TW201109291A - Deuterated compounds for electronic applications - Google Patents

Abstract

This invention relates to deuterated aryl-anthracene compounds that are useful in electronic applications. It also relates to electronic devices in which the active layer includes such a deuterated compound.

Description

201109291 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to an at least partially deuterated anthracene derivative compound. The invention also relates to electronic devices in which the active layer comprises such compounds. [Related application materials] This patent application is based on 35 XJ.SC § 119(e) Proposal on US Provisional Patent Application No. 61/156,181 of February 27, 2009, in 2009 The priority of U.S. Provisional Patent Application No. 61/179, No. 4, filed on May 19, s, and U.S. Provisional Patent Application No. 61/239,574, filed on Sep. 3, 2009, the entire disclosure of Completely incorporated into this specification. [Prior Art] An organic electronic device that emits light (for example, a light-emitting diode constituting a display) exists in many different kinds of electronic devices. In all such devices, an organic active layer is sandwiched between two electrical contact layers. At least one of the electrical contact layers is permeable to light such that light can pass through the electrical contact layer. The organic active layer, i.e., illuminates through the permeable electrically conductive layer, when electrical power is applied across the two electrical contact layers. It is well known that organic electroluminescent compounds are used as active compounds in light-emitting diodes. It is known that simple organic molecules such as onions, spirulina derivatives and coumarin derivatives can exhibit electroluminescent properties. A semiconductor co-host polymer can also be used as the electroluminescent compound, which is disclosed in, for example, U.S. Patent No. 5,247,190, U.S. Patent No. 5, Tobacco, No. 9-9, and the published European patent application. No. 443 861. In many cases, the electroluminescent compound acts as a dopant in a host material. 14548I.doc 201109291 There is a continuing need for novel materials for electronic devices. SUMMARY OF THE INVENTION The present invention provides a substituted aryl-substituted anthracene having at least one anthracene substituent. The present invention also provides an electronic device having an active layer comprising the above compound. The present invention further provides an electroactive composition comprising (a) a monosubstituted aryl hydrazine having at least one anthracene substituent and (b) an electroactive dopant capable of electroluminescence having a maximum emission wavelength Between 380 nm and 750 nm. [Embodiment] The various aspects and specific embodiments disclosed herein are illustrative and not restrictive. Other aspects and specific embodiments of the present invention will be apparent to those skilled in the art of the present invention. The detailed description of the invention and the scope of the claims are apparent. The detailed description of the present invention focuses first on the definition and clarification of the terms, followed by a description of the deuterated compound, the electronic device, and finally an illustration. 1. Definitions and Illuminations Before describing the details of the specific embodiments described below, some terms are defined or clarified. The term "aliphatic ring" as used herein means a cyclic group which does not have a delocalized pi electron. In some embodiments 145481.doc 201109291, the aliphatic ring is not unsaturated. In some embodiments, the ring has a double bond or a bond. The 4 suffix "alkoxy" means an R 〇 group "wherein R is an alkyl group. The term "alkyl group" means a group derived from an aliphatic hydrocarbon having a point of attachment, and the alkyl group includes a linear group, a branched group and a cyclic group. The above terms are intended to include heteroalkyl groups. The term "hydrocarbylalkyl" refers to a alkyl group having no heteroatoms. The "gasification base" has at least one hydrocarbon alkyl group which can be substituted with D. In certain embodiments, the monoalkyl group has from 1 to 20 carbon atoms. "A branched alkyl group" means an alkyl group having at least one secondary carbon or tertiary carbon. The term "secondary alkyl" refers to a branched alkyl group having a secondary carbon atom. The term "tertiary alkyl" means a branched alkyl group having one tertiary carbon atom. In certain embodiments, the branched alkyl group is bonded via a primary or tertiary carbon. The term "π aryl" means a group derived from an aromatic cigarette having a point of attachment. The term "aromatic compound" means an organic compound comprising at least one unsaturated cyclic group having a delocalized pi eleetron. The above terms are intended to include heteroaryl groups. The term "hydrocarbon aryl" means an aromatic compound having no hetero atom in the ring. The term "aryl" includes groups having a monocyclic and polycyclic ring, and the polycyclic ring may be bonded via a single bond or fused to a body. The term "deuterated aryl" refers to an available substituted group having at least one direct linkage to an aryl group. The term "tetra" is intended to mean a group derived from an aromatic cigarette having two points of attachment. In some embodiments, the aryl group 145481.doc 201109291 has from 3 to 60 carbon atoms. The term "aryloxy" refers to an RO- group in which R is an aryl group. The term "compound" is intended to mean an uncharged material which consists of molecules which are further composed of atoms which are not physically separated. When the phrase "adjacent" is used to refer to a layer in a device, the phrase "adjacent" does not necessarily mean that the layer is immediately adjacent to the other layer. On the other hand, the monthly "adjaeent R gr〇ups" is used to refer to the bases adjacent to each other in a chemical formula (i.e., the R groups on the atoms grouped by the bonds). The term "gasification" means that at least one of the oximes has been replaced by D. It is said to be at least twice as large as the natural abundance level. A "deuterated derivative" of compound X has the same structure as the compound hydrazine, but has at least one substituted hydrazone d. The term "dopant" means a material located within a layer comprising a host material that changes the layer compared to the electronic properties of the layer in which the material is absent or the wavelength of radiation emitted, received or chopped. The target wavelength of the electric wave and the receiving money wave. 4 When the term "electrically active" means a layer or material, the term "electrical activity means a layer or material that exhibits electronic or electrical radiation characteristics. Electrically in an electronic: two'-electroactive material The operation of the device. Examples of electrical activity include, but are not limited to, conduction, injection, and material (where 咭雷^电或在接射的:: 疋电子 or hole)' or light A material that changes the concentration of the active material in the field. Examples include, but are not limited to, planarizing materials, insulating materials, and environmental barrier materials. The child "hetero" means that one or more carbon atoms have been replaced by a different atom. In some embodiments, different atomic groups n, 或 or S. 5 "Main material" means a material to which a dopant is added. The host material may or may not have electronic properties, or the ability to emit, receive or pulsate. In some embodiments, the host material present has a greater concentration. The term "layer" and the term "film" are used interchangeably and refer to a coating that covers a desired area. The above terms are not limited by size. The area can be as large as the entire device or as small as a specific functional area (eg, actual visual display or as small as a single sub-pixel. 1 by any conventional deposition technique (eg, vapor deposition, liquid deposition (continuous) And discontinuous techniques) and thermal transfer) to form layers and films. Continuous deposition techniques include, but are not limited to, spin coating shouting _t|ng), gravure coating (gravure c〇ating), curtain coating _ting ), dip c〇ating, slit coating, spray c〇ating, and continuous nozzle capping. Discontinuous deposition techniques include, but are not limited to, ink jet printing, gravure printing (four) coffee printmg), and screen pHnting. The term "organic electronic device" or sometimes only "electronic device" refers to a device comprising - or - a plurality of organic semiconductor layers. Unless otherwise indicated, 'all groups may be substituted or unsubstituted. In one embodiment, the substituents are selected from the group consisting of 0, a dentate, a thiol 145481.doc 201109291 oxy group, an aryl group, an aryloxy group, a cyano group, and NR 2 , wherein R Department base or aryl. All technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the invention pertains, unless otherwise defined. The methods and materials similar or equivalent to those described herein can be used to practice or test the invention, but the appropriate methods and materials are described below. All a case, patent application, patent, and other references mentioned herein are referred to in the manner in which they are inconsistent with each other. In addition, the materials, methods, and examples are illustrative only and not limiting. The full text uses the International Union of Purification and Applied Chemistry (IUPAC) numbering system from beginning to end, with families from the Periodic Table of the Elements numbered from left to right as 1-18 (CRC Handbook of Chemistry -, 81st edition, 2000) . 2. Deuterated compounds The novel deuterated compounds are - substituted aryl having at least one D. In some embodiments, the compound is at least 1% deuterated. The second line means at least a difficult replacement. In some embodiments, the compound is at least 20% deuterated; in the present embodiment, the compound is at least molyzed; in some embodiments, the compound is to 4 Saturation; in some embodiments, the compound is at least 50. Dimerization; In some embodiments, the compound is at least 60% entrapped - some specifically formulated, the compound being at least 7Q. In the present embodiment, the compound is at least 8% by gasification; in some embodiments 145481.doc 201109291 Example I, the compound is at least 9% by weight. In some embodiments, the 3H compound is 100% sterilised. In a specific embodiment, the deuterated compound has a chemical formula: R2 R3

R4

Ar2—Αι4 Formula I R5 wherein: R1 to R8 are the same or different at each occurrence, and are selected from Η 'D, alkyl, alkoxy, aryl, aryloxy, decane, and decyl Group of

Ar1 and Ar2 are the same or different, and are selected from the group consisting of aryl groups;

Ar and Ar4 are the same or different and are selected from the group consisting of H, D and aryl groups; wherein the compound has at least one D. In some embodiments of Formula I, the at least one D is positioned on a substituent (group) on an aromatic ring. In some embodiments, the substituent (group) is selected from the group consisting of alkyl and aryl. In some embodiments of Formula I, at least one of R1 to R8 is D. In some embodiments, at least two of them are d. In a specific embodiment, at least three are D; in some embodiments, 145481.doc •9-201109291 at least four are D; in some embodiments, in some embodiments, at least six Person D; in - some: implementation: at least seven are D. In some embodiments, ... to 8 are all D. In some embodiments,! ^ to! ^ is selected from H&D. In some embodiments, one of the R^r8 and the other seven systems h4 - in some embodiments, two of the R^ and the other six are. In some embodiments, ... to three of the rulers 8 and the other five systems. In some embodiments, four of the sizes of the ruler to the ruler 8 and the other four systems are used. In some embodiments, five of the R's to R8's and the other three of the two systems are in some embodiments, ... to 8 of which are 8 of the D and the other two. In some embodiments, one of the two from D to R8 is D and the other is η. In some embodiments, all eight of R1 through R8 are D. In some embodiments, at least one of R丨 to r8 is selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an anthraquinone group, and a shixi (10), and the remainder of r^r8 It is selected from i^D. In some embodiments, the towel is selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a sulphuric acid, and a sulphuric acid. In some cases, the R 2 is selected from the group consisting of an alkyl group and an aryl group. In some embodiments, R: is selected from the group consisting of a halogenated alkyl group and a halogenated aryl group. In some embodiments, R2 is selected from the group consisting of deuterated aryl groups having at least 1% deuteration. In some embodiments, R2 is selected from an aromatic aryl group having at least 2 G% vaporization; in some embodiments, it has at least 3% deuteration; in some embodiments, Having at least 4%% deuteration; in one embodiment having 145481.doc 201109291, which has at least an cyclization effect; in some embodiments, 'having at least 6 G% 1 chemistry; In a particular embodiment, it has at least 70% deuteration; in some embodiments, it has an 80% deuteration; in some embodiments it has at least (iv) gasification. In some embodiments, the ruler 2 is selected from the group consisting of a physician. Deuterated aryl groups by gasification. In some embodiments of Chemical Formula 1, at least one of Ar1 to Ar4 is a deuterated aryl group. In some embodiments, Ar3 and A are selected from the group consisting of d and deuterated aryl. In some embodiments of Formula I, eight to four are at least 〇% decidated. In some specific embodiments of Formula I, Afl to A are at least 20 / deuterated, in some embodiments at least 3; in some embodiments, 'i is less than 4% deuterated; In some embodiments, at least 50% is singulated; in some embodiments, at least 6% is vaporized; in some embodiments, at least is liquefied; in some embodiments, at least 80 〇 / Deuteration; in some embodiments, at least 9% deuterated; in some embodiments, 100% deuterated. In some embodiments, the compound of the formula is at least 1% deuterated; in some embodiments, at least 2% deuterated; in some embodiments, at least 30% deuterated; In some embodiments, at least 4%% is deuterated; in some embodiments, at least 5% is deuterated; in some specific embodiments, at least 60〇/〇氘; in some embodiments, at least 7〇/〇化化' In some embodiments, at least 80% is normalized; in some embodiments, 'at least 9% is saturated. In some embodiments, the 145481.doc •11· 201109291 compound is 100% deuterated. In some embodiments, Ar1 and Ar2 are selected from the group consisting of phenyl, naphthyl, phenanthryl, anthracenyl, and their sinking derivatives. In some embodiments, Ar1 and Ar2 are selected from the group consisting of phenyl, naphthyl, and their deuterated derivatives. In some embodiments, Ar3 and Ar4 are selected from the group consisting of phenyl, naphthyl, phenanthry G, anthracenyl, phenylnaphthylene, naphthylphenylene. ), their gasified derivatives and groups of groups of formula II:

Wherein: R9 is the same or different at each occurrence, and is selected from the group consisting of ruthenium, D, alkyl, alkoxy, decane, and decyl; or adjacent R9 may be Together to form an aromatic ring; and m is the same or different and is an integer from 1 to 6 at each occurrence.

In some embodiments, Ar3 and Ar4 are selected from the group consisting of phenyl, naphthyl, phenylnaphthylene, naphthylphenylene, their gasified derivatives, and chemical formulas. III 145481.doc -12- 201109291 The group consisting of:

Wherein Rh is as defined above in the chemical formula „. In some embodiments, m is an integer from 1 to 3. *- In some specific embodiments, at least one of Arl to Ar4 is a heteroaryl group. In some embodiments, the heteroaryl group is deuterated. In some specific embodiments, the heteroaryl group is at least 丨〇0/. In some embodiments, at least 20% Gasification; in some embodiments, at least 30% deuteration; in some embodiments, at least 氘%; in some embodiments, at least 50% deuteration; in some specific embodiments, At least 60% deuterated; in some embodiments, at least deuterated; in some embodiments, at least 80% deuterated; in some specific embodiments, at least 90% deuterated. In some embodiments The heteroaryl group is 100% deuterated. In some embodiments, the heteroaryl group is selected from the group consisting of carbazole, benzfuran, dibenzofuran (benzfuran) Dibenzofuran) and their deuterated derivatives. In some embodiments of formula I, r to R8 are at least D, and at least one of Ar1 to Ar4 is a deuterated aryl group. In some embodiments, the compound is at least 10% deuterated. In some embodiments, the compound is at least 20% deuterated; In some embodiments, at least 30% deuterated; in some embodiments, at least 4% deuterated; in some embodiments 145481.doc -13· 201109291, at least 50% deuterated; In some embodiments, at least 60% deuterated; in some embodiments, at least 70% deuterated; in some embodiments, at least 80° per deuterated; in some embodiments, at least 90% In some embodiments, the compound is 100% deuterated. Some non-limiting examples of compounds of formula I include the following compounds H1 to H14: compound H1:

Wherein x+y+z+n=l-26 compound H2:

Wherein x+y+z+p+n=l-30 145481.doc 14 201109291 Compound H3:

Wherein x+y+z+p+n+r=l-32 compound H4 :

Wherein x+y+z+p+n=l-18 compound H5:

Wherein, x+y+z+p+n+q=l-34 -15- 145481.doc 201109291 Compound H6:

Wherein x+y+z+n=l-18 compound H7:

Wherein x+y+z+p+n=l-28 compound H8:

Compound H9:

145481.doc -16- 201109291 Compound H10:

Compound Hll:

Compound H12:

Compound H13:

145481.doc •17- 201109291

Non-deuterated analogs of the novel compounds can be prepared from known coupling and substitution reactions. Then, in a similar manner, a new gasification compound is prepared using a deuterated precursor material; or more generally, a Lewis acid H/D exchange catalyst such as trichlorin or ethane gasification (Lewis acid H/D exchange) The non-vaporized compound is treated with a gasification solvent such as hexa-benzene (d6-benzene) in the presence of an acid such as CF3COOD, DC1 or the like. An exemplary preparation method is illustrated in the examples. The degree of deuteration is determined by NMR analysis and mass spectrometry, such as atmospheric pressure solid state analytical probe mass spectrometry (AS ΑΡ-MS). Starting materials of fully deuterated or partially deuterated aromatic or alky compounds are commercially available or can be obtained using known methods. Some examples of such methods are listed below: a) Hiroyoshi Esaki, Fumiyo Aoki, Miho Umemura, Masatsugu Kato, Tomohiro Maegawa, Yasunari Monguchi and Hironao Sajiki are published in the European Chemical Journal Chem. Eur. J. "Efficient H/D Exchange Reactions of Alkyl_Substituted

Benzene Derivatives by Means of the Pd/C-H2-D20 System" 2007, No. 13, pp. 4052-4063; b) GUO Qiao-Xia, SHEN Bao-Jian, GUO Hai-Qing, TAKAHASHI 145481.doc - 18 · 201109291

Tamotsu is published in the Chinese chemical journal c/n’wese.Jowma/ 〇/

R Aromatic H/D Exchange Reaction Catalyzed by Groups 5 and 6 Metal Chlorides" 2005, No. 23, pp. 341-344; c) Richard J. Watts, Shlomo Efrima and Horia Metiu, published in the American Chemical Society "A novel deuterium effect on dual charge-transfer and ligand-field emission of the cis-dichlorobis (2,2'-bipyridine) iridium (Ill)ion" by J. C/ze/w. Soc. , 101(10), pp. 2742-2743; d) Carmen Boix and Martyn Poliakoff, "Efficient HD Exchange of Aromatic Compounds in Near-Critical D20 Catalysed by a Polymer-Supported Sulphonic Acid" 1999, "Tetrahedron Letters" Year, Vol. 40, pp. 4433-4436; e) US Patent No. 3849458; f) Hironao Sajiki, Fumiyo Aoki, Hiroyoshi Esaki, Tomohiro Maegawa, and Kosaku Hirota, published in the Organic Chemistry Journal Or Rong. CD Exchange Reaction on the Alkyl Side Chain of Aromatic Compounds Using Heterogeneous Pd/C in D20", 2004, Vol. 6, No. 9, pp. 1485-1487. The compounds described herein can be formed into a film using liquid deposition techniques. Unexpectedly, the properties of these compounds are greatly improved compared to similar non-deuterated compounds. If the electronic device comprises an active layer having a compound as described herein, it has a greatly improved lifespan. In addition, high quantum efficiency and good color saturation are achieved, in addition to extending the lifespan. In addition, the chemical compounds described in this paper are similar to those of non-gasification. 145481.doc •19· 201109291 八 八 has a higher air stability (air t〇lerance). This can result in greater process tolerances in the preparation and purification of the materials' and in the use of such materials to form electronic devices. 3. Electronic Devices Organic electronic devices (which may benefit from having one or more layers of electroluminescent materials included herein) include, but are not limited to, (1) devices that convert electrical energy into radiant energy (eg, light-emitting diodes) Body, LED display or diode laser); (2) devices that detect signals electronically (eg, photodetector photocells, photoresistors, photoswitches, optoelectronic crystals, optoelectronics, Infrared detectors; (3) devices that convert radiant energy into electrical energy (eg, photovoltaic devices or solar cells); q and (4) devices that include - or multiple electronic components (eg, transistors or diodes) And wherein the (etc.) electronic component comprises one or more organic semiconductor layers. Figure 1 shows an illustration of the structure of an organic electronic device. The device 100 has a first electrical contact layer, an anode layer 110 and a second electrical contact layer, a cathode layer 160' and an electroactive layer 14 therebetween. A hole injection layer (3) can be positioned next to the anode. The hole transport layer 130 may be located beside the hole injection layer, the hole transport layer including the hole transport material. An electron transport layer 150 can be located next to the § Xuan cathode, which is earlier than 恳6 & and the electric kilolayer has an electron transfer material. The device may use - or multiple additional hole injection or hole transport layers (not shown) adjacent to the anode 11 and/or one or more additional electron injection or electron transport layers (not shown) adjacent to the cathode 16 . Layers 120 through 150 are individually and collectively referred to as active layers. In a specific embodiment, the thickness of the (four) layer is as follows: 14548 丨.doc • 20· 201109291 The anode layer 110 is 500-5000 A, and in one embodiment is 1 〇〇〇 2 〇〇〇 The hole injection layer 120 is 50-2000 A, in one embodiment 200-1000 A; the hole transport layer 130 is 5 〇 2 〇〇〇 A, in one embodiment 200-1000 a; the electroactive layer 14〇 is 1〇2〇〇〇a, in a specific embodiment 100-1000 a; the electron transport layer 15〇 is 5〇2〇〇〇A, in a specific embodiment 100·1000 A; the cathode layer 16〇 is 2〇〇1〇〇〇〇A, and in one embodiment is 300_5〇〇〇A. The relative thickness of each layer can affect the position of the electron-hole recombination zone in the device, & thus affecting the emission spectrum of the device. The desired 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 14 can be a light-emitting layer activated by an applied voltage (eg, in a light-emitting diode or a light-emitting electrochemical cell) or with or without an external application. A material layer that responds to the Korean energy and generates a signal under a bias voltage (for example, an optical detector in a photodetector includes a photoconductive battery, a photoresistor, a light control switch, a photoelectric crystal, a photocell, and a photovoltaic Batteries, these terms are described in John's (Electronics and Nucleonics Dicti, page W and page 476 (McGraw-HUUnc., 1966). One or more new deuterated materials may be present in a device. In one or more active layers, the materials may be used alone or in combination with a non-inviting material. In some embodiments, the neo-inhibiting compounds are useful for use as electricity in layer 130. Hole transport material. In some embodiments, at least one additional layer comprises an m material. In some embodiments, the additional I45481.doc -21 - 201109291 layer electrical/injection layer 12〇. Example The additional layer is electrically active! The green layer is 14G ° - in some embodiments, the additional layer is an electron transport layer 150. In some embodiments, the new layered compounds are useful for use as electricity, The host material of the electroactive dopant material in the tongue layer 140. In some embodiments, the emissive material is also deuterated. In some implementations,: a small additional layer includes a smectified material. In a specific embodiment, the additional layer is a hole injection layer 12. In some embodiments, the additional layer is a hole transport layer 13 . In some embodiments, the additional layer is an electron transport layer 150. In some embodiments, the new gasification compounds are useful as electron transport materials in layer 150. In some embodiments, at least one additional layer comprises a germanium material. In some embodiments The additional layer is a hole injection layer 12 〇. In some implementations _ _ ^ τ the additional layer is a hole transport layer 130. In some embodiments, the layer (4). 5 玄 extra layer is an electroactive deuterated material, Electroactive layers and electrons in some In an embodiment, an electronic device has any combination present in a layer selected from the group consisting of a hole injection layer, a hole transport layer, and a transport layer. In some embodiments, the process or functionality is improved. In some specific embodiments, the material is composed. In some embodiments, the material is composed of materials. Α Any or all of these layers may not contain all of the organic device layers. 22· 145481.doc 201109291 a·Electroactive layer The new deuterated compound of the winter formula 1 is useful as a host material for the electric f doping material in the electroactive layer 140. These compounds may be used alone or in combination with the first host material. These novel compounds can be used as a host having a dopant of any emission color. In some embodiments, the novel gasification compounds can be the bulk of the (iv), green or blue emissive material. In some embodiments, the electroactive layer consists essentially of a host material of formula I and one or more electroactive dopants. In some embodiments, the "electro-active layer" consists essentially of a first host material having the formula r, a second host material, and an electroactive dopant. Examples of second host materials include, but are not limited to, chrysenes, phenanthrenes, triphenylenes, phenanthrolines, naphthalenes, anthracenes, quinolines, Isoquinolines, quin〇xaHnes, phenylpyridines, benz〇difurans, and metal quinolinate complexes. 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, from 5 to 15% by weight. When a second host material is present, the ratio of the first body material having a chemical formula to the far first body material is typically in the range of ι:2〇 to 20:1; in some embodiments, 5:15 To 15:5. In some embodiments, the first host material of Formula I comprises at least 50 wt% of the total host material, and in some embodiments, at least wt%. In some embodiments, the second host material has the chemical formula IV: 145481.doc -23· 201109291

Ar5 is the same or different 'and one aryl group at each occurrence; Q is selected from the group consisting of polyatomic aryl groups, and

T is selected from the group consisting of (CR,) a, SiR2, S, S02, PR, p〇, p〇2, BR and R; R is the same or different at each occurrence and is selected from the group consisting of a group consisting of a group and an aryl group; R' is the same or different at each occurrence and is selected from the group consisting of η and an alkyl group; a is an integer from 1 to 6; and η is 0 to 6 Integer. While η may have a value from 〇 to 6, it should be understood that for some q groups, the value of η is limited by the chemistry of the group. In some implementations: 11 is 0 or 1. In some embodiments of Formula IV, the gland J can be joined together to form a ring, such as a carbazole. In the chemical formula ιν φ Ning '"adjacent" means that the base is bonded to the same N. In some specific examples, the Ar system is independently selected from the group consisting of 145481.doc -24-201109291 (phenyl), biphenyl, terphenyl, quaterphenyl, naphthyl ( Naphthyl), phenanthryl, naphthylphenyl, and phenanthrylphenyl. Analogs higher than biphenyl (having 5-10 benzene rings) can also be used. In some embodiments, at least one of Ar5 has at least one substituent. The reason for the presence of a substituent is to change the physical or electronic properties of the host material. In some embodiments, the substituents enhance the processability of the host material. In some embodiments, the substituents increase solubility and/or increase the Tg of the host material. In some embodiments, the substituents such as <s> are selected from the group consisting of D, a group based on a group, an alkoxy group, a oxazide group, a decane, and combinations thereof.

In some embodiments, Q is an aryl group having at least two fused rings. In some embodiments, Q has 3 to 5 aromatic fused rings. In a group = specific embodiment, the Q system is selected from the group consisting of disease, phenanthrene triphenyl, phenanthroline, nai, anthracene, quinoline, and isoquine. The dopant is an electroluminescent material capable of electroluminescence having an emission wavelength maximum between 38 G nm and 75 G nm. In some embodiments, the dopant emits red, green or blue light. Electroluminescent (tetra) materials useful as dopants in the electroactive layer include, but are not limited to, 'small molecule organic luminescent compounds, luminescent metal complexes, conjugated polymers, and mixtures thereof. Examples of the small molecule luminescent compound include: not limited to, a mixture of brook red fluorene, coumarin, onion, bismuth, a mixture of β metal complexes including, but not limited to, 'metal ehelated. It is called a compound. 145481.doc -25· 201109291 Examples of conjugated polymers include, but are not limited to, poly(phenylenevinylenes), polyg (P〇lyflu〇renes), poly(snails) (P〇ly (Spir〇biflu〇reneS)), Polythiophene (Phenes), poly(p-phenylenes), their copolymers, and their mixing & Examples of red luminescent materials include, but are not limited to, 'periflanthenes, fluoranthenes, and perylenes. For example, U.S. Patent No. 6,875,524 and U.S. Patent Application Serial No. 2005 Red luminescent materials are disclosed in -015 8577. Examples of green luminescent materials include, but are not limited to, diaminoanthracenes and polystyrene polymers

(polyphenylenevinylene polymers). The green luminescent material is disclosed in, for example, the published PCT application No. WO 2007/021117. Examples of blue luminescent materials include, but are not limited to, diarylanthracenes, diamin〇chrysenes, diaminopyrenes, and polypolymers. The blue luminescent material is disclosed in, for example, U.S. Patent No. 6,875, 524, the disclosure of which is incorporated herein by reference. In some embodiments, the etchant is an organic compound. In some embodiments, the dopant #harmonic is a group of a non-polymerized spirobi compound and a fluorescein compound. In some embodiments, the 掺杂 她 ^ ^ ^ 掺杂 具有 具有 具有 has an arylamine group compound. In some embodiments, the earthworm 忒 electrically active dopant is selected from the group consisting of the following chemical formula: 14548 丨.doc -26- 201109291

Wherein: a system - an aromatic group having 3 to 60 carbon atoms in each occurrence of the same or different atoms; Q' is a single bond or an aromatic group having 3 to 60 carbon atoms. q is an integer from 1 to 6, respectively.

In some embodiments of the above chemical formula, each of A and Q to v in the formula has at least two condensed rings. In some embodiments, p and q are equal to one. In some embodiments, Q is a styryl or stylyl phenyl group. In some embodiments, Q' is an aromatic group having at least two fused rings. In some embodiments, Q is selected from the group consisting of naphthalene, anthracene, chrysene, pyrene, tetracene, xanthene, and perylene. ), coumarin 14548 丨.doc •27- 201109291 (coumarin), rhodamine (rh〇damine), 喧. Anthrone (4) (10) is a group consisting of a core (tetra) and a rubrene. In some embodiments, the A is selected from the group consisting of phenyl, biphenyl, tolyl, and naphthalene. a group of naphthyl, naphthylphenyl, and anthracenyi. In some embodiments, the dopant has the following chemical formula:

Wherein: Y is the same or different 'and one is an aromatic group having 3_6〇 carbon atoms at each occurrence; Q" is an aromatic group, a divalent trisamine residue (residue gr〇up) or A single button. In some embodiments, the dopant is a poly aryl acene. In some embodiments, the dopant is an asymmetric poly aryl acene. In some embodiments, the dopant is a Hui derivative having the chemical formula v:

Wherein: 145481.doc •28· 201109291 R is the same or different at each occurrence, and is selected from the group consisting of D, alkyl, alkoxy and aryl groups, wherein adjacent R10 groups can be combined Together to form a 5 or 6 member aliphatic ring;

Ar to Ar9 are the same or different and are selected from the group consisting of aryl groups; d is the same or different at each occurrence, and is an integer from 4 to 4; and in some embodiments, The dopant in the chemical formula is deuterated. In some specific embodiments, the aryl groups are deuterated. In some embodiments, the alkyl groups are deuterated. In some embodiments, the dopant is at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 7% deuterated; In an embodiment, at least 80% i; in some embodiments, at least 90% deuterated; in some embodiments, 1% deuterated. In some embodiments, the dopant is a chopstick derivative of formula VI:

Wherein: R is the same or different at each occurrence, and is selected from the group consisting of d, alkane 145481.doc -29- 201109291, alkoxyaryl, fluoro, cyano, nitro, a so2r12 Wherein R12 is an alkyl or perfluoroalkyl group, wherein adjacent R11 groups may be grouped together to form a 5- or 6-membered aliphatic ring; ΑΓ to Ar are the same or different 'and are selected from aryl a group of groups; and e is the same or different 'and an integer from 0 to 5 at each occurrence. In some embodiments, the dopants of Formula VI are encapsulated. In some embodiments, the aryl groups are deuterated. In one embodiment, the alkyl groups are deuterated. In some embodiments, the dopant is at least 50% deuterated; in some embodiments, at least 60% deuterated; in some embodiments, at least 7% deuterated; in some implementations In the example, at least 80»/. Deuteration; at least 90% gasification in some embodiments; in some embodiments, 1% gasification. Some non-limiting examples of green dopants are Compound 01 to Compound D8 shown below. D1:

145481.doc •30· 201109291 D2

D3

D4

145481.doc -31 · 201109291 D5 :

D6:

J45481.doc -32- 201109291 D7 :

Some non-limiting examples of blue dopants are compounds D9 through D16 as shown below. D9:

145481.doc -33- 201109291 DIO:

Dll:

D12:

145481.doc 34· 201109291 D13 :

D14:

145481.doc 35- 201109291 D15 :

D16:

In some embodiments, the electroactive dopant is selected from the group consisting of an amino-substituted bacterium and a substituted amide. In some embodiments, the novel deuterated luminescent material described herein is a eucalyptus leaf and is present as an electroactive material. b. Its agrostrates The layer of the layer in the Dunhuang can be made of any known material 145481.doc • 36- 201109291 for such layers. The anode layer 11 is an electrode which is particularly effective for injecting a positively charged positive carrier. It may be made of, for example, a material containing a metal, a metal, an alloy, a metal oxide or a mixed metal oxide, or it may be a conductive polymer, or a mixture thereof. Suitable metals include Group VIII metals, Groups 4-6 metals, and Group 8-10 transition metals. If the anode is light transmissive, a mixed metal of Group 12, Group 13, and Group 14 metals is typically used to oxidize $', such as indium tin oxide. The anode 11G may also include an organic material such as polyaniline, which is described in 7\^仏~Vol. 357, page 477.479, "FIexible light-emitting diodes made from soluble conducting polymer" (Ua June 1992) e) at least one of the anode and the cathode should be at least partially transparent to allow for the observed light to be produced. The hole injection layer 120 includes a hole injection material and may have one or more functions within an organic electronic device including, but not limited to, planarization of its underlying layer, charge transport and/or charge injection characteristics, Removal of impurities such as oxygen or metal ions and other functions that contribute to the performance of the organic electronic device. The hole injection material can be a polymer, an oligomer or a small molecule. The channels and the like may be vapor deposited or deposited from a liquid 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 acids may be, for example, polystyrenesulfonic acid (polyfluorene acid), poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (poly (2-acrylamido-2-) Methyl-l-propanesulfonic acid)) and class 145481.doc ·37· 201109291 Like. The hole injection layer may include a charge transport compound and the like, such as copper phthalocyanine and tetrathiafulvalene-tetracyanoquinodimethane 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 in, for example, the published U.S. Patent Application Serial Nos. 2004-01,2577, 2004-0 127,637, and 2005/205,860. In some embodiments, the hole transport layer 130 comprises a neodymium compound of formula I. Others for layer i3 are outlined in, for example, Yirk Wang's Kirk-Othmer Encyclopedia of Chemical Technology, 4th Edition, Vol. 18, pp. 837-860 (1996). An example of a hole transport material. Holes can be used to transport both molecules and polymers. Common commonly used hole transport molecules are: N, N, -diphenyl·Ν, Ν'--(3_methylbenyl-biphenyl]-4,4'-diamine)]^,]^1-^ . !^!!)^-]^,]^1-bis(3-methylphenyl)-[l,l'-biphenyl]-4,4'-diamine5 TPD); 1,1-di[(double-4- Phenylamino)phenyl]cyclohexane tolylamino) phenyl]cyclohexane,TAPC); Ν,Ν·-bis(4-tolyl)-oxime, fluorene,-bis(4-ethylphenyl)-[1, 1'-(3,3,-dimercapto)biphenyl]_4,4,-diamine (1^,>1'-1^8(4-11^1^1卩1161^1)-1 ^,^['-1^(4-6111)^11611丫1)-[1,1'- (3,3'-dimethyl)biphenyl]-4,4'-diamine, ETPD); four-(3 -曱 )))-N,N,N,N'-2,5-present diamine (161:1*&]<;13-(3-1116111}^1卩1161^1)-N, N,N',N'-2,5-phenylenediamine,PDA); α-phenyl Ν-Ν, Ν-diphenyl 14548 丨.doc -38- 201109291 Aminophenyl benzene (a-phenyl-4-N, N-diphenylaminostyrene, TPS); p-(diethylamino)benzaldehyde diphenylhydrazone (DEH) triphenylamine (TPA); bis[4-(N,N-diethylamine) (4-[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl) ethane, MPMP) ; 1-phenyl-3 -[p-(diethylamino)styrene]-5-[p-(diethylamino) Phenyl] stone ratio (l-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl] pyrazoline, PPR or DEASP); 1,2-trans-di (9H - °C°°-9-base) Cyclobutanol (1,2-trans-bis(9H-carbazol-9-yl) yclobutane, DCZB) ; N,N,N',N'-tetra (4-曱Phenyl)-(1,Γ-biphenyl)-4,4'-diamine (N,N,N',N'-tetrakis(4-methylphenyl)-(l,l'-biphenyl) 4,4' -diamine,TTB); N,N'-bis(naphthalen-1-yl)-N,N'-di-(phenyl)benzidine (N,N'-bis(naphthalen-l-yl)-N, N'-bis-(phenyl)benzidine, α-ΝΡΒ); and a ruthenium compound such as copper indigo. Commonly used holes for transporting polymers are polyvinyl carbazole, (benzoyl)-polydecane and polyaniline. It is also possible to obtain a hole transporting polymer by doping the above-mentioned hole transporting molecules into a polymer such as polystyrene and polycarbonate. In some cases, triarylamine polymers, especially triarylamine-ruthenium copolymers, are used. In some cases, the polymers and the copolymers are crosslinkable. Examples of the cross-linkable hole-transporting polymer can be found in U.S. Patent Application Publication No. 2005-0184287, the disclosure of which is incorporated herein by reference. In some embodiments, the hole transport layer is doped with a p-dopant, such as tetrafluorotetracyanoquinodimethane and 145481.doc-39-201109291 茈- 3,4,9,10-tetracarboxy-3,4,9,10-dianhydride. In some embodiments, the electron transport layer 150 comprises a neodymium compound of formula I. Other electron transporting materials may be used in layer 150, examples of which include metal-clamped octyl compounds, such as tris(8-hydroxyquinolato) aluminum, Alq3) bis(2-indenyl) -8-喧琳)(p-phenylphenylhydrazine) Ming (III) (bis(2-methyl-8-quinolinolato) para-phenyl-phenol at o)aluminum(III) >BA1Q); The azole compound 'such as 2-(4-biphenyl)-5-(4-dibutylphenyl)-1,3,4_ dioxin 2(2-(4-biphenylyl)-5- (4-t-butylphenyl)-l,3,4-oxadiazole, PBD) and 3-(4-biphenyl)-4_phenyl-5-(4-tri-butylphenyl)_1,2, 4_三^^(3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole,TAZ) and 1,3,5-tris(phenyl- 2-, 3,5-tri(phenyl-2-benzimidazole)benzene (TPBI); 啥p-lin derivative] such as 2,3-bis(4-fluorophenyl)喧吟琳(2,3-bis(4-fluorophenyl) uinoxaline); phenanthroline derivatives such as 9,10-diphenylphenanthroline (DPA) and 2,9-dimercapto-4,7 -diphenyl_ 1,10-morphine (2,9-dimethyl-4,7-diphenyl -1,10-phenanthroline, DD PA), and mixtures thereof. The electron transport layer may also be doped with an n-dopant such as Cs or other alkali metal. Layer 150 can be used to facilitate electron transport' and also acts as a buffer or confinement layer to prevent quenching of exciton layers. Preferably, this layer enhances electron mobility and reduces exciton quenching. The cathode 160 is an electrode that is particularly effective for injecting electrons or negative charge carriers. The cathode can be any metal or non-metal' which has a work function 145481.doc • 40- 201109291 The number is lower than the anode. r. ρ, heart u for the cathode η τ is selected from the group 1 alkali metal (for example

Li, Cs), the second private (alkaline earth;) metal. The younger brother knows the metal (including the rare earth element and the 7G element of the genus and the season of the fishing season). It can be used for materials such as aluminum, indium, calcium, strontium, #, and magnesium, and combinations thereof. It is also possible to deposit a metal containing Li or a Cs-containing metal such as CsF or Li2〇 between the organic layer and the cathode layer to lower the operating voltage. It is known that an organic electronic device can have its ruthenium layer. For example, there may be a layer (not shown) between the anode 110 and the hole injection layer 120 to control the 'positive power' and/or provide the band gap matching of the layers (4) Read (4)), or material - protective layer. Layers well known in the art, such as copper indocyanine, cerium oxynitride, fluorocarbons, decane; or metallic-ultra-thin layers such as Pt. Alternatively, some or all of the anode layer ιι, the active layer 120-150 or the cathode layer 16〇 may be surface treated to increase charge carrier transport efficiency. It is preferred to determine the material selection of each of the compound layers by balancing the positive and negative charges in the emitter layer so that the device has high electroluminescence efficiency. It should be understood that each functional layer may be composed of more than one layer. The apparatus can be prepared by a variety of techniques including sequential vapor deposition of the individual layers on a suitable substrate. Substrates such as glass, plastic and metal can be used. Conventional vapor deposition techniques such as thermal evaporation, chemical vapor deposition, and the like can be used. Alternatively, the organic layer may be applied from a solution or dispersion in a suitable solvent using conventional coating or printing techniques, including, without limitation, spin coating (dip-coating), dip coating (dip-coating). ), roll-to-roll coating technology (r〇ll_t〇_r〇U), inkjet printing (ink_jet printing), web 145481.doc -41·201109291 version (screen-printing), gravure printing (gravure printing) and Similar. The invention also relates to an electronic device comprising at least one active layer positioned between two electrical contact layers, wherein the at least one active layer of the device comprises a bismuth compound of formula 1. Devices often have additional hole transport layers and electron transport layers. In order to achieve a high efficiency LED, the highest occupied molecular orbita (HOMO) of the hole transport material must match the work function of the anode and the lowest unoccupied molecular orbital domain of the electron transport material (lowest un-0ccupied m 〇lecuiar orbita (3) The river (7) must match the work function of the cathode. The chemical compatibility and sublimation temperature of these materials are also important considerations when selecting electron and hole transport materials. It should be understood that The efficiency of the device made of the ruthenium compound can be further improved by optimizing the other layers in the device. For example, a more efficient cathode such as Ca, Ba or LiF can be used. The shaped substrate can also be applied and novel The hole transport material, which causes a reduction in operating voltage or an increase in quantum efficiency. Additional layers may be added to tailor the energy levels of the various layers and contribute to electroluminescence. The compounds of the present invention are often photoinduced. Luminescent (ph〇t〇 luminescent), and can be used for applications other than OLEDs, such as oxygen sensitive indicators and luminescence indicators in biometrics (lumines) The following examples are intended to illustrate the specific features and advantages of the invention. The examples are intended to illustrate the invention, and are not intended to be limiting, unless otherwise indicated, all percentages of 14548l.doc -42- 201109291 used herein are by weight. Synthesis of dopant materials (The preparation process of bismuth dopant D6 is as follows. Synthesis of t-substrate (a):

\OH

5 + CCO 35 g (300 mM) of 2-methylhexanol and 178 g of onion were added to 50 mL of trifluoroacetic acid, and the mixture was refluxed overnight under nitrogen. The solution quickly darkens into a brown heterogeneous material. The solution was cooled to room temperature, evaporated under a nitrogen stream and extracted to decane. The organic layer was separated and dried over magnesium sulfate and evaporated to dryness. The resulting solid was extracted with hexane through a silica column and a pale yellow solution was recovered. The solution was evaporated to a thick oil and recrystallized from acetone/methanol by slow cooling and recrystallization from methanol. The structure was confirmed using NMR analysis. Synthesis of intermediate (b):

6.0 g (16 mM) of intermediate (a) (pure isomer) was placed in 1 mL of di-hexane, and 2.10 mL of Mo (4 mM) was added dropwise at room temperature. I45481.doc -43- 201109291 Stir for 4 hours. The mixture was then poured into water and sodium sulfite was added to consume the remaining bromine. This product is then extracted to vaporize methane and the organic layer is dried over the town of sulfuric acid. The obtained material was passed through an oxidation column (eluent), passed through an alumina column, and then evaporated, and then methanol was added to precipitate a pale yellow solid. Yield is ~7.2 g of intermediate (c) synthesis:

25 g of Moji-Leica saliva (77.7 mM) was added to 18.9 g (155 mM) of boric acid in a gl〇ve box. Join 1.〇 g

Pd2DBA3 (l. 〇 mM), 0.5 g of P(t-Bu) 3 (2.1 mM) and 20 g of sodium carbonate (200 mM) ' and dissolve all the substance in 200 mL of dioxane And 50 mL of water. The resulting product was mixed and heated at 50 ° C for 1 hour in a mantle in a hand-held work box, followed by gentle warming under a nitrogen atmosphere (the lowest point of the varistor setting) overnight. The solution immediately turned dark purple and became dark after reaching ~5 〇〇c. Outside the handle box, water was added to the brown solution, which separated into an oily yellow layer. DCM was added and the organic layer was separated. EtOAc was dried <RTI ID=0.0>(M)</RTI> <RTI ID=0.0> After evaporation to low capacity and addition of hexane, the white solid was removed. The solid was thoroughly washed with decyl alcohol until the washings became colorless, then washed with diethyl ether and then dried in vacuo to give 21 g of a white solid. The structure was confirmed using nmR analysis. I45481.doc -44· 201109291 Synthesis of intermediate (d):

Bis(diphenylphosphine)ferrocene) (DPPF) and 4.3 g of sodium t-butoxide were mixed together and dissolved in 200 mL of xylene in a hand-held work box. Stir for 15 minutes and then add 25 g of 3-iodo-bromobenzene. Mix for 15 minutes, then add 10 g of carbazole and then reflux the mixture. Perform a reflow procedure (Refluxed o/n.) using an air condenser. The solution immediately turned into a dark purple/standard color, but as long as the temperature reached ~8 〇. (:, the solution will turn cloudy and dark reddish brown. After heating close to the overnight reflux, the solution will turn into a clear dark brown. Evaporate the solution in a nitrogen flow environment outside the handle box and dissolve it in DCM Then, using DCM/hexane, the solution was soxhlet passed through a bed of cerium oxide and basic alumina (stacked in a rope extractor). The dark orange solution was collected and e evaporated to dryness. Dark orange (tetra) m alcohol filaments, then dissolved in B., re-precipitated with methanol. The brown oil was evaporated to a low volume f' in B (four) and then added to the propyl/methanol to precipitate a grayish white Solid, yield: 6.4 g. #. The off-white solid was collected by filtration, then washed with less s. k. and vacuum dried. The structure was confirmed by NMR analysis. Synthesis of intermediate (e) · 145481. Doc -45- 201109291

4.8 g (〇.〇i M) of intermediate (d) was added to i 7 g (0.01 Μ) of the amine in a hand-held work box. 0.10 g of pd2DBA3 (0_ll ηιΜ), 0.045 g of P(t-Bu)3 (0.22 mM) and 1.1 g of t_BuONa were added, and then all the substances were dissolved in 25 mL of toluene. Once the catalyst material is added, a slight exothermic reaction occurs. The resulting product was heated in a heating pack of a hand-held work box at a temperature of 80 ° C for 2 hours under a nitrogen atmosphere until a dark brown solution (concentrated) was present. After cooling, the solution was excited by β-oxidation chromatography by DCM chromatography. A dark yellow solution with a bright violet/blue photoluminescence was then collected. The solution was evaporated to a low capacity in a nitrogen atmosphere to form a viscous orange oil which solidified to a dark yellow glass upon cooling. It was stirred into methanol/DCM and crystallized to give a pale yellow/white solid. The structure was confirmed using NMR analysis. Synthesis of dopant D6:

14548l.doc 201109291 In a hand-operated box, add 2.81 g (5 mM) of intermediate (e) and 0.5 g (5 mM) of t-Bu〇Na and 50 mL of toluene to 1.32 g (2_5 mM) ) in intermediate (b). Add 0.2 g of the solution dissolved in 10 mL of toluene.

Pd2DBA3 (0.2 福) and (.〇 8 g of p(t-Bu)3 (0.4 mM). After mixing, the solution slowly exothermed and turned yellow brown. The resulting product was mixed in a heating pack of a hand-held work box under a nitrogen atmosphere at a temperature of ~丨〇〇〇c and heated for 1 hour. The solution immediately turned dark purple, but as soon as the temperature reached ~80 C, it turned dark yellow green and had a distinct green illuminant. Stir overnight at the lowest varistor set point. After cooling, the material was removed from the kit and filtered through an acid alumina plug which was chromatographed with toluene and methyl chloride. The dark orange solution is then evaporated to a low capacity. This solution was passed through a ruthenium dioxide column (using 6 Torr: 4 Torr in toluene: hexane). A yellow-orange solution was collected which showed a blue guide point (leadmg Sp〇t) on TLC. This solution was redissolved in hexane:toluene (80:20) and passed through an acidic oxidation of 80% hexane/toluene. Discard the fast-moving blue bands (蒽 and monoamine). The resulting yellow ribbon was evaporated to a low capacity and crystallized from toluene/acetone/methanol. The resulting product was washed with methanol and hexane and vacuum dried to obtain a free-flowing single crystal yellow powder. The structure was confirmed using NMR analysis. (7) Dressing agent D12, N6, N12_ bis(2,4-dimethylphenyl)_N6, bis(4 _isopropylidene triphenyl _4_ 浓 仏 仏 diamine (NhNm Μ dimethylphenyl)-N65Nl2- The preparation process of bis(4--is〇pr〇pylterphenyl.4_yl)chrySene-6,12-diamine) is as follows. 145481.doc -47· 201109291

In a dry phase, '6,12-dibromochrysene (0.54 g, 1.38 mmol), N-(2,4-didecylphenyl)_N-(4,- Isopropyltriphenyl-4-yl)amine (1.11 g, 2.82 mmol), tris(ieri-butyl)phosphine (0.028 g, 〇·1 4 mmol) ) and tris(di-amylidene) tris(dibenzylideneacetone) dipalladiUm(0)) (0.063 g'0_069 millimolar) in a round bottom flask' and dissolve it in 20 ml of dry In benzene. The solution was mixed for one minute, followed by the addition of sodium tributoxide (0.29 g, 3.03 mmol) and 10 ml of dry toluene. The reaction was heated to 6 ° C for 3 days by adding a heating pack. The reaction mixture was then cooled to room temperature and filtered through a 1 inch gelatin plug and 1 inch Celite, and then washed with 500 mL of benzene. The volatiles were removed under reduced pressure to give a yellow solid. Further, the crude product was purified by silica gel column chromatography using a gradient distribution (〇% to 40%) of chloroform in hexane. Recrystallization from DCM and acetonitrile, and the yield of the product obtained was 〇.54 g (4%) as a yellow solid. The results of 1H NMR (CDC13) were consistent with this structure. (3) Using a procedure similar to the synthesis of dopant D12, a dopant 〇13, N6, N12-bis(2,4-dimethylphenyl)-N6, N12-di(4,,-three) was prepared. Grade - 辛基联三145145.doc •48- 201109291 Benzene-4-yl) -6,12-diamine (N6,N12-bis(2,4-dimethylphenyl)- N6,N12-bis(4&quot;- Tert-octylterphenyl-4-yl)chrysene-6,12-diamine).

Comparative Example A This example illustrates the preparation of a non-deuterated compound, i.e., Comparative Compound A.

This compound can be prepared according to the following method:

145481.doc • 49- 201109291 b heart; &gt;8 —- —- ϊβ^-8

Synthesis of Compound 2: Dry gasification at 1.5 L in a 3 L flask equipped with a mechanical stirrer, a dropping funnel, a thermometer, and a N2 bubbler (N2 bubbler) 54 g (275.2 mmol) of onion ketone was added to the decane. The flask was cooled in an ice bath, and then 83.7 ml (559.7 mmol) of 1,8-dioxinbicyclo[5.4.0]undec-7-ene (1,8-diazabicyclo[5.4] was added using a dropping funnel. .0]undec-7-ene, DBU) until more than 1,5 hours. The solution turned opaque orange and then turned dark red. 58 ml (345.0 mmol) of triflic anhydride was added to the still cooling solution over a period of about 1.5 hours via a syringe, and the temperature of the solution was kept below. The reaction was allowed to continue at room temperature for 3 hours, after which an additional 1 mL of trifluoromethanesulfonic anhydride was added and stirring was continued at room temperature for 3 minutes. Slowly add 5 〇〇 mL of water and then leave the layer formed. The aqueous layer (aque〇us Uyer) was extracted with 3 parts of 200 mL of dichlorohydrazine (DCM), and the organic matter of group 5 was dried over magnesium sulfate, and then evaporated under reduced pressure (r〇tary evap〇rati〇n). Filtered and concentrated to give a red oil. The ruthenium column chromatography was carried out, followed by recrystallization from hexane to yield 43. i g of light brown powder (43%). 145481.doc •50· 201109291 Synthesis of Compound 3: Anthracen-9-yl trifluoromethanesulfonate (6.0 g, 18.40 mmol), in a nitrogen-filled hand-held work box, Napthalen-2-yl-boronic acid (3.78 g '22.1 mmol), potassium phosphate tribasic (17.50 g»82.0 mmol), acetic acid (II) (palladium) (II) acetate) (0.41 g, 1.8 mmol), tricyclohexylphosphine (0.52 g, 1.8 mmol) and THF (100 mL) were added to a 200 mL gram equipped with a magnetic stirring bar. Kjeldahl reaction flask. After the reaction mixture was removed from the dry box, the reaction mixture was flushed with nitrogen, and 50 mL of degassed water was added by a syringe. A condenser was then added and the reaction was allowed to reflux overnight. The reaction was monitored using TLC. Once the reaction was complete, the reaction mixture was cooled to room temperature. The organic layer was separated and the aqueous layer was extracted with DCM. The organic components were combined and washed with brine and dried over magnesium sulfate. The solvent is removed under reduced pressure. The resulting solid was washed with acetone and hexane and filtered. Purification was carried out by silica gel column chromatography to yield 4.03 g of product (72%) which was a pale yellow crystalline material. Synthesis of Compound 4: 11 · 17 g (36.7 mmol) of 9-(naphthalen-2-yl) anthracene was suspended in 100 mL of DCM. 6.86 g (38.5 mmol) of N-bromosuccinimide (NBS) was added and the mixture was stirred under the illuminance of a 100 W lamp. A clear yellow solution is first formed and then a precipitate appears. The reaction was monitored using TLC. After 5 hours, the reaction was partially concentrated to remove the vaporized methane and then crystallized from acetonitrile to yield 12.2 g of pale yellow crystals (87%). Synthesis of Compound 7: Naphthalen-l-yl-l-boronic acid (14.2 g, 82.6 mmol), 1-ML base in a nitrogen-filled hand-held working chamber 1-Ethyl-2-iodobenzene (25.8 g, 91.2 mmol), tetrakis(triphenylene) II! Tetrakis (triphenylphospine) palladium(O)) (1.2 g, 1.4 mmol), sodium carbonate (25.4 g, 240 mmol) and toluene (120 mL) were added to a 500 mL round bottom flask equipped with a stir bar. After the reaction mixture was removed from the dry box, the reaction mixture was flushed with nitrogen, and 120 mL of deaerated water was added by a syringe. Next, a condenser was attached to the reaction flask, and the reactant was refluxed for 15 hours. The reaction was monitored using TLC. The reaction mixture was cooled to room temperature. The organic layer was separated and the aqueous layer was extracted with DCM. The organic components are combined and the solvent is removed under reduced pressure to yield a butter. Purification was carried out by column chromatography using Shixi gum, yielding 13.6 g of clear oil (58%). Synthesis of compound 6: 4-bromophenyl-l-naphthalene (28.4 g, 10.0 mmol), bis(pinacolate) diboron (40.8 g '16.0 mmol) , Pd(dppf)2Cl2 (1.64 g '2.0 mmol). Acetate If (potassium acetate) (19.7 g, 200 mmol) and DMSO (350 mL) were added to a 1 liter flask equipped with a magnetic stir bar and a reflux condenser. The reflux condenser was connected to a nitrogen line and an oil bath. The mixture was bubbled with nitrogen for 15 minutes and then added to 145481.doc -52- 201109291

Pd(dppf)2Cl2 (1.64 g ' ο.· m〇i). During this process, the mixture gradually changes to a dark fading color. The reaction was allowed to pass in an oil bath for 18 hours under a nitrogen atmosphere. After cooling the mixture, the mixture was poured into ice water and extracted with a gas (3x). The organic layer was then washed with water (3x) and saturated brine (1×) and then dried over MgS04. After filtration and removal of the solvent, the residue was purified using silica gel column chromatography. The product containing the components was combined and the solvent was removed using rotary vacuum evaporation (r〇tary evap〇rati〇n). The resulting white solid was crystallized from hexane/methanol and dried to afford a white flaky crystal product yield of 15 〇g (45%) at 4 rc in a vacuum oven. 1H and 13C-NMR spectra The results are consistent with the expected structure. Comparison of Compound A Synthesis 4,4,5,5-Tetramethyl-2-(4-(naphthalen-4-yl)phenyl)-1 in a Handle Box ,3,2-di.,^^(4,4,5,5-tetramethyl-2-(4-(naphthalen-4-yl)phenyl)-1,3,2-dioxaborolane) (1.90 g &gt; 5.74 Ment) 'Tris(dibenzylideneacetone) dipalladium(O) (0.24 g, 0.26 mmol), and toluene (50 mL) were added to a 250 mL flask (2·00 g, 5.23 mmol). Remove the reaction flask from the dry box. Attach a condenser and nitrogen inlet to the reaction flask. Add sodium carbonate (2 Μ, 20 mL) degassed and dissolved in water via a syringe. The reaction was stirred and heated overnight at a temperature of 90 ° C. The reaction was monitored using HPLC. After the reaction was cooled to room temperature, the organic layer was separated. The aqueous layer was washed twice with DCM. Concentrate using rotary evaporation The combined organic layer produces a gray powder which is purified by filtration of neutral alumina, precipitation of hexane and purification by gel column chromatography to yield 2.28 g of white. Powder (86%). The resulting product is further purified as described in the published U.S. Patent Application Serial No. 2008-01:38655, to achieve an HPLC purity of at least 99.9% and an impurity absorbance of not more than 〇.〇1 Figure 2 illustrates the 1H NMR spectrum of Compound a. Example 1 This example illustrates the preparation of a compound of Formula I, Compound Η14.

Comparative Compound A H14 A1C13 (0.48 g, 3.6 mmol) was added to the perdeuterobenzene or benzene-D6 (C6D6) (1 〇〇 mL) of Comparative Compound A from Comparative Example A under a nitrogen atmosphere. In solution (5 g, 9.87 mmol). After adding D2 hydrazine (50 mL) to the resulting mixture, the mixture was stirred at room temperature for 6 hours. The layers were separated and the aqueous layer was washed with CH.sub.2Cl.sub.2 (2.times.30 mL). The combined organic layers were dried over magnesium sulfate and the volatiles were removed using rotary evaporation. The crude product was purified via column chromatography. The product obtained by deuteration H1 (x + y + n + m = 21 - 23) was a white powder (4.5 g). 145481.doc •54· 201109291 further purification of the resulting product, as described in the published U.S. Patent Application Serial No. 2008 0138655, to achieve a purity of at least 99 9% and an impurity absorbance of not more than 0.0 It is known above that the material determined has the same purity level as Comparative Compound A. Figures 3 and 4 show iH NMR (10) heart coffee ASAp MS, respectively. The structure of the compound is as follows: D Π

Where 'D/H' indicates that Η or D has approximately equal probability of being at this atomic position. This structure was confirmed by H NMR, 13C NMR, 2d NMR and 1H-13C HSQC (nuclear single quantum coherence). Example 2 and Example 3 and Comparative Example b and Comparative Example c These examples show the production and performance of a device having a blue emitter. The device has the following structure on a glass substrate: Anode = indium tin oxide (IT0): 5 〇 nm hole injection layer = HIJ1 (50 nm), which is a conductive dispersion of a conductive polymer and a fluorinated polymerized acid liquid. Such materials are described in, for example, the published U.S. Patent Application Serial No. 2004/0102577, No. 2004/0127637, No. 2005/0205860, and the entire disclosure of the entire disclosure of the entire disclosures of Hole transport layer = polymer Pi, which is a non-crosslinkable arylamine polymer (2〇145481.doc -55· 201109291 nm) Electroactive layer = 13:1 host material and dopant (40 nm) As shown in Table 1, the electron transport layer = ET 1, which is a metal leaching derivative (10 nm) cathode = CsF / Al (1.0 / 100 nm) Table 1. Device electroactive layer example host material dopant comparison Sexual Example B-1 Comparative Compound A D12 Comparative Example B-2 Comparative Compound A D12 Comparative Example B-3 Comparative Compound A D12 Comparative Example B-4 Comparative Compound A D12 Example 2-1 H14 D12 Example 2-2 H14 D12 Example 2-3 H14 D12 Example 2-4 H14 D12 Comparative Example C-1 Comparative Compound A D13 Comparative Example C-2 Comparative Compound A D13 Example 3-1 H14 D13 Example 3-2 H14 D13 Processed by Solution And one of the thermal evaporation techniques to produce an OLED device. The glass substrate was coated using patterned indium tin oxide (ITO) from Thin Film Device, Inc. These ITO substrates were based on Corning 1737 glass coated with ruthenium 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. Subsequently, the patterned ITO was ultrasonically cleaned in acetone, rinsed with isopropyl alcohol, and then dried in a nitrogen stream environment. The cleaned patterned ITO substrates were treated with UV ozone for 10 minutes just prior to the fabrication of the device. Immediately after cooling 145481.doc -56-201109291, an aqueous dispersion of HIJ1 was spin-coated on the surface of the ITO and then heated to remove the solvent. After cooling, the substrates are then spin coated with a solution of a hole transport material and then heated to remove the solvent. After cooling, the substrates are spin coated with an emissive layer solution and then heated to remove the solvent. The substrates are masked and placed in a vacuum chamber. The electron transport layer is deposited using a hot flash bond followed by a CsF layer. The mask is then replaced in a vacuum and an A1 layer is deposited using thermal evaporation. The vacuum chamber is vented and the devices are packaged using a glass cover, dessicant, and UV curable epoxy. The characteristics of the OLED sample are described by measuring the following data: (1) current_voltage (I-V) curve, (2) electroluminescence intensity versus voltage, and (3) electroluminescence spectrum versus voltage. All three measurements above are performed at the same time and are controlled by a computer. The current efficiency of the device at a particular voltage is determined by dividing the intensity of the electroluminescent radiant of the LED by the current required to operate the device. Its unit is cd/A. Multiplying the current efficiency by ρί(π) and dividing by the operating voltage yields a power efficiency ❶ in lm/w. Table 2 shows the information of the device. Table 2·Device Performance Example CIE (x,y) Voltage (V) CE (cd/A) EQE (%) PE (lm/W) Life Test Current Density (mA/cm2) Life Test Luminous Intensity (nits) Original T50 (8) Lifetime prediction period T50 @1000 nits Comparative example B-1 0.135, 0.124 4.4 6.1 6.0 4.3 129 6837 410 10766 Comparative example B-2 0.135, 0.127 4.3 6.4 6.1 4.7 125 7002 410 11211 Comparative example B-3 0.136, 0.123 4.4 5.7 5.6 4.1 127 5906 430 8804 145481.doc -57- 201109291 Comparative example Β-4 0.134, 0.129 4.3 6.4 6.1 4.7 123 7021 430 11813 Example 2-1 0.136, 0.119 4.4 5.7 5.7 4.1 136 7040 870 24010 Example 2 -2 0.137, 0.117 4.2 5.4 5.5 4.1 126 6244 830 18679 Example 2-3 0-136, 0.118 4.2 5.7 5.7 4.2 129 6467 830 19828 Example 2-4 0.136, 0.118 4.3 5.5 5.6 4.1 121 6148 870 19071 Comparative example c_ 1 0.135, 0.128 4.3 6.2 6.0 4.6 141 8018 490 16871 Comparative example C-2 0.135, 0.128 4.3 6.3 6.0 4.6 125 7136 510 14403 Example 3-1 0.135, 0.122 4.3 6.0 5.9 4.4 121 6741 950 24356 Example 3-2 0.135, 0.124 4.2 6 5.8 4.4 126 69 74 930 25257 *All information is @1000 nits,CE=current efficiency; ciEx and CIEy are based on the x and y color coordinates of the C.I.E. Chromaticity Diagram (Commission)

Internationale de L'Eclair age, 1931). The original T50 is the time (in hours) at which the device reaches half of the initial luminous intensity, which is given at the lifetime test luminous intensity. The predicted lifetime of T50 is predicted at 1 〇〇〇 nits, which uses an acceleration factor of 7.7. From this, it can be seen that with the deuterated host material of the present invention, the service life of the device is greatly increased while maintaining other device characteristics. When the emitter D12 was used, the comparison device (Comparative Examples B-1 to B-4) having the non-deuterated host material had an average predicted T5 〇 of 1 〇, 649 hours. When using a similar host material Η 14 (Examples 2-1 to 2-4), the devices have an average predicted 50 of 20,379 small 8 ounces. When the emitters 1) 13 were used, the comparison devices (Comparative Examples C-1 and C-2) had an average prediction of 15 〇 of 15,637 hours. When using a similar host material Η14 (Examples 31 and 3_2), the average predicted Τ50 was 24,807 hours. 145481.doc •58- 201109291 EXAMPLE 4 This example illustrates the preparation of some deuterated intermediate compounds, which can be used to synthesize the chemical intermediates 4A using a controlled level of deuteration:

A portion of anhydrous copper dibromide (45 g, 0.202 mole) was added to a solution of 蒽-dl0 (18.8 g, 0.10 mole) in CC14 (500 mL). Under reflux conditions, the reaction mixture was stirred and heated for 12 hours. The brown copper dichloride gradually changed into white copper dibromide, and gradually released the desert hydrogen (connected to the alkaline bath absorber (base) Bath absorber)). At the end of the reaction, the copper dibromide was removed by filtration, and then the four vaporized carbon solution was passed through a 35-mm chromatography column packed with 200 g of alumina. The column was eluted with 200 ml of CH2C12. The combined precipitate was evaporated to dryness to give 24 g of 9-bromoanthracene-d9, which was a lemon-yellow solid (87%). The solid included impurities (~2%) of the starting material and by-products of dibromide (~2%). This material is used directly in the additional coupling reaction and does not require purification. The intermediate can be further purified by recrystallization using hexane or cyclohexane to give a pure compound. Intermediate 4B:

L2/Nal〇4 ^------ H2SO4/HAC

201109291 A mixture of 93 mL of 50% H2S04 and 494 mL of HOAc was added to d5-bromobenzene (MW 162, 100 g, 0.617 mol) at room temperature. Next, powdered I2 (MW 254, 61.7 g '0.243 moles) was added, followed by powdered NaIO4 (MW214, 26.4 g, 0.123 mol). The mixture was vigorously disturbed and heated to 90 ° C for 4 hours. The dark purple solution turned into a light orange mixture containing a very fine white precipitate. The mixture was then cooled to room temperature overnight. During this time, the resulting product precipitated into plate-like microcrystals. The mixture was passed through and the mixture was washed twice with 1 〇 % sodium thiosulfate Na 2 S 2 〇 3 (50 mL) and then washed with water. The s-synthesis mixture was dissolved in CHAl2 and then subjected to a rapid column column. 124 g of pale yellow crystalline material (70%) was obtained. The filtrate was extracted with CH.sub.2Cl.sub.2 (50 mL.sub.3) and combined. /. Sodium thiosulfate Na2S2〇3 (5〇mL) was washed twice and washed with water ci^ci2 ^ After drying and evaporating the solvent and performing rapid flash column chromatography, another 32 g of pure product was obtained. (17.5%). The total weight is 156 g (yield 88%). Intermediate 4C:

Hydrogen peroxide (FW: 34, d = 11 g/mL, 56 g, 51.5 mL of 30 ° / aqueous solution; 〇 5 m 〇 1) was slowly added to CH 2 C 12 (800 mL) at the temperature: Naphthalene_d8 (MW 136,68 g' Ο·5 Moule) in H20 (80 mL) and hydrobromic acid (MW: 81, d = 1.49, 100 g; 67.5 mL of 49% aqueous solution; 〇6 Mo The ear) is stirred for 3 minutes - 145481.doc -60 · 201109291 cycle. The reaction was kept at room temperature for 4 hrs while the process was monitored using TLC. After completion of the bromination, the solvent was removed under reduced pressure and ίο% sodium thiosulfate Na2S2O3 ( 50 mL) was washed twice and the resulting crude product was washed with water. The pure product was isolated by hexane (1% by weight) by silica gel flash column chromatography (100-200 mesh) and then distilled to give 85 g of pure 1-bromo-naphthalene-d7. It is a clear liquid with a yield of about 80%. Intermediate 4D:

Bubbling 300 ml of 丨-bromonaphthalene _d7 (21 4 g, 〇·1〇mol) and bis(pinac )) in a dry 1,4-dioxanthine with nitrogen (bis(pinac〇lat) 〇)dib〇r〇n) (38 g, 〇·15 mol), potassium acetate (19.6 g, 0.20 mol) mixture for 15 minutes ° then add 卩(1咐1^)2(:12-( ^2(:12(1.63§, 0.002 111〇1). The mixture was heated in ioo °c (oil tank) for 18 hours. After cooling the mixture, the mixture was filtered through diatomaceous earth and then concentrated. To 5 〇mL, then water was added and extracted three times with diethyl ether (1 〇〇 mL x 3). The organic layer was washed with water (3×) and brine (1×) then dried over EtOAc, then filtered and concentrated. It is submitted to a ruthenium column (leaching solution: hexane) to give a white liquid with by-product naphthalene and diboronic ester. Therefore, further purification is carried out by distillation to obtain a clear viscosity. Liquid. Yield 21 g, 82%. 145481.doc •61 · 201109291 Intermediate 4E:

: So

D D

D D

Pd(Ph3P)4 甲笨-H20/2M Na2C03 Add Na2C03 (12.6 g, 〇·12 mol) and H2O (50 mL), Aliquat® (3 g) to 1-bromo- in benzene (300 mL) A mixture of 4-iodo-benzene-D4 (10.95 g, 0.0382 mole) and 1 naphthalene boronate-D7 (10.0 g, 0.0383 mole). The mixture was bubbled with nitrogen for 15 minutes. Then pd(PPh3)4 (0.90 g '2°/.) was added. The mixture was refluxed under a nitrogen atmosphere for 12 hours. After cooling the reaction mixture, the reaction mixture was separated, and then the organic layer was washed with water, dried, and concentrated. Add cerium oxide and concentrate. After evaporating the residual solvent, fast column chromatography was carried out using hexane as the eluent to give a crude product. Further work by distillation (collected at 135-140 C/100 mt rrrr) gave a clear liquid (8.76 g, yield 78%). , sticky 'intermediate 4F:

Pd(dppf)2CI2, AcOK 1,4 氡 氡, 90〇C, 18h

145481.doc -62- 201109291 Bubbling 200 ml of dry coke with nitrogen, bromine-benzene 'naphthalene- dll (22 g '0.075 mole), di(pinacene) diboron in 4_dioxanthine A mixture of 23 g, 〇〇9〇mole), potassium acetate (22 g, 0.224 mole) for 15 minutes. Then Pd(dppf)2Cl2 CH2C12 (1.20 g, 〇_〇〇147 mol) was added. The mixture was heated at 100 ° C (oil sump) for 18 hours. After cooling the mixture, the mixture was filtered through crushed vine, then concentrated to 5 〇 mL, then water was added and extracted with acetonitrile three times. (1 〇〇mL&gt;&lt;3). The organic layer was washed with water (3x) and brine (1x) and then dried on MgS 4, then transitioned and concentrated. The residue was submitted to a Shixi rubber column (solution: burned) to give a white liquid which had by-products naphthalene and diboron. Therefore, further purification was carried out by performing the gel column chromatography again using hexane as a bath. After evaporating the solvent and concentrating it to about 80 mL of hexane and forming a white crystal product, the product was filtered to yield 20.1 g, yield 81%. Intermediate 4G:

Add Na2C〇3 (31.8 g) and H2〇 (120 mL), Aliquat® (5 g) to intermediate 4A (18.2 g) in toluene (500 mL) and boron ester (25.5 g) of intermediate 4F in. The mixture was bubbled with nitrogen for 15 minutes. Then Pd(PPh3)4 (1.5 g, 1.3%) was added. The mixture was refluxed under a nitrogen atmosphere for 12 hours. After cooling the reaction mixture, the reaction mixture was separated, and then the organic layer was washed with water, 145481.doc -63 - 201109291 and separated, dried and concentrated to ~50 mL, then poured into MeOH. The solid was filtered to give a crude yellow material (~28.0 g). The crude product was washed with water, HC1 (10%), water and methanol. The crude product was redissolved in CHCh, dried over MgS04 and filtered. The phthalocyanine was added to the filtrate to 'concentrate and dry, and then hexane was used as the lysate alone (all 50 L of hexane were passed through - only 5 L of hexane was recovered) to carry out the purification of lycopene (〇.5 Kg). To get a white product. Intermediate 4H:

Add bromine (MW 160, 8.0 g, 〇.〇5 mole) dissolved in CH2C12 (150 mL) slowly (20 min) to 9-(4-naphthalen-1-yl) benzene onion in CH2C12 (450 mL) -D20, a solution of intermediate 4G (MW 400.6, 20.3 g, 0.05 mol) (cooled in ice bath). The reaction occurs immediately and the color turns pale yellow. A solution of Na2S203 (2 Μ 100 mL) was added and stirred for 15 minutes. The aqueous layer was then separated and the organic phase was washed three times with Na.sub.2CO.sub.3 (10%, 50 mL) then water. Next, it was separated and dried using MgS 4, and then the solvent was evaporated until 1 〇〇 mL was left. It was poured into methanol (200 mL) and filtered to give 23.3 g of pure compound (MW 478.5, yield 97.5%). /. Purity. 145481.doc -64- 201109291 Intermediate 41 :

D D

Naphthalene-D8 (13_6 g '0.10 mol), di(pinacol) diboron (27 93 g, 0.11 mol), di-μ-methoxy (1,5-cyclooctadiene) dioxime (i) (di-mu-methox〇bis( 1,5-cyclooctadiene)diiradium(I)) [Ir(OMe) COD]2 (1.35 g, 2 mmole, 2%) and 4,4'-double three Butyl-2,2'-linked. A mixture of bite (1·1 g, 4 mmole) was added to cyclohexane (200 mL). The mixture was degassed with N2 for 15 minutes and then heated at 85 (oil tank) overnight (dark brown solution). The mixture was passed through a silicone pad. Collect the components' and concentrate until dry. Add hexane. The filtrate (liquid) was concentrated and passed through a ruthenium column and rinsed with hexanes to give a clear liquid which was not a pure liquid, so it was repurified by a hydrazine column and then rinsed with hexane, followed by 13 51: / 1 Distillation under 〇〇mmtorr' yields a pure white viscous liquid which is then solidified to give a white powder (18.5 g, yield 70%). Intermediate 4J:

In a round bottom flask (100 mL) was added 9-bromoindole-d9 (MW 266, 2.66 g '0.01 mole), naphthalene-2-boronic acid (MW 172, 1.72 g, 0.01 m〇ie), followed by hydrazine Benzene (30 mL). Rinse the mixture with N2 for 1 〇 minutes. 145481.doc • 65- 201109291 Then add Na2C03 (2 Μ, 10 mL (2.12 g) 0_02 mole) dissolved in water (10 mL). The mixture was purged with A for 10 minutes. Adding catalyst

Pd(PPh3)4 (dose 0.25 g, 2.5%, 0.025 mmol). The mixture was refluxed overnight. The organic layer was separated, then poured into methanol and washed with water, HCl (10 〇 / 〇), water and methanol. A 2.6 g pure white product was obtained. (Yield: 83%). Intermediate 4K:

A solution of 9-21-naphthalene-onion-d9, intermediate 4J (2.6 g, 0.0083 mole) in CH2C12 (50 mL) was added dropwise to a solution of bromine (1.33 g, 0.0083 mole) in ch2C12 (5 mL). Medium and stir for 3 minutes. A solution of Na2S2〇3 (2 Μ ' 10 mL) was added and stirred for 5 minutes. The aqueous layer was then separated and the organic phase was washed three times with Na.sub.2CO.sub.3 (10% &apos; Next, it was separated using MgS04 and dried, and then the solvent was evaporated until 2 mL of mL was left. Methanol (1 〇 0 mL) was injected and filtered to give a pure compound (3" g, yield 96%). 145481.doc -66 - 201109291 Intermediate 4L:

Add Na2CO3 (4.0 g, 0.04 mole) and H2O (20 mL) to 9-bromoindole-D9' intermediate 4K (2.66 g, 0.01 mol) and 4,4,5 in a stupid (~6 mL) , 5_ Tetramethyl 2 - (naphthalen-2-yl-D7)-l, 3, 2 dioxin boron (2.7 g, 0.011 mole) in a mixture. The mixture was bubbled with nitrogen for 5 minutes. Then Pd(PPh3)4 (0.20 g, 2.0%) was added. The mixture was refluxed under a nitrogen atmosphere for 18 hours (yellow solid). After cooling the reaction mixture, it was poured into MeOH (2 mL). The solid was filtered to give a yellow color. π. The crude product was washed with water and methanol. It was redissolved, dried on MgS04 and filtered. The tannin extract was added to the filtrate, and then concentrated and dried, and the purification was carried out using hexane as a solution to obtain a pure product (3.0 g, yield 94%). Intermediate 4M:

145481.doc •67· 201109291 A solution of 9-2,-naphthalene-onion-d9, intermediate 4L (2.8 g, 0.00875 mole) in CH2C12 (50 mL) was added dropwise to bromo in ch2C12 (5 mL). 1·4 g, 0.00875 mole) in the solution and mix for 3 minutes. A solution of Na2S203 (2 Torr, 10 mL) was added and the mixture was stirred for 15 min. The aqueous layer was then separated and the organic phase was washed three times with Na.sub.2CO.sub.3 (10. Next, it was separated and dried using MgS04, and then the solvent was evaporated until 20 mL remained. Injected sterol (丨 00 mL) and filtered to give a pure compound (3·3 g, yield 95%). Example 5 This example illustrates the combination of compound H8 from intermediate 4H and intermediate 41.

Add K2C03 (12.8 g, 0.093 mole) and H20 (4 〇mL) to 9-bromo-l-(4-naphthalen-1-yl) phthalate-D19 intermediate 4H (14.84 g) in DME (350 mL) , 0.03 1 mole) and 2-naphthyl boronate intermediate 41 (10.0 g, 0.038 mole) in a mixture. The mixture was bubbled with nitrogen for 15 minutes. Then Pd(PPh3)4 (0.45 g, 1.3%) was added. The mixture was refluxed under a nitrogen atmosphere for 12 hours. After cooling the reaction mixture, the reaction was concentrated to 145481.doc - 68 · 201109291 s to ~150 mL and then poured into MeOH. The solid was filtered to give a pale yellow crude product. The crude product was washed with water and methanol. It was redissolved in CHCU, dried on MgS〇4, and filtered. The tannin extract was added to the liquid, concentrated and dried, and purified by hydrazine (0.5 Kg) using hexane:methanol (3:1) as a solvent to give a white product. (15 g, yield 91%) Example 6 This example illustrates the synthesis of the compound H1 oxime from Intermediate 4K.

9-Deep-10-(naphthalene-2-yl)anthracene intermediate 4Κ〇 96 g, 〇 〇5 *

g » 0.06 mol) was added to a round bottom flask (丨〇〇 mL) followed by toluene (3 〇 mL). #N2 Purge the mixture for (7) minutes. Next, Na2C〇3 (1 9 〇 ^, .018 mole) dissolved in water (8 mL) was added followed by AH quat 8 (1 mL). Continue to sweep the mixture for 10 minutes. Catalyst Pd(PPh3)4 (dose 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 white solid. Further purification was carried out by performing filtration on a silica gel column chromatography using gas-purified hexanes (1:3) to give a pure white compound (2.3 g, yield 9 〇〇/0). 145481.doc -69- 201109291 Example 7 This example illustrates the synthesis of compound H9 from intermediate 4K and intermediate 4F.

9-Bromo-10-(naphthalen-2-yl)indole-D8 intermediate 4K (0.70 g, 0.0018 mol), 4-(naphthalen-1-yl)benzeneboronic acid-Dll intermediate 4F (0.7 g, 0.002 mol Add a round bottom flask (100 mL) and then add toluene (1 〇 mL). The mixture was purged with N2 for 10 minutes. Then added to dissolve in water (3 mL)

Na2CO3 (0.64 g' 0.006 mole) followed by Aliquat® (0.1 mL). Continue to rinse the mixture with N2 for 1 minute. Catalyst pd(pph3)4 (dose of 0.10 g) was added. The mixture was refluxed overnight. After separating the aqueous phase, the organic layer was poured into methanol (1OmL) to collect a white solid. Further purification was carried out by performing a silica gel column chromatography using a gas-like:hexane (1:3) to give a pure white compound (〇 9 g, yield 95 〇 / 〇). The compounds Η10, Η12 and Η13 were prepared in a similar manner. Examples 8 - 10 and Comparative Examples D and Ε These examples show the production and performance of a device having a blue emitter. The device has the following structure on a glass substrate: 145481.doc •70· 201109291 Anode = ΙΤΟ (50 nm) Hole injection layer = HIJ1 (50 nm) Hole transport layer = polymer P1 (20 nm) Electroactive layer =13 : 1 host material: dopant (40 nm), as shown in Table 3 electron transport layer = ET1 (10 nm) cathode = CsF / Al (1.0 / 100 nm) Table 3. Device electroactive layer example host material D13 Comparative Example D-1 Comparative Compound A D13 Comparative Example D-2 Comparative Compound A D13 Example 8-1 H11 D13 Example 8-2 H11 D13 Example 9-1 H8 D13 Example 9-2 H8 D13 Comparative Example E- 1 Comparative Compound A D13 Comparative Example E-2 Comparative Compound A D13 Example 10-1 H10 D13 Example 10-2 H10 D13 An OLED device was produced by a combination of solution processing and thermal evaporation techniques. The glass substrate was coated using patterned indium tin oxide (ITO) from Thin Film Device, Inc. These ITO substrates were based on Corning 1737 glass coated with ruthenium 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. Subsequently, the patterned ITO was ultrasonically cleaned in acetone, rinsed with isopropyl alcohol, and then dried in a nitrogen stream environment. 145481.doc -71 - 201109291 These cleaned patterned IT0 substrates were treated with UV ozone for 10 minutes just prior to the production of the device. After cooling, an aqueous dispersion of HIJ1 was spin-coated on the surface of the crucible and then heated to remove the solvent. After cooling, the substrates are then spin coated with a solution of a hole transport material and then heated to remove the solvent. After cooling, the substrates are spin coated with an emissive layer solution and then heated to remove the solvent. The substrates are masked and placed in a vacuum chamber. The electron transport layer was deposited using thermal evaporation followed by a CSF layer. The mask is then replaced in a vacuum and a tantalum layer is deposited using thermal evaporation. The vacuum chamber is vented and the device is packaged using a glass cover, desiccant, and UV curable epoxy. ' The characteristics of the 〇LED sample can be described by measuring the following data, ("current-voltage (ΐ-v) curve, (2) electroluminescence intensity versus voltage, and electroluminescence spectrum versus voltage. All three above Measurements are performed at the same time and are controlled by a computer. The unit's electrical efficiency is determined by dividing the electroluminescence intensity of the LED by the current required to operate the device. It is Cd/A. Multiply the current efficiency by pi(7t) and divide by the operating voltage to obtain the power efficiency. The unit is lm/w. Table 4 shows the information of the farm. 145481.doc -72- 201109291 Table 4. Device Performance Example CIE (, y) Voltage (V) CE (cd/A) EQE (%) PE (!m/W) Life Test Current Density (mA/cm2) Life Test Luminous Intensity (nits) Original T50 (h) Lifetime forecast period T50@1000 nits Comparative example D-1 0.136, 0.126 4.4 5.7 5.5 -_ — 4.1 127 6686 455 11503 Comparative example D-2 0.136, 0.123 4.4 5.8 5.7 4.2 129 6572 450 11048 Example 8- 1 0.136, 0.121 4.4 5.S 5.8 4.2 128 6669 555 13970 Example 8-2 0.136, 0.124 4.3 5. 9 5.7 4.2 130 6599 590 14587 Example 9-1 0.136, 0.121 4.3 5.8 5.8 4.2 127 6475 940 22503 Example 9-2 0.136, 0.121 4.4 5.8 5.8 4.2 124 6254 955 21551 Comparative example E-1 0.136, 0.123 4.4 6.1 6.0 4.3 124 6670 400 10071 Comparative Example E-2 0.135, 0.124 4.4 5.8 5.6 4.1 131 7006 388 10620 Example 10-1 0.136, 0.121 4.4 6.0 5.9 4.2 123 6403 622 14610 Example 10-2 0.136, 0.118 4.4 5.7 5.8 4.1 121 6050 675 14398 *All data is @ 1000 nits, CE=current efficiency; ciEx and CIEy are based on the X and y color coordinates of the CIE·chromaticity diagram (c〇mmissi〇n

Internationale de L Eel airage ’ 1931). The original T50 is the time (in hours) at which the device reaches half of the initial luminous intensity, which is given at the lifetime test luminous intensity. The predicted lifetime of T5 tethers at 1 〇〇〇 nits is predicted using an acceleration factor 丨7. It can be seen that the right body material of the present invention having the deuteration of the present invention greatly increases the service life of the device while maintaining other device characteristics. Table 5 below shows the average life expectancy for different host materials. -73- 145481.doc 201109291

Table 5. Apparatus lifetime life material average life expectancy period T50@1000 nits, comparing compounds A 11,276 and 10,346 H8 22,027 H10 14,504 H11 14,279 in hours Example 11 and Comparative Example F This example shows a device with an electroactive layer The production and performance of the electroactive layer has a green dopant, a first host material of Formula I, and a second host material. The electron transport material is ET2, as explained below.

The apparatus has the following structure on a glass substrate: Anode = ITO (50 nm) Hole injection layer = HIJ2, (50 nm), which is an aqueous dispersion of a conductive polymer and a fluorinated polymerized acid. Such materials are described in, for example, the published U.S. Patent Application Serial Nos. 2004/0102577, 2004/0127637, 2005/0205 860, and PCT Application No. WO 2009/018009. Hole transport layer = polymer P1 (20 nm) electroactive layer = 82.5 : 5 : 12.5 of the first host material: second body material 145481.doc -74- 201109291 material: dopant (60 nm), as shown Electron transport layer shown in 6 = ET2 (10 nm) Cathode = CsF / Al (0.7 / 100 nm) Table 6. Device electroactive layer example First host material Second host material dopant Comparative example F Comparative compound A D12 D6 Example 11 H8 D12 D6 Examples 8-10 describe the fabrication and evaluation of the device. Table 7 shows the information for this device. Table 7. Device Performance Example CIE (x, y) Voltage (V) CE (cd/A) EQE (%) PE, (lm/W) Life Test Current Density (mA/cm2) Life Test Luminous Intensity (nits) Original T50 (8) Lifetime prediction period T50 @1000 nits Comparative example F 0.265, 0.649 4.8 26.1 7.2 17.1 134 29167 1800 557,000 Example 11 0.257, 0.650 4.7 25.4 7.1 16.9 127 27232 4160 1,144,800 *All information is @1000 nits, ACE=current efficiency CIEx and CIEy are based on the X and y color coordinates of the CIE chromaticity diagram (Commission Internationale de L'Ecl air age, 1931). The original T50 is the time (in hours) at which the device reaches half of the initial illuminance, which is given at the lifetime test luminescence intensity. The predicted lifetime of the T50 at 1 000 nits is predicted using an acceleration factor of 1.7. From this, it can be seen that with the deuterated host material of the present invention, the service life of the device can be greatly increased while maintaining other device characteristics. The predicted lifetime is more than doubled, even for non-deuterated second host materials. It should be noted that the activities described above in the general description or examples are 145481.doc -75-201109291 to be unnecessary&apos; and in addition to one or more other activities. The order of these activities. It is not necessary that a part of the specific activities may be performed other than those described, and that the order of activities listed is not necessarily performed. In the above description, the concept of a specific embodiment has been described. However, it will be understood by those skilled in the art that various modifications and changes can be made without departing from the scope of the invention. Therefore, the specification and drawings are to be regarded as illustrative and not restrictive, and all such modifications are within the scope of the invention. Benefits, other advantages, and problem resolutions for particular embodiments have been described above. 'However, benefits, advantages, problem solutions, and any features that may create or highlight any of these benefits, benefits, or problem solutions' are not to be construed as a critical or essential feature of any or all patent claims. It is to be understood that the particular features of the present invention, which are described in the above and the various embodiments of Instead, the features of the invention as set forth in the Detailed Description of the Invention may be provided separately or in any sub-combination. Moreover, the relevant numerical values described in the specification refer to each value within the range. BRIEF DESCRIPTION OF THE DRAWINGS [0007] The specific embodiments are described in the accompanying drawings in the claims 1 includes an illustration of an example of an organic electronic device; FIG. 2 includes a 1H NMR spectrum of a comparative compound of Comparative Example A; 145481.doc -76-201109291 FIG. 3 includes an NMR spectrum of a deuterated compound of Example 1; A mass spectrum of the gasified compound of Example 1 was included. Those skilled in the art will understand that the elements in the figures are not drawn to scale for the sake of clarity and clarity. For example, the dimensions of some of the items in the drawings may be exaggerated to enhance the understanding of the specific embodiments. [Main component symbol description] 100 organic electronic device 110 first electrical contact layer/anode layer 120 hole injection layer 130 hole transport layer 140 electroactive layer 150 electron transport layer 160 second electrical contact layer/cathode layer 145481.doc - 77-

Claims (1)

201109291 VII. Patent application scope: 1. A substituted aryl hydrazine compound having the chemical formula I: R2 R3 R4 Ar2—Ar4 Formula I R1 wherein: R1 to R8 are the same or different at each occurrence and are selected from the group consisting of H, D, alkyl, alkoxy, aryl, aryloxy, decane and stone. a group consisting of: the Ar1 and the Ar2 are the same or different, and are selected from the group consisting of aryl groups; and the Ar3 and Ar4 are the same or different, and are selected from the group consisting of H, D and aryl. a group of groups; wherein the compound has at least one D. 2. A compound as claimed in claim 1 which is at least 10% deuterated. 3. The compound of claim 1, which is at least 50% deuterated. 4. A compound as claimed in claim 1 which is 100% deuterated. The compound of claim 1, wherein the at least one D 201109291 is a mono-substituent (group) on an aromatic ring. 6. The compound of claim 1, wherein at least one of R1 to R8 is D. 7. The compound of claim 1, wherein R1 to R8 are selected from the group consisting of hydrazine and D. 8. The compound of claim 1, wherein at least one of Ri to R8 is selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a decane, and a group The remainder of 〇 to 1^ is selected from Η and 〇. 9. The compound of claim 8, wherein R2 is selected from the group consisting of an alkyl group and an aryl group. 10. A compound according to the scope of the patent application, wherein at least one of Ari to Ar4 is a deuterated aryl group. 11. The compound of claim 1, wherein the Ar3 and Ar4 are selected from the group consisting of D and a gasified aryl group. 1 2. The compound of claim 1, wherein the Ari to Ar4 system is at least 20% vaporized. 13. The compound of claim 1, wherein the Ari and Ar2 are selected from the group consisting of a phenyl group, a naphthyl group, a phenanthryl group, an anthracenyl group, and their deuteration. a group of objects. 14. The compound of claim 5, wherein the Ar3 and Ar4 are selected from the group consisting of phenyl, naphthyl, phenanthryl, anthracenyl, and phenylnaphthyl ( Phenylnaphthylene), naphthylphenylene 'a group of deuterated derivatives and groups of formulas: 145481.doc 201109291 Chemical formula π wherein: R9 is the same or different at each occurrence, and is selected from the group consisting of ruthenium, D, alkyl, alkoxy, decane, and decyl, or may be attached to adjacent R9 Collected together to form an aromatic ring; and m is the same or different at each occurrence, and is an integer from 1 to 6. 15. The compound of claim 1, wherein the Ar3 and Ar4 are selected from the group consisting of phenyl, naphthyl, phenylnaphthylene, naphthylphenylene, a group of deuterated derivatives and groups having a chemical formula: R9 R9 wherein: R9 is the same or different at each occurrence, and is selected from the group consisting of hydrazine, d, alkyl, alkoxy, decane, and decyl, or may be attached to adjacent R9 Collected together to form an aromatic ring; and m is the same or different at each occurrence, and is an integer from 1 to 6. 145481.doc 201109291. The compound of claim 3, wherein at least one of Afi to a is a heteroaryl group. 17. The compound of claim 16, wherein the heteroaryl group is selected from the group consisting of carbazole, benzofuran, dibenzofuran, and the like. The compound according to item 1, wherein at least one of Ri to R8 is D, and at least one of Ari to Ar4 is a deuterated aryl group. I9· A compound selected from the group consisting of the intermediate VIII to the intermediate m and the intermediate to the H14. 20. An organic t-sub-device comprising a first electrical connection (four), a second electrical contact layer, and at least an active layer therebetween, wherein the active layer comprises a substituted aryl ruthenium compound having a chemical formula · R2 R3 R4 Ar2 - Ar4 Formula I R5 wherein: R to R are the same or different at each occurrence, and are selected from the group consisting of H, D, phenotype, alkoxy, aryl, aryloxy, shi oxi a group consisting of a decyl group; Ar and Ar2 are the same or different, and are selected from the group consisting of aryl groups 145481.doc 201109291; and Ar and Ar are the same or different, and are selected from η a group consisting of ρ and an aryl group; wherein the compound has at least one D. 21. 22. The device of claim 20, wherein the active layer is an electroactive layer, further comprising an electroactive dopant compound. The device of claim 20, wherein the active layer is an electroactive layer and consists essentially of a compound of formula I and an electroactive dopant compound. The device of claim 20, wherein the active layer is an electroactive layer and consists essentially of a compound of formula I, a second host material, and an electroactive dopant compound. The apparatus of claim 21, wherein the electroluminescence &amp; system L is a group of freely substituted amino groups (amin〇 substituted chrysenes) and substituted amine groups. The device of claim 23, further comprising a hole injection layer between the first electrical contact layer and the active layer. The device of claim 25, wherein the hole injection layer comprises: a conductive polymer and at least one fluorinated acid polymer. 145481.doc