirred for 4 hours and heated to 90 &lt; 0 &gt; C. The dark purple solution turned into a light orange mixture containing very fine white precipitates. The mixture was allowed to cool to room temperature overnight. During this time, the product precipitated as a microcrystalline plate. The mixture was filtered and washed twice with 10% sodium thiosulfate Na ₂ S ₂ O ₃ (50 mL) and then with water. This was dissolved in CH ₂ Cl ₂ and the flash column was allowed to proceed. Light yellow, 124 g (70%) of crystalline material were obtained. The filtrate was extracted with CH ₂ Cl ₂ (50 mL × 3), combined with CH ₂ Cl ₂ , washed _twice with 10% sodium thiosulfate Na ₂ S ₂ O ₃ (50 mL) and then with water. After drying and solvent evaporation, the flash column was further advanced to give an additional 32 g of pure product (17.5%). The total amount is 156 g (88% yield).

Intermediate 4C:

A solution of naphthalene-d8 (MW 136, 68 g, 0.5 mol) in hydrobromic acid (MW: 81, d = 1.49, 100 g; 67.5 ml of a 49% aqueous solution; 0.6 mol) and CH2Cl2 (800 ml) Hydrogen peroxide (FW: 34, d = 1.1 g / ml, 56 g; 51.5 ml of 30% aqueous solution; 0.5 mol) was added slowly to the stirred solution over a period of 30 min at 10 to 15 캜. The reaction was kept at room temperature for 40 hours while monitoring the progress of the reaction with TLC. After completion of the bromination, the solvent was removed under reduced pressure and the crude product was washed twice with 10% sodium thiosulfate Na2S2O3 (50 mL) and then with water. The pure product was isolated by flash column chromatography on silica gel (100-200 mesh) with hexane (100%) and subsequent distillation to give pure 1-bromo-naphthalene-d7 as 85 g of clear liquid, The yield is approximately 80%.

Intermediate 4D:

1-Bromonaphthalene-d7 (21.4 g, 0.10 mol), bis (pinacolato) diboron (38 g, 0.15 mol) and potassium acetate (19.6 g, 0.20 mol) in 300 ml of dry 1,4- Was bubbled with nitrogen for 15 min. Then Pd (dppf) ₂ Cl ₂ -CH ₂ Cl ₂ (1.63 g, 0.002 mol) was added. The mixture was heated at 100 &lt; 0 &gt; C (oil bath) for 18 hours. After cooling, the mixture was filtered through Celite and then concentrated to 50 ml, then water was added and extracted three times with ether (100 ml x 3). The organic layer was washed with water (3x) and brine (1x), and dried with MgSO _4, filtered and concentrated. The residue was subjected to silica gel column (eluent: hexane) to give a white liquid, which had a byproduct of naphthalene and diboronic acid ester. Thus, further purification was carried out by distillation to obtain a viscous, clear liquid. Yield, 21 g, 82%.

Intermediate 4E:

Toluene (300 ㎖) of 1-bromo-4-iodo-benzene -D4 (10.95 g, 0.0382 ㏖) and 1-naphthalene boronic acid ester Na ₂ CO ₃ in a mixture of -D7 (10.0 g, 0.0383 ㏖) ( 12.6 g, 0.12 mol) and H2O (50 mL), aliquat (TM) (3 g). The mixture was bubbled with nitrogen for 15 minutes. Pd (PPh3) 4 (0.90 g, 2%) was then added. The mixture was refluxed under a nitrogen atmosphere for 12 hours. After cooling, the reaction mixture was separated and the organic layer was washed with water and separated, dried and concentrated. Silica was added and concentrated. After evaporation of the residual solvent, flash column was eluted with hexane as eluent to give a crude product. Further purification was performed by distillation (collected at 135-140 占 폚 / 13.3 Pa (135-140 占 폚 / 100 mtorr)) to obtain a clear viscous liquid (8.76 g, yield 78%).

Intermediate 4F:

(22 g, 0.075 mol), bis (pinacolato) diboron (23 g, 0.090 mol) and potassium acetate (22 g, 0.075 mol) in 200 ml of dry 1,4- g, 0.224 mol) was bubbled with nitrogen for 15 minutes. Then Pd (dppf) ₂ Cl ₂ .CH ₂ Cl ₂ (1.20 g, 0.00147 mol) was added. The mixture was heated at 100 &lt; 0 &gt; C (oil bath) for 18 hours. After cooling, the mixture was filtered through celite and then concentrated to 50 mL, then water was added and extracted three times with ether (100 mL x 3). The organic layer was washed with water (3x) and brine (1x), and dried with MgSO _4, filtered and concentrated. The residue was subjected to silica gel column (eluent: hexane) to give a white liquid, which had a byproduct of naphthalene and diboronic acid ester. Thus, silica gel column was again run using hexane as the eluent to carry out further purification. The solvent was evaporated and concentrated to about 80 mL hexanes and after formation of the white crystalline product, it was filtered to give 20.1 g of product, yield 81%.

Intermediate 4G:

Na ₂ CO ₃ (31.8 g) and H ₂ O (120 mL), Aliquat (5 g) were added to Intermediate 4A (18.2 g) and intermediate 4F boronic acid ester (25.5 g) in toluene (500 mL) Was added. The mixture was bubbled with nitrogen for 15 minutes. Pd (PPh3) 4 (1.5 g, 1.3%) was then added. The mixture was refluxed under a nitrogen atmosphere for 12 hours. After cooling, the reaction mixture was separated and the organic layer was washed with water and separated, dried, concentrated to about 50 mL and poured into MeOH. The solid was filtered to give a yellow crude product (about 28.0 g). The crude product was washed with water, HCl (10%), water and methanol. Re-dissolving it in CHCl _3, dried over MgSO4, and filtered. The filtrate was added to silica gel, concentrated and dried, and purified on silica gel (0.5 Kg) using only hexane as the eluent (total 50 L of hexane passed through --- only 5 L of hexane was used Lt; / RTI &gt; to give a white product.

Intermediate 4H:

To an ice cold solution of 9- (4-naphthalen-1-yl) phenylanthracene-D2O, intermediate 4G (MW 400.6, 20.3 g, 0.05 mol) in CH2Cl2 (450 mL) Bromine (MW 160, 8.0 g, 0.05 mol) was added slowly (20 min). The reaction occurred immediately and the color changed to light yellow. A solution of Na2S2O3 (2M 100 mL) was added and stirred for 15 min. The aqueous layer was then separated and the organic phase was washed with Na2CO3 (10%, 50 mL) and then three times with water. After separation and drying over MgSO4, the solvent was then evaporated until 100 ml remained. Pouring into methanol (200 mL) and filtration afforded 23.3 g of pure compound (MW 478.5, yield 97.5%). HPLC shows 100% purity.

Intermediate 4I:

(13.6 g, 0.10 mol), bis (pinacolato) diboron (27.93 g, 0.11 mol), di-m-methoxobis (1,5-cyclooctadiene) (OMe) COD] ₂ (1.35 g, 2 mmol, 2%) and 4,4'-di-tert- butyl-2,2'- bipyridine (1.1 g, 4 mmol) in cyclohexane Ml). The mixture was degassed using N2 for 15 minutes and then heated at 85 &lt; 0 &gt; C (oil bath) overnight (dark brown solution). The mixture was passed through a pad of silica gel. The fractions were collected and concentrated to dryness. Hexane was added. The filtrate was concentrated (liquid), rinsed with hexane and passed through a silica gel column to give a clear liquid which was not purified, rinsed with hexane and then purified again into silica gel column and then purified by column chromatography at 135 ° C / 0.013 Pa / 100 mmtorr) to obtain a pure white viscous liquid, which solidified to obtain a white powder (18.5 g, yield 70%).

Intermediate 4J:

9-bromoanthracene-d9 (MW 266, 2.66 g, 0.01 mol) and naphthalene-2-boronic acid (MW 172, 1.72 g, 0.01 mol) were added to a round bottom flask (100 mL) ML) was added. The mixture was purged with N2 for 10 minutes. Was then added and dissolved in water _{(10 ㎖) Na 2 CO 3} (2M, 10 ㎖ (2.12 g) 0.02 ㏖). The mixture was continuously purged with N ₂ for 10 minutes. A catalytic amount of _{Pd (PPh 3) 4 (0.25} g, 2.5%, 0.025 mmol) was added. The mixture was refluxed overnight. The separated organic phase was then poured into methanol and washed with water, HCl (10%), water and methanol. 2.6 g of pure white product was obtained. (Yield: 83%).

Intermediate 4K:

A solution of 9-2'-naphthyl-anthracene-d9, intermediate 4J (2.6 g, 0.0083 mol) in CH2Cl2 (50 mL) was added dropwise to a solution of bromine (1.33 g, 0.0083 mol) in CH2Cl2 (5 mL) Lt; / RTI &gt; A solution of Na2S2O3 (2M in 10 mL) was added and stirred for 15 min. The aqueous layer was then separated and the organic phase was washed with Na2CO3 (10%, 10 mL) and then three times with water. After separation and drying over MgSO4, the solvent was then evaporated until 20 ml remained. Pouring into methanol (100 mL) and filtration afforded pure compound (3.1 g, 96% yield).

Intermediate 4L:

To a solution of 9-bromoanthracene-D9, intermediate 4K (2.66 g, 0.01 mol) and 4,4,5,5-tetramethyl-2- (naphthalen- the 3,2- dioxaborolan (2.7 g, 0.011 ㏖) Na 2 CO 3 (4.0 g, 0.04 ㏖) and H2O (20 ㎖) was added to a mixture of. The mixture was bubbled with nitrogen for 15 minutes. The _{next, Pd (PPh 3) 4 (} 0.20 g, 2.0%) was added. The mixture was refluxed under a nitrogen atmosphere for 18 h (yellow solid). The reaction mixture was cooled and then poured into MeOH (200 mL). The solid was filtered to give a yellow crude product. The crude product was washed with water and methanol. Re-dissolving it in CHCl _3, dried over MgSO4, and filtered. The filtrate was added to silica gel, concentrated, dried and purified on silica gel using hexane as eluent to give pure product (3.0 g, 94% yield).

Intermediate 4M:

A solution of 9-2'-naphthyl-anthracene-d9, intermediate 4L (2.8 g 0.00875 mol) in CH2Cl2 (50 mL) was added dropwise to a solution of bromine (1.4 g, 0.00875 mol) in CH2Cl2 (5 mL) Lt; / RTI &gt; A solution of Na2S2O3 (10 ml of 2M) was then added and the mixture was stirred for 15 minutes. The aqueous layer was then separated and the organic phase washed with Na2CO3 (10%, 10 mL) and then three times with water. After separation and drying over MgSO4, the solvent was then evaporated until 20 ml remained. Pouring into methanol (100 mL) and filtration afforded pure compound (3.3 g, 95% yield).

Example 5

This example illustrates the synthesis of compound H8 from intermediate 4H and intermediate 4I.

To a solution of 9-bromo-10- (4-naphthalen-1-yl) phenylanthracene-D19 intermediate 4H (14.84 g, 0.031 mol) and 2-naphthaleneboronic acid ester intermediate 4I (10.0 g, 0.038 mol) in DME (350 mL) ) Was added K ₂ CO ₃ (12.8 g, 0.093 mol) and H 2 O (40 mL). The mixture was bubbled with nitrogen for 15 minutes. Pd (PPh3) 4 (0.45 g, 1.3%) was then added. The mixture was refluxed under a nitrogen atmosphere for 12 hours. After cooling, the reaction mixture was concentrated to about 150 mL and poured into MeOH. The solid was filtered to give a light yellow crude product. The crude product was washed with water and methanol. Re-dissolving it in CHCl _3, dried over MgSO4, and filtered. The filtrate was added to silica gel, concentrated to dryness and purified on silica gel (0.5 Kg) using hexane: chloroform (3: 1) as eluent to give a white product (15 g, 91% yield).

Example 6

This example illustrates the synthesis of compound H11 from intermediate 4K.

Intermediate 4K (1.96 g, 0.05 mol) and 4- (naphthalen-1-yl) phenylboronic acid (1.49 g, 0.05 mmol) were added to a round bottom flask (100 mL) 0.06 mol) was added followed by the addition of toluene (30 mL). The mixture was purged with N2 for 10 minutes. The next, followed by the addition of _{Na 2 CO 3 (1.90 g,} 0.018 ㏖) dissolved in water (8 ㎖), Ally Quattro (R) (1 ㎖) was added. The mixture was continuously purged with N2 for 10 minutes. A catalytic amount of Pd (PPh3) 4 (116 mg) was added. The mixture was refluxed overnight. After separating the aqueous phase, the organic layer was poured into methanol (100 mL) to collect a white solid. This was filtered and the silica gel column was eluted with chloroform: hexane (1: 3) to carry out further purification to obtain a pure white compound (2.30 g, yield 90%).

Example 7

This example illustrates the synthesis of compound H9 from intermediate 4K and intermediate 4F.

To a round bottom flask (100 mL) were added 9-bromo-10- (naphthalen-2-yl) anthracene-D8, intermediate 4K (0.70 g, 0.0018 mol) , Intermediate 4F (0.7 g, 0.002 mol) was added followed by toluene (10 mL). The mixture was purged with N2 for 10 minutes. Then, after addition of the _{Na 2 CO 3 (0.64g, 0.006} ㏖) dissolved in water (3 ㎖), was added to the Ally Quattro (R) 0.1 ㎖. The mixture was continuously purged with N2 for 10 minutes. A catalytic amount of Pd (PPh3) 4 (0.10 g) was added. The mixture was refluxed overnight. After separating the aqueous phase, the organic layer was poured into methanol (100 mL) to collect a white solid. This was filtered and the silica gel column was eluted with chloroform: hexane (1: 3) to carry out further purification to obtain a pure white compound (0.90 g, yield 95%).

Compound H10, compound H12, and compound H13 were prepared in a similar manner.

Examples 8 to 10 and Comparative Examples D and E

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

The device had the following structure on a glass substrate:

Anode = ITO (50 nm)

Hole injection layer = HIJ1 (50 nm).

Hole transport layer = polymer P1 (20 nm)

Electroactive layer = 13: 1 host: dopant (40 nm) (as shown in Table 3)

Electron transport layer = ET1 (10 nm)

Cathode = CsF / Al (1.0 / 100 nm)

[Table 3]

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

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 HIJ1 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 the solvent was removed by heating. 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. The mask was then changed in vacuum and the layer of Al was deposited by thermal evaporation. The chamber was vented 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) electroluminescent emission luminance versus voltage, and (3) electroluminescent spectral versus voltage. All three measurements were performed simultaneously and computer controlled. The current efficiency of the device at a given voltage is determined by dividing the electroluminescent emission luminance of the LED by the current required to operate the device. The unit is cd / A. Power efficiency is the current efficiency multiplied by pi and divided by the operating voltage. The unit is lm / W. The device data is given in Table 4.

[Table 4]

It can be seen that with the deuterated host of the present invention, the lifetime of the device is greatly increased while maintaining other device characteristics. The average life expectancy for the various hosts is provided in Table 5 below.

[Table 5]

Example 11 and Comparative Example F

This example shows the fabrication and performance of a device having a green dopant, a first host with formula I, and an electroactive layer with a second host material. The electron transporting material was ET2 shown below.

The device had the following structure on a glass substrate:

Anode = ITO (50 nm)

Hole injection layer = HIJ2 (50 nm), which is an aqueous dispersion of electrically conductive polymer and polymeric fluorinated sulfonic acid. Such materials are disclosed, for example, in U.S. Patent Application Publication Nos. 2004/0102577, 2004/0127637, 2005/0205860, and International Patent Publication WO 2009/018009.

Hole transport layer = polymer P1 (20 nm)

Electroactive layer = 82.5: 5: 12.5 First host: second host: dopant (60 nm) (as shown in Table 6)

Electron transport layer = ET2 (10 nm).

Cathode = CsF / Al (0.7 / 100 nm)

[Table 6]

The devices were fabricated and evaluated as described in Examples 8-10. Device data is provided in Table 7.

[Table 7]

It can be seen that with the deuterated host of the present invention, the lifetime of the device is greatly increased while maintaining other device characteristics. Even in the presence of the non-deuterated second host material, the expected life is more than two-fold.

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 (1)

All uses described herein.

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