TW201109291A

TW201109291A - Deuterated compounds for electronic applications

Info

Publication number: TW201109291A
Application number: TW098144112A
Authority: TW
Inventors: Daniel David Lecloux; Adam Fennimore; Wei-Ying Gao; Nora Sabina Radu; Weishi Wu; Vsevolod Rostovtsev; Michael Henry Howard Jr; Hong Meng; yu-long Shen; Jeffrey A Merlo; Eric Maurice Smith
Original assignee: Du Pont
Priority date: 2009-09-03
Filing date: 2009-12-21
Publication date: 2011-03-16
Also published as: CN102482570A; JP2013503860A; JP5714014B2; WO2011028216A1; CN104370686A; EP2473580A4; EP2473580A1; CN102482570B; KR20120058602A; KR20150036725A

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 六、發明說明：【發明所屬之技術領域】本發明係關於至少部分氘化之蒽衍生物化合物。本發明亦關於電子裝置，其内的活性層包括此類的化合物。 [相關申請案資料] 本專利申請案依據35 XJ.S.C. § 119(e)主張於2009年2月 27曰申睛的美國臨時專利申請案第61/156，181號、於2〇〇9 年5月19曰申請的美國臨時專利申請案第61/179,4〇7號及於 2009年9月3日申請的美國臨時專利申請案第61/239,574號之優先權，其全部皆以引用方式完整併入本說明書中。【先前技術】發光之有機電子裝置（例如，構成顯示器的發光二極體）存在於許多不同種類的電子設備中。在所有這類裝置中，一有機活性層係夾置於兩個電接觸層間。該等電接觸層中之至少一者為可透光的，以致於光可通過該電接觸層。在施加橫跨該兩個電接觸層之電力時，該有機活性層即發光穿過該可透光電接觸層。眾所皆知，有機電致發光化合物用以做為發光二極體中的活性化合物。已知簡單的有機分子，如葱…塞二唾衍生物及香豆素衍生物可顯示電致發光特性。亦可使用半導體共輛聚合物用作電致發光化合物，其已揭示在例如美^ 利案第5,247，190號、美國專利案第5，烟，1〇9號及已公開之歐洲專利申請案第443 861號中。在許多情況中，該電致發光化合物在一主體材料中係作為一摻雜劑。 14548I.doc 201109291 對於用於電子裝置的新穎材料有持續的需求。【發明内容】本發明提供一種取代芳基（aryl_substituted)蒽，其具有至少一個氘取代基。本發明亦提供一種具有包括上述化合物之活性層的電子裝置。本發明進一步提供一種電活性組成物，其包括（a)具有至少一個氘取代基的一取代芳基蒽’以及（b)能夠電致發光的一電活性摻雜劑’其發射波長最大值介於380 nm及750 nm 之間。【實施方式】本文所揭示的各種態樣及具體實施例皆為範例性，而並非為限制拘束。在研讀本說明書後，熟習技藝者應理解在不脫離本發明之範疇内，本發明仍存有其它態樣及具體實施例》任何一個或多個具體實施例之其它特徵及益處將於下文針對本發明的詳細描述及申請專利範圍中顯而易見。本發明的詳細描述首先著重在解釋術語的定義和闡明，接著依序說明気化化合物、電子裝置，最後為實例說明。 1.術s吾的定義和闡明在說明下述之具體實施例的細節之前，定義或闡明一些術語。本文所使用的術語「脂族環」係意指一不具有非定域冗電子（delocalized pi electron)之環狀基。在一些具體實施 145481.doc 201109291 例中’該脂族環不是為不飽和性的。在某些具體實施例中，該環具有一個雙鍵或參鍵。 4标語「烷氧基」係指R〇_基團’其中R係烷基。術語「烧基」意指一衍生自具有一個連結點之脂族烴的基團，以及該烷基包括直鏈基、支鏈基及環狀基。上述術語意欲包括雜烷基。術語「烴烷基」係指一不具有雜原子的烧基基團。術§吾「氣化烧基」係一具有至少一個可用Η 被D取代的烴烷基。在某些具體實施例中，一烷基基團具有1-20個碳原子。術支鏈烷基」係指一具有至少一個二級碳或三級碳的烷基基團。術語「二級烷基」係指一具有一個二級碳原子的支鏈烷基基團。術語「三級烷基」係指一具有一個三級碳原子的支鏈烷基基團。在某些實施例中，該支鏈烷基基團係經由一二級或三級碳結合。術π芳基」意、指一衍生自具有一個連結點之芳族煙的基團。術語「芳族化合物」意指一包括至少一個不飽和環狀基之有機化合物，該不飽和環狀基具有非定域兀電子 (delocalized pi eleetron)。上述術語意旨包括雜芳基。術語「烴芳基」意指在該環中不具有雜原子之芳族化合物。術語「芳基」包括具有單環及多環的基團，且此多環可經由一單鍵結合或經稠合為-體。術語「氘化芳基」係指一具有至少一個直接鏈結至芳基的可用取代的芳^其團。術語「伸芳基㈣ene)」意旨在指—衍生自具有二連結點之芳族煙的基團。在—些具體實施例中，—芳基基 145481.doc 201109291 團具有3-60個碳原子。術語「芳氧基」係指RO-基團，其中R係芳基。術語「化合物」意旨在指一未帶電荷的物質，其由分子組成’該等分子進一步由原子所組成，其中該等原子無法用物理方法为離。S片s吾「鄰接於」係用以提及一裝置中的層時，該片語「鄰接於」不必然表示一層緊鄰於另一層。另一方面，月語「相鄰R基（adjaeent R gr〇ups)」用以提及在一化學式中彼此緊鄰之尺基（亦即，在以鍵所聯集之原子上的R基）。術語「氣化」意指至少-個Η已被D取代。所存在的說比天然豐度含量（natural abundance level)多出至少丨〇〇倍。化合物X的一「氘化衍生物」與化合物χ具有相同的結構，但是具有至少一個取代Η的d。術語「摻雜劑」意指位於包含一主體材料之一層内的一材料，與不存有此種材料之層的電子特性或輻射發射、接收或遽波之波長相比，該材料改變該層之電發射、接收錢波的目標波長。 4射當術語「.電活性」係指一層或材料時，該術語「電活意指呈現電子或電輻射特性的—層或材料。在一電子 :二’ 一電活性材料電性上有助於該裝置的操作。電活 =之實例包括但不偈限於傳導、注入、= 何之材料（其中咭雷 ^電或在接”射時呈：：以疋電子或電洞)’或者發出輕射活性材料田一 _電洞對之濃度變化之材料。非之貫例包括但不侷限於平坦化材料、絕緣材料及 145481.doc 201109291 環境障壁材料。子首「雜原子（hetero)」表示已經以一不同原子取代一或多個碳原子。在一些具體實施例中，不同原子係n、〇或S。術5吾「主體材料」意指一添加有摻雜劑的材料。該主體材料可具有或不具有電子特性，或發射、接收或渡波轄射的能力。在一些具體實施例中，所存在的主體材料具有較南的濃度。術語「層」及術語「膜」可替換地使用，其係指一覆蓋所需區域的塗覆。上述術語並未受限於大小。該區域可大至包含整個裝置或小至一特定功能性區域（例如，實際視覺顯或小至一單次像素。1藉由任何習知沉積技術（例如，氣相沉積、液相沉積（連續及不連續技術）及熱轉印）來形成層及膜。連續沉積技術包括但不侷限於旋轉塗佈喊 _t|ng)、凹板塗佈（gravure c〇ating)、簾塗佈 _ting)、浸塗（dip c〇ating)、狹縫模具式塗佈（_士 coating)、噴塗（spray c〇ating)及連續式噴嘴塗佈 (continuous nozzle c〇ating)。不連續沉積技術包括但不侷限於喷墨印刷（ink jet printing)、凹版印刷㈣咖 printmg)及網版印刷（screen pHnting)。術語「有機電子裝置」或有時候僅為「電子裝置」惫指 -包括-或多個有機半導體層3 戈半導體材料的冑置。除非另行指示’所有基團可以是取代的或未取代的。在一此且體實施例中，該等取代基係選自由0、齒化物、烧基y烧 145481.doc 201109291 氧基、芳基、芳氧基、氰基及NR2所組成之群，其中R係院基或芳基。除非另外加以定義，否則此處所用的全部技術及科學術語與熟悉本發明所屬之技術的專業人士通常所理解的含義相同。儘官類似或等效於此處所說明之方法及材料可用於實踐或測試本發明，但下文說明適當的方法及材料。全部 a開案、專利申凊案、專利及此處提及的其他參考文獻以提及方式全部併人本文中m矛盾的情況下，以本說明書為準’包括定義在内。此外’材料、方法與實例僅係說明性質，而非為限制性。全文從頭到尾使用國際純化學暨應用化學聯合會 (IUPAC)編號系統，其中來自元素週期表的族皆從左至右編號作 1-18(CRC Handbook of Chemistry —，第 81 版，2000年）。 2.氘化化合物該新穎的氘化化合物係-具有至少-個D的取代芳基蒽。在-些具體實施例中’該化合物係至少1〇%氘化。二係意謂至少難的取代。在一些具體實施例中，合物係至少20%氘化；在—此且 " 2具體貫施例中，該化合物係至少錢化；在—些具體實施例中，該化合物係至^ 4崎化；在一些具體實施例中，該化合物係至少50。二化；在一些具體實施例中，該化合物係至少60%氛化 -些具體實施射，該化合物係至少7Q。錢化；在—此且體實施例中’該化合物係至少8〇%氣化；在一些具體實施 145481.doc 201109291 例I，該化合物係至少9〇%氘化。在—些具體實施例中， 3亥4化合物係1 00%氛化。在—具體實施例中，該氘化化合物具有化學式工： R2 R3201109291 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

R4R4

Ar2—Αι4 化學式I R5 其中： R1至R8在每次出現時係相同或不同的，及係選自由Η ' D、烷基、烷氧基、芳基、芳氧基、矽氧烷及矽烷基所組成之群；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及Ar2係相同或不同的，及係選自由芳基基團所組成之群；以及Ar1 and Ar2 are the same or different, and are selected from the group consisting of aryl groups;

Ar及Ar4係相同或不同的，及係選自由H、D及芳基基團所組成之群；其中該化合物具有至少一個D。在化學式I的一些具體實施例中，該至少一個D係位在一芳環上的取代基（基團）上。在一些具體實施例中，該取代基（基團）係選自烷基及芳基。在化學式I的一些具體實施例中，R1至R8之至少一者係 D。在一些具體實施例中，以至以之至少二者係d。在某一具體實施例中，至少三者係D ;在一些具體實施例中， 145481.doc •9- 201109291 至少四者係D;在一些具體實施例中， -些具體實施例中，至少六者係D;在-些具:實施：中，至少七者係D。在一些具體實施例中，…至尺8全部皆係D。在一些具體實施例中，！^至！^係選自H&D。在一些且體實施例中，r^r8之其中一個係D及其它七個係h 4 -些具體實施例中，Ri^之其中兩個係D及其它六個係 Η。在一些具體實施例中，…至尺8之其中三個係D及其它五個係Η。在一些具體實施例令，尺丨至尺8之其中四個係〇及其它四個係Η。在一些具體實施例中，R〗至R8之其中五個係D及其它三個係Ηβ在一些具體實施例中，…至汉8之其中8六個係D及其它兩個係η。在一些具體實施例中，^ 至R8之其中七個係D及另一個係η。在一些具體實施例中，R1至R8之全部八個皆係D。在-些具體實施例中，R丨至r8之至少一者係選自烷基、烧氧基、芳&、芳氧基、石夕氧烧及石夕⑽，及r^r8二其餘部分係選自i^D。在—些具體實施例巾，以選自燒基、烧氧基、芳基、芳氧基、石夕氧烧及石夕烧基。在一些具邊實施2例中’ R2係選***基及芳基。在-些具體實施例中，R:係選自氘化烷基及氘化芳基。在一些具體實施例中，R2係選自具有至少1〇%氘化作用之氘化芳基。在一些具體實施例中，R2係選自具有至少2G%氣化作用之氛化芳基；在一些具體實施例中，其具有至少3〇%氘化作用；在某些具體實施例中，其具有至少4〇%氘化作用；在一此具 145481.doc 201109291 體實施例中，其具有至少·氛化作用；在—些具體實施例中’其具有至少6G%1化作用；在—些具體實施例中，其具有至少70%氘化作用；在一些具體實施例中，其具有至夕80 /〇氘化作用；在一些具體實施例巾其具有至少㈣氣化作用。在—些具體實施例中，尺2係選自具有醫。氣化作用之氘化芳基。在化學式1的一些具體實施例中，Ar1至Ar4之至少一者係氘化芳基。在一些具體實施例中，Ar3及A〆係選自d及氘化芳基。在化學式I的一些具體實施例中，八—至^4係至少ι〇%氘化的。在化學式I的—些具體實施例中，Afl至A〆係至少 20 /〇氘化的，在一些具體實施例中至少3氘化；在一些具體實施例中’ i少4〇%氘化；在一些具體實施例中，至少50%氛化；在一些具體實施例中，至少6〇%氣化；在一些具體實施例中，至少爲氛化；在—些具體實施例中，至少80〇/〇氘化；在一些具體實施例中，至少9〇%氘化；在一些具體實施例中，為100%氘化的。在一些具體實施例中，化學式〗的化合物係至少1〇%氘化的；在一些具體實施例中，至少2〇%氘化；在一些具體實施例中，至少30%氘化；在一些具體實施例中，至少4〇% 氘化；在一些具體實施例中，至少5〇%氘化；在—些具體貫施例中，至少60〇/〇氘化；在一些具體實施例中，至少 7〇 /〇氛化’在一些具體實施例中，至少80%說化；在一些具體實施例中’至少9〇%氛化。在一些具體實施例中，該 145481.doc •11· 201109291 化合物係100%氘化。在一些具體實施例中，Ar1及Ar2係選自由苯基 (phenyl)、萘基（naphthyl)、菲基（phenanthryl)、蒽基 (anthracenyl)及它們的沉化衍生物所組成之群。在一些具體實施例中，Ar1及Ar2係選自由苯基、萘基及它們的氘化衍生物所組成之群。在一些具體實施例中，Ar3及Ar4係選自由苯基 (phenyl)、萘基（naphthyl)、菲基（phenanthryG、蒽基 (anthracenyl)、苯伸萘基（phenylnaphthylene)、萘伸苯基 (naphthylphenylene)、它們的氣化衍生物及具有化學式II之基所組成之群：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:

其中： R9在每次出現時係相同或不同的，及係選自由Η、D、烷基、烷氧基、矽氧烷及矽烷基所組成之群；或可將相鄰R9基聯集在一起以形成一芳族環；以及 m在每次出現時係相同或不同的及係1至6之整數。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.

在一些具體實施例中，Ar3及Ar4係選自由苯基（phenyl)、萘基（naphthyl)、苯伸萘基（phenylnaphthylene)、萘伸苯基 (naphthylphenylene)、它們的氣化衍生物及具有化學式III 145481.doc -12- 201109291 之基所組成之群：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:

其中Rh係如上化學式„所定義般。在一些具體中，m係1至3的整數。 *-些具體貫施例中，Arl至Ar4之至少—者係—雜芳基基團。在一些具體實施例中，該雜芳基基團係氘化的。2 些具體貫施例中，该雜芳基基團係至少丨〇0/。氘化的在 -些具體實施例中，至少20%氣化；在一些具體實施例中，至少30%氘化；在一些具體實施例中，至少仰％氘化；在一些具體實施例中，至少50%氘化；在一些具體= 施例中，至少60%氘化；在一些具體實施例中，至少氘化；在一些具體實施例中，至少80%氘化；在一些具體貫施例中，至少90%氘化。在一些具體實施例中，該雜芳基基團係100%氘化的。在一些具體實施例中，該雜芳基基團係選自由咔唑（carbazole)、苯并呋喃（benz〇furan)、二苯并呋喃（dibenzofuran)及它們的氘化衍生物。在化學式I的一些具體實施例中，r〗至R8之至少—者係 D，且Ar1至Ar4之至少一者係氘化芳基。在一些具體實施例中，該化合物係至少10%氘化的。在一些具體實施例中’該化合物係至少20%氘化的；在一些具體實施例中，至少30%氘化；在一些具體實施例中，至少4〇。/。氘化；在 145481.doc -13· 201109291 一些具體實施例中，至少50%氘化；在一些具體實施例中，至少60%氘化；在一些具體實施例中，至少70%氘化；在一些具體實施例中，至少80°/。氘化；在一些具體實施例中，至少90%氘化。在一些具體實施例中，該化合物係100%氘化。具有化學式I之化合物的一些非限定實例包括以下化合物H1至化合物H14 : 化合物H1 :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:

其中，x+y+z+n=l-26 化合物H2 :Wherein x+y+z+n=l-26 compound H2:

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

其中，x+y+z+p+n+r=l-32 化合物H4 :Wherein x+y+z+p+n+r=l-32 compound H4 :

其中，x+y+z+p+n=l-18 化合物H5 :Wherein x+y+z+p+n=l-18 compound H5:

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

其中，x+y+z+n=l-18 化合物H7 :Wherein x+y+z+n=l-18 compound H7:

其中，x+y+z+p+n=l-28 化合物H8 :Wherein x+y+z+p+n=l-28 compound H8:

化合物H9 :Compound H9:

145481.doc -16- 201109291 化合物H10 :145481.doc -16- 201109291 Compound H10:

化合物Hll :Compound Hll:

化合物H12 :Compound H12:

化合物H13 :Compound H13:

145481.doc •17- 201109291145481.doc •17- 201109291

可由已知的偶聯反應及取代反應來製備新化合物的非氘化類似物。接著以一類似的方式，使用氘化先質材料製備新的氣化化合物；或者更一般而言，在如三氯化銘或乙氣化紹之路易斯酸氫氣交換催化劑（Lewis acid H/D exchange catalyst)或在如CF3COOD、DC1等之酸存在的情況中，以氣化溶劑，如六氣苯（d6-benzene)，處理該非氣化化合物。於實例中說明實例性製備方法。由NMR分析及質譜測定法決定氘化作用鉍程度，如大氣壓力固態分析探針質譜測定法（AS ΑΡ-MS)。可從商業來源購得全氘化或部分氘化芳族化合物或烷基（alky)化合物的原料，或者可使用已知方法獲得。如下列出上述此種方法的某些實例：a) Hiroyoshi Esaki 、 Fumiyo Aoki 、 Miho Umemura 、 Masatsugu Kato、Tomohiro Maegawa、Yasunari Monguchi 及Hironao Saj iki刊載於〈歐洲化學期刊Chem. Eur. J.>的「Efficient H/D Exchange Reactions of Alkyl_SubstitutedNon-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年，第 13期，第 4052-4063 頁；b) GUO Qiao-Xia、SHEN Bao-Jian、GUO Hai-Qing、TAKAHASHI 145481.doc -18 · 201109291Benzene 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刊載於〈中國化學期刊c/n’wese .Jowma/ 〇/Tamotsu is published in the Chinese chemical journal c/n’wese.Jowma/ 〇/

少〉的 r Aromatic H/D Exchange Reaction Catalyzed by Groups 5 and 6 Metal Chlorides」 2005年，第 23期，第 341-344 頁；c) Richard J. Watts、Shlomo Efrima及 Horia Metiu刊載於〈美國化學學會言志J. C/ze/w. Soc.〉的「A novel deuterium effect on dual charge-transfer and ligand-field emission of the cis-dichlorobis (2,2'-bipyridine) iridium (Ill)ion」1979 年，第 101(10)期，第 2742-2743 頁；d) Carmen Boix 及 Martyn Poliakoff 刊載於「Tetrahedron Letters」的「Efficient H-D Exchange of Aromatic Compounds in Near-Critical D20 Catalysed by a Polymer-Supported Sulphonic Acid」1999年，第 40卷，第 4433-4436 頁；e)美國專利案 US 3849458 ; f) Hironao Sajiki、Fumiyo Aoki、 Hiroyoshi Esaki、Tomohiro Maegawa及 Kosaku Hirota刊載於〈有機化學期刊Or容.的「Efficient C-H/C-D Exchange Reaction on the Alkyl Side Chain of Aromatic Compounds Using Heterogeneous Pd/C in D20」2004年，第6卷第9期，第1485-1487頁。可使用液相沉積技術將本文所述之化合物形成為薄膜。出乎意料之外，與類似的非氘化化合物相比，此等化合物的特性大幅度改善。若電子裝置包括具有本文所述之化合物的一活性層，則其具有大幅度改善的使用期限。此外，除了使用期限可延長之外’亦會達到高量子效率及良好的色彩飽和度。另外’本文所述之免化化合物比非氣化類似 145481.doc •19· 201109291 物八有更而的空氣穩定性（air t〇lerance)。此可導致在製備及純化該等材料’及在使用該等材料形成電子裝置的過程中具有更大的製程容差。 3·電子裝置有機電子裝置（可以因具有包括在此所述之電致發光材料的一或多層而受益）包括但不限於，（1)將電能轉換成輻射能之裝置（例如，發光二極體、發光二極體顯示器或二極體雷射）；（2)以電子方法偵測信號之裝置（例如，光偵測器光導電池、光敏電阻器、光控開關、光電晶體、光電官、紅外線偵測器）；（3)將輻射能轉換成電能之裝置（如，光伏打裝置或太陽能電池）；q及（4)包括—或多個電子組件之裝置（例如，電晶體或二極體），其中該（等）電子組件包括一或多個有機半導體層。圖1顯示一有機電子裝置結構之說明。該裝置100具有一第一電接觸層，陽極層110及一第二電接觸層，陰極層 160’及在其等之間的一電活性層14〇。一電洞注入層⑶ 可位在該陽極旁邊。-電洞傳輸層130可位在該電洞注入層旁邊，該電洞傳輸層包括電洞傳輸材料。一電子傳輸層 1 5 0可位在§玄陰極旁邊’該雷早值於恳6 &而电千得輸層包括電子傳輪材料。裝置可使用-或多個緊鄰該陽極11〇之額外電洞注入或電洞傳輸層(未顯示)及/或一或多個緊鄰該陰極16〇之額外電子注入或電子傳輸層（未顯示）。層120至層150個別地及統稱為活性層。在-具體實施例中，不㈣層所具有的厚度範圍如下： 14548 丨.doc •20· 201109291 陽極層110為500-5000 A，在一具體實施例中為1〇〇〇_2〇〇〇入’電洞注入層120為50-2000 A，在一具體實施例中為 200-1000 A;電洞傳輸層130為5〇·2〇〇〇 A，在一具體實施例中為200-1000 a ;電活性層14〇為1〇 2〇〇〇 a，在一具體貫施例中為100-1000 a ;電子傳輸層15〇為5〇2〇〇〇 A，在一具體實施例中為100·1000 A;陰極層16〇為2〇〇1〇〇〇〇 A，在一具體實施例中為300_5〇〇〇 A。每一層之相對厚度可影響電子-電洞再結合區在裝置中的位置，&因而影響該裝置之發射光譜。層厚度的期望比率將會取決於所用之材料的確切性質。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.

取決於裝置100的應用，該電活性層14〇可為一由外施電壓啟動的發光層(例如’在一發光二極體中或發光電化電池中）或為在具有或不具有一外施偏壓下回應以韓射能量及產生信號之材料層（例如，在一光侦測器中卜光偵測器之實例包括光導電池、光敏電阻器、光控開關、光電晶體、光電管及光伏打電池，此等術語描述於John —所箸（Electronics and Nucleonics Dicti刪 W 頁及第 476 頁（McGraw-HUUnc.出版，1966年）。本文描述之一或多個新氘化材料可出現在一裝置之一或多個活性層中。該等氛化材料可單獨使用，或者與非氛化材料結合使用。在-些具體實施例中，該等新氛化化合物有益於用作層 130中的電洞傳輸材料。在-些具體實施例中，至少一個額外層包括m材料。在—些具體實施例中，該額外 I45481.doc -21 - 201109291 層係電/同注入層12〇。在一些具體實施例令，該額外層係電活!·生層14G °在-某些具體實施例巾，該額外層係電子傳輸層150。在一些具體實施例中，該等新說化化合物有益於用作電，舌f生層140中之電活性摻雜劑材料的主體材料。在一些具體實施例中，亦氘化發射材料。在一些具體實施财，：少-個額外層包括一氛化材料。在一些具體實施例中，該額外層係電洞注入層12◦。在—些具體實施例中，該額外層係電洞傳輸層13〇。在—些具體實施例中，該額外層係電子傳輸層150。在-些具體實施例中，該等新氣化化合物有益於用作層 150中的電子傳輸材料。在-些具體實施例令，至少一個額外層包括Ή材料。在—些具體實施例中該額外層係電洞注入層12〇。在一些具體實施 _ _ ^ τ 該額外層係電洞傳輸層130。在一些具體實施例中層⑷。 5玄額外層係電活性氘化材料，其可電活性層及電子在一些具體實施例中，一電子裝置具有存在於選自由電洞注入層、電洞傳輸層、傳輸層所組成之群之層的任何組合中。在一些具體實施例中，處理過程或改善功能性。料。在一些具體貫施例中料。在一些具體實施例中化材料構成。 Η Α巧任何或所有此等層可包未 ’所有的有機裝置層包本 ’所有的有機裝置層基4 •22· 145481.doc 201109291 a·電活性層冬式1的新氘化化合物有益於用作電活性層140中之電 f乜雜刈材料的主體材料。該等化合物可單獨使用，或者與第—主體材料結合使用。該等新1化化合物可用作具有任何發射顏色之摻雜劑的主體。在一些具體實施例中，該等新穎氣化化合物可㈣、綠色或藍色發射材料的主體。在一些具體實施例中，該電活性層基本上由一具有化學式I之主體材料和一或多個電活性摻雜劑構成。在一些具體實施例中’肖電活性層基本上由—具有化學式r之第一主體材料、—第二主體材料和—電活性摻雜劑構成。第二主體材料之實例包括但不限於，筷（chrysenes)、菲 (Phenanthrenes)、聯伸三苯（triphenylenes)、啡啉 (phenanthrolines)、萘（naphthalenes)、蒽（anthracenes)、喹啉（quinolines)、異啥琳(isoquinolines)、七号琳(quin〇xaHnes)、苯吡啶（phenylpyridines)、苯并二呋喃（benz〇difurans)及金屬喹啉複合物（metal quinolinate complexes)。電活性組成物中所存在之摻雜劑的量一般而言佔該組成物總重量3-20 wt%(重量百分比）；在一些具體實施例中，佔5-15 wt%。當存在一第二主體材料時，具有化學式工之第一主體材料與遠第一主體材料的比率通常在ι:2〇到20:1 的範圍中；在一些具體實施例中，為5:15到15:5。在一些具體實施例中’具有化學式I之第一主體材料占總主體材料至少50 wt%，在一些具體實施例中，占至少wt%。在一些具體實施例中，該第二主體材料具有化學式IV : 145481.doc -23· 201109291Depending 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在每次出現時係相同或不同的’及係一芳基基團； Q 係選自由多原子價芳基基團所組成之群，以及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 係選自由（CR，）a、SiR2、S、S02、PR、p〇、p〇2、 BR及R所組成之群； R 在每次出現時係相同或不同的’及係選自由烷基及芳基所組成之群； R'在每次出現時係相同或不同的’及係選自由η及烷基所組成之群； a 係1至6的整數；以及 η 係0至6的整數。雖然η可具有從〇至6中的一值，但應理解，對於一些q基而言，η的值受限於該基的化學性質。在一些具體實施: 中，11係0或1。在化學式IV的一些具體實施例中，可腺 J將相鄰Ar基聯集一起以形成環，如咔唑。在化學式ιν φ 宁’「相鄰」意謂基鍵結至相同的N。在一些具體貫施例中，Ar係獨立 ’立地選自由笨 145481.doc -24- 201109291 (phenyl)、聯苯（biphenyl)、聯三苯（terphenyl)、聯四苯 (quaterphenyl)、萘基（naphthyl)、菲基（phenanthryl)、萘苯基（naphthylphenyl)及菲苯基（phenanthrylphenyl)所組成之群。亦可使用高於聯四苯（具有5_10個苯環）的類似物。在一些具體實施例中，Ar5之至少一者具有至少一個取代基。取代基存在的原因係為了改變主體材料的物理或電子特性。在一些具體實施例中，該等取代基提升了主體材料的可加工性。在一些具體實施例中，該等取代基增加了溶解性及/或增加了主體材料之Tg。在一些具體實施例中’ s亥等取代基係選自由D、院基基團、院氧基基團、石夕烷基基團、矽氧烷及它們的組合所組成之群。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.

-些具體實施例中，Q係一具有至少兩個稠環的芳基。在-些具體實施例中，Q具有3_5個芳族稠環。在一基團 =具體實施例中，Q係選自由疾、菲 '聯伸三苯、啡啉、奈、蒽、喹琳及異喹琳所組成之群。該摻雜劑係-能夠電致發光的電活性材料，其發射波長最大值介於38G nm及75G nm之間。在—些具體實施例中，該摻雜劑發出紅色、綠色或藍色光。可用作電活性層中之-摻雜劑的電致發光㈣材料包括但不限於’小分子有機發光化合物、發光金屬複合物、共扼聚合物及它們的混合物。小分子發光化合物之實例包括 :不限於，溪ϋ紅螢烯、香豆素、葱、嗟二嗤、的混合物β金屬複合物之實例包括但不限於’金屬甜合類啊（metal ehelated。咖。叫化合物。 145481.doc -25· 201109291 共軛聚合物之實例包括但不限於聚（苯伸乙婦）(poly (phenylenevinylenes))、聚 g (P〇lyflu〇renes)、聚（螺二第） (P〇ly(Spir〇biflu〇reneS))、聚噻吩（Polythi〇Phenes)、聚（對伸苯）(p〇ly(p-phenylenes))、它們的共聚物及匕們的混& 物。紅色發光材料之實例包括但不限於’二節并茈 (periflanthenes)、费蒽（fluoranthenes)及茈（perylenes)。已於例如美國專利案第6,875,524號和已公開之美國專利申請案第2005-015 8577號中揭示紅色發光材料。綠色發光材料之實例包括但不限於，二胺蒽 (diaminoanthracenes)及聚伸苯乙稀聚合物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)。已於例如已公開之PCT 申請案第WO 2007/021117號中揭示綠色發光材料。藍色發光材料之實例包括但不限於，二芳基蔥 (diarylanthracenes)、二胺基筷（diamin〇chrysenes)、二胺基花（diaminopyrenes)及聚第聚合物。已於例如美國專利案第 6,875,524號和已公開之美國專利中請案第2〇㈣㈣㈣及第2007-0063638號中揭示藍色發光材料。在一些具體實施例中，該旅蚀杰丨7么豕摻雜劑係一有機化合物。在一些具體實施例中，該摻雜劑#谐 "丨係遥自一非聚合螺二第化合物及一熒惹化合物所組成之群。在一些具體實施例中，兮狹她^ °亥摻雜劑係一具有芳胺基基團化合物。在一些具體實施例中，土丞圓忒電活性摻雜劑係選自下的化学式· 14548 丨.doc -26- 201109291(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

其中：及係—具有3-60個碳 A在每次出現時係相同或不同的原子的芳族基； Q'係一單鍵或一具有3-60個碳原子的芳族基. p及q分別係1至6的整數。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.

在上述化學式之一些具體實施例中，每—化學式中的A 及Q之至v者具有至少二個縮合環。在一些具體實施例中，p及q係等於1。在一些具體實施例中，Q，係苯乙烯基（styryl)或苯乙烯基苯基（styrylphenyl)基團。在一些具體實施例中，Q’係具有至少兩個縮合環的芳族基。在一些具體實施例中，Q·係選自由萘（naphthalene)、蒽（anthracene)、筷（chrysene)、芘（pyrene)、稠四苯 (tetracene)、p山p星（xanthene)、花（perylene)、香豆素 14548 丨.doc •27- 201109291 (coumarin)、若丹明（rh〇damine)、喧。丫酮（㈣⑽以心㈣及紅螢烯（rubrene)所組成之群。在一些具體實施例中，A係選自由苯基（phenyl)、聯苯基 (biphenyl)、甲苯基（tolyl)、萘基（naphthyl)、萘苯基 (naphthylphenyl)及蒽基（anthracenyi)所組成之群。在一些具體實施例中，該摻雜劑具有化學式如下：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:

其中： Y每次出現時係相同或不同的’及係一具有3_6〇個碳原子的芳族基； Q"係一芳族基、一二價三笨胺殘基（residue gr〇up)或一單鍵。在一些具體實施例中，該摻雜劑係一多并苯芳基（aryl acene)。在一些具體實施例中，該摻雜劑係一非對稱多并苯芳基（aryl acene)。在一些具體實施例中，該摻雜劑係一具有化學式v之慧衍生物：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:

其中： 145481.doc •28· 201109291 R在每次出現時係相同或不同的，及係選自由D、烷基、烷氧基及芳基所組成之群，其中可將相鄰Rl0 基聯集在一起以形成一 5員或6員脂族環；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至Ar9係相同或不同的，及係選自由芳基基團所組成之群； d 在每次出現時係相同或不同的，及係〇至4的整數；以及在一些具體實施例中，化學式¥中的摻雜劑係氘化的。在一些具體貫施例中，該等芳基基團係氘化的。在一些具體貫施例中，該等烷基基團係氘化的。在一些具體實施例中，該摻雜劑係至少50%氘化的；在一些具體實施例中，至少60%氘化；在一些具體實施例中，至少7〇%氘化；在某些具體實施例中，至少80%i化；在—些具體實施例中，至少90%氘化；在一些具體實施例中，1〇〇%氘化。在一些具體實施例中，該摻雜劑係一具有化學式VI之筷衍生物：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:

其中： R 在每次出現時係相同或不同的，及係選自由d、烷 145481.doc -29- 201109291 基、烷氧芳基、氟基、氰基、硝基、一so2r12所組成之群，其中R12係烷基或全氟烷基，其中可將相鄰R11基聯集在一起以形成一 5員或6員脂族環； ΑΓ至Ar係相同或不同的’及係選自由芳基基團所組成之群；以及 e 在每次出現時係相同或不同的’及係0至5的整數。在一些具體實施例中，化學式VI中的摻雜劑係氛化的。在一些具體實施例中’該等芳基基團係氘化的。在一此且體實施例中，該等烷基基團係氘化的。在一些具體實施例中，該摻雜劑係至少50%氘化的；在一些具體實施例中，至少60%氘化；在一些具體實施例中，至少7〇%氘化；在一些具體實施例中，至少80»/。氘化；在—些具體實施例中至少90%氣化；在一些具體實施例中，1 〇〇%氣化。綠色摻雜劑的一些非限定實例為如下顯示之化合物01至化合物D8。 D1 ：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 D2145481.doc •30· 201109291 D2

D3D3

D4D4

145481.doc -31 · 201109291 D5 ：145481.doc -31 · 201109291 D5 :

D6 :D6:

J45481.doc -32- 201109291 D7 ：J45481.doc -32- 201109291 D7 :

藍色摻雜劑的一些非限定實例為如下顯示之化合物D9至化合物D16。 D9 ：Some non-limiting examples of blue dopants are compounds D9 through D16 as shown below. D9:

145481.doc -33- 201109291 DIO ：145481.doc -33- 201109291 DIO:

Dll ：Dll:

D12 ：D12:

145481.doc 34· 201109291 D13 ：145481.doc 34· 201109291 D13 :

D14 ：D14:

145481.doc 35- 201109291 D15 ：145481.doc 35- 201109291 D15 :

D16 ：D16:

在一些具體實施例中，該電活性摻雜劑係選自由取代胺基（amino-substituted)疾及取代胺基蒽所組成之群。在—些具體實施例中，本文所述之新氘化化合致發光材料 ^ 你冤叶，且存在作為一電活性材料。 b.它農复層在該敦薏中之中之其匕層可以由有用於這樣的層之任何已知 145481.doc •36- 201109291 材料所製成。該陽極層11 〇係一對於注入正雷入正電何载子而言特別有效的電極。其可由例如，含有今屬 3爷金屬、此合金屬、合金、金屬氧化物或混合金屬氧化物的材料製成，或者其可為一導電聚合物，或它們的混合物。合適的金屬包括第u族金屬、第 4-6族中的金屬及第8_10族過渡金屬。若該陽極係透光的，則通常使用第12族、第13族及第14族金屬的混合金屬氧化 $ ’如氧化銦錫。該陽極11G亦可包括—有機材料，如聚苯胺，其說明在7\^仏〜第357卷，第477·479頁，「FIexible light-emitting diodes made from soluble conducting polymer」（1992年6月Ua)e該陽極及該陰極之至少一者應該為至少部分透明的，以可觀察到所產生的光。該電洞注入層120包括電洞注入材料，且可在一有機電子裝置内具有一或多個功能，其包括但不限於，使其下之層平坦化、電荷傳輸及/或電荷注入特性、像氧或金屬離子之雜質的清除以及其他有助於增進該有機電子裝置之性能的功能。電洞注入材料可為聚合物、寡聚物或小分子。渠等可氣相沉積，或從溶液、分散液、懸浮液、乳狀液、膠態混合物或其它組成物形式的液體沉積。該電洞注入層可用聚合材料，如聚苯胺（PANI)或聚乙烯二氧噻吩（PED0T)加以形成，該等聚合材料經常以質子酸加以摻雜。該等質子酸可以是例如聚苯乙烯磺酸（p〇ly (styrenesulfonic acid))、聚（2-丙烯醯胺-2-甲基-1-丙磺酸） (poly (2-acrylamido-2-methyl-l-propanesulfonic acid))及類 145481.doc ·37· 201109291 似者。該電洞注入層可包括電荷傳輸化合物及類似者，如銅酞青（copper phthalocyanine)與四硫富瓦烯-四氰蓖對醌二甲烧系.(tetrathiafulvalene-tetracyanoquinodimethaneTTF- TCNQ)。在一些具體實施例中，該電洞注入層包括至少一個導電聚合物及至少一個氟化酸聚合物。已於例如已公開之美國專利申請案第2004-01〇2577號、第2004-0 127637號及第 2005/205860號中說明此種材料。在一些具體實施例中’該電洞傳輸層130包括化學式I的新氘化化合物。已於’例如Y. Wang之Kirk-Othmer化工百科全書（Kirk-Othmer Encyclopedia of Chemical Technology)，第4版’第18卷’第837至860頁（1996年）中概述用於層i3〇之其它電洞傳輸材料的實例。可使用電洞傳輸分子及聚合物兩者。一般常用之電洞傳輸分子為：N，N，-二苯基·Ν，Ν'-一（3_ 甲本基-聯苯]-4,4’ -二胺）]^，]^1-^。!^!!)^-]^，]^1-bis(3-methylphenyl)-[l,l'-biphenyl]-4,4'-diamine5 TPD)； 1，1-二[(雙-4-曱苯胺基）苯基]環己烷 tolylamino) phenyl]cyclohexane，TAPC) ; Ν，Ν·-二（4-甲苯基）-Ν，Ν，-二（4-乙基苯基）-[1，1'-(3,3，-二曱基）聯苯]_4,4，-二胺（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);四-(3-曱本基）-N，N，N，N’-2,5-本二胺（161：1*&]<;13-(3-1116111}^1卩1161^1)-N，N，N'，N’-2,5-phenylenediamine，PDA) ; α-苯基ί-Ν，Ν-二苯 14548 丨.doc -38- 201109291 胺苯乙稀（a-phenyl-4-N，N-diphenylaminostyrene, TPS); 對（二乙胺）苯曱酸二苯腙（p-(diethylamino)benzaldehyde diphenylhydrazone, DEH)三苯胺（triphenylamine，TPA); 二[4-(N，N-二乙胺基）-2-甲苯基](4-甲苯基）曱烷（1^[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl) ethane, MPMP) ; 1-苯基-3-[對（二乙胺基）苯乙烯]-5-[對（二乙胺基）苯基]石比 °坐琳（l-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl] pyrazoline，PPR 或 DEASP); 1,2-反-二（9H- °卡 °坐-9 -基）環丁烧（1，2-trans-bis(9H-carbazol-9-yl) yclobutane, DCZB) ; N，N，N'，N'-四（4-曱苯基）-(1，Γ-聯苯）-4,4'-二胺（N，N，N'，N'-tetrakis(4-methylphenyl)-(l，l’-biphenyl) 4,4'-diamine，TTB); N，N’-二（萘-1-基）-N，N’-二-(苯基）聯苯胺（N，N'-bis(naphthalen-l-yl)-N，N’-bis-(phenyl)benzidine， α-ΝΡΒ);以及如銅酞青之紫質化合物。一般常用之電洞傳輸聚合物為聚乙烯咔唑、（苯曱基）-聚矽烷及聚苯胺。亦可能藉由將上述所提及之該等電洞傳輸分子摻雜入如聚苯乙烯（polystyrene)及聚碳酸酯（polycarbonate)之聚合物中而獲得電洞傳輸聚合物。在一些情況中，使用三芳胺聚合物，尤其係三芳胺-苐共聚合物。在一些情況中，該等聚合物及該等共聚合物係可交聯的。可交聯之電洞傳輸聚合物的實例可見於如公開之美國專利申請案第2005-0184287號與公開之PCT申請案第W0 2005/052027號。在一些具體實施例中，該電洞傳輸層摻雜有p型摻雜劑（p-dopant)，如四氟四氰蓖對酿二甲烧（tetrafluorotetracyanoquinodimethane)和 145481.doc -39- 201109291 茈-3,4,9,10-四羧-3,4,9，10-二酐。在一些具體實施例中，該電子傳輸層150包括化學式I之新氘化化合物。可於層150中使用其它電子傳輸材料，其實例包括金屬钳合類号辛化合物，如三（8 -經基啥琳）紹 (tris(8-hydroxyquinolato) aluminum，Alq3)二（2-曱基-8-喧琳）（對苯基苯酴）铭（III) (bis(2-methyl-8-quinolinolato) para-phenyl-phenol at o)aluminum(III) > BA1Q);及号口坐 (azole)合物’如2-(4-聯苯基）-5-(4-二級丁基苯基）-1，3，4_ 口惡二0坐（2-(4-biphenylyl)-5-(4-t-butylphenyl)-l，3,4-oxadiazole， PBD)和3-(4-聯苯基）-4_苯基-5-(4-三級丁基苯基）_1，2,4_三 ^ ^ (3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole，TAZ)及 1，3,5-三（苯基-2-苯并咪唑）苯（l，3,5-tri(phenyl-2-benzimidazole)benzene，TPBI);啥 p号琳衍生物’如 2,3-二（4-氟苯基）喧吟琳（2,3-bis(4-fluorophenyl) uinoxaline);啡啉衍生物，如9,10-二苯啡啉（9，l〇-diphenylphenanthroline，DPA)及 2,9-二曱基-4,7-二苯基 _ 1，10-啡琳（2,9-dimethyl-4,7-diphenyl -1，10-phenanthroline， DDPA)，及它們的混合物。該電子傳輸層亦可播雜有η型摻雜劑（n-dopant)，如Cs或其它鹼金屬。層150可用以促進電子傳輸’及亦當作一緩衝層或幽禁層（confinement layer)，以防止層介面之激子的淬滅。較佳而言，此層提昇電子移動率及減少激子淬滅。該陰極160係一對於注入電子或負電荷載子而言特別有效的電極。該陰極可為任何金屬或非金屬’其具有的功函 145481.doc •40- 201109291 數低於陽極。用於陰極的 r. ρ、心u 竹η τ選自第1族鹼金屬（例如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)、第2私（鹼土;)金屬 . 弟12知金屬（包括稀土元素及鑭族7G素以及釣季开去、坍糸兀素）。可使用諸如，鋁、銦、鈣、鋇、#和鎂及其組合的材付种。亦可在有機層及陰極層之間沉積含Li或含Cs有機金屬化入匕0物，如、CsF或Li2〇，以降低操作電壓。已知在有機電子裝置中可丁 J具有其匕層。例如，在該陽極 110和電洞注入層120之間可具有-層(未顯示)，以控制所 ’主入之正電何的罝’及’或提供該等層之帶隙匹配㈣心辦讀㈣），或者料—保護層。可❹本技術領域中已熟知之層，如銅酞青、氮氧化矽、氟碳化物、矽烷；或金屬的-超薄層’如Pt。或者係，可對陽極層ιι〇、活性層120-150或陰極層16〇之一些或全部進行表面處理，以增加電荷載子傳輸效率。較佳係藉由平衡發射體層中的正電荷及負電荷來決定每-化合物層之材料的選擇，以使-裝置具備高電致發光效率。應理解，每一功能性層可由多於一層的層構成。可以各種技術來f備該裝置，該等技術包括在—合適基板上依序氣相沉積該等個別層。可使用如玻璃、塑膠及金屬的基板。可使用如熱蒸鍍、化學氣相沉積及類似者之傳統氣相沉積技術。或者係，可使用傳統塗佈或印刷技術，自合適溶劑中的溶液或分散液塗敷有機層，該等技術包括仁不限於，旋塗（sPin-c〇ating)、浸塗（dip-coating)、卷對卷塗佈技術（r〇ll_t〇_r〇U)、噴墨印刷（ink_jet printing)、網 145481.doc -41· 201109291 版印刷（screen-printing)、凹版印刷（gravure printing)及類似者。本發明亦關於一種電子裝置，其包括位在兩個電接觸層之間的至少一個活性層，其中該裝置之該至少一個活性層包括化學式1的蒽化合物。裝置經常具有額外電洞傳輸層及電子傳輸層。為了達到一高效率LED，電洞傳輸材料之最高佔用分子軌域（highest occupied molecular orbita 卜 HOMO)必須與陽極的功函數匹配，及電子傳輸材料之最低未佔用分子轨域 (lowest un-0ccupied m〇lecuiar orbita卜⑶河⑺必須與陰極的功函數匹配。於選擇電子和電洞傳輸材料時，該等材料之化學相容性及昇華溫度亦為重要的考量因素。應理解，由本文所述之蒽化合物製成的裝置的效率可進一步藉由最佳化該裝置中的其它層而改進。例如，可使用更高效率的陰極，如Ca、Ba或LiF。亦可應用定型的基板及新穎的電洞傳輸材料，其等造成操作電壓減小或量子效率增加。亦可增添額外層，以裁製各種不同層之能階，且有助於電致發光。本發明之化合物經常為光致發光的（ph〇t〇luminescent)，且可用於除了 OLED以外的應用+，如氧氣敏感指示器及生物鑑定中的發光指示器（luminescent indieat〇幻。實例下列實例說明本發明之特定特徵及優點。該等實例旨於說明本發明’而非限制。除非另外指示，否則本文所用的 14548l.doc -42- 201109291 全部百分比係以重量計。摻雜劑材料之合成 (Ό摻雜劑D6的製備過程如下。 t間體（a)之合成：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\OH

5 + CCO 將35 g(300 mM)的2_甲基己醇及178 g(i〇〇福）的葱加入50 mL的三氟乙酸後，置於氮環境中回流一整夜。溶液快速地變暗成一棕色非均質材料。將此溶液冷卻至室溫，於氮氣流環境下蒸發並萃取至氯化曱烷。在硫酸鎂上分離並乾燥有機層，且將其蒸發至乾燥。透過二氧化矽管柱（silica column)以己烷萃取所得之固體，並回收淺黃色溶液。藉由緩慢冷卻及從甲醇中再結晶，將上述溶液蒸發成一厚黃油（yellow oil)且從丙酮/甲醇中再結晶。使用 NMR分析確認該結構。中間體（b)之合成：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):

將6.0 g(l6 mM)的中間體（a)(純異構物）放入1〇〇 mL的二氣乙烷中，並滴狀加入2.10 mL的漠（4〇 mM) ’於室溫下 I45481.doc -43- 201109291 攪拌4小時。然後將此混合液倒入水中，加入亞硫酸鈉，以消耗剩餘的溴。接著萃取此產物至氣化甲烷，及在硫酸鎮上乾燥該有機層。以氣化曱烧溶析液（eluent)使所得的材料通過氧化紹管柱（alumina column)，然後蒸發，再加入甲醇，以沈澱一淺黃色固體。產量為〜7.2 g 中間體（c)之合成：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:

在套手工作箱（gl〇ve box)中將25 g的漠基-〇卡唾（77.7 mM)加至18.9 g(155 mM)的硼酸中。加入1.〇 g的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 的 P(t-Bu)3(2.1 mM)和 20 g 的碳酸納（200 mM) ’及將所有的物質溶解於200 mL的二氧陸園 (dioxane)和50 mL的水中。於套手工作箱中的加熱包 (mantle)中將所得產物於50°C的溫度下混合並加熱1小時，接著在氮氣環境下緩和地暖和（變阻器設定最低點）一整夜。該溶液立即變成暗紫色，而且在到達〜5 〇〇c時變成暗掠色❶於套手工作箱外’將水加入棕色溶液中，其會分離成一油狀黃色的層。加入DCM，且分離有機層◎在硫酸鎂上乾燥濾液（Filtrate) ’得出一淡橙色溶液，其經蒸發後會產生白色固體。在蒸發至低容量及加入己烷之後，將該白色固體遽除。以曱醇徹底洗滌該固體，直到洗滌液變成無色為止’接著以***清洗，然後真空乾燥（sucti〇ned dry) ’得出21 g的白色固體。使用nmR分析確認該結構。 I45481.doc -44· 201109291 中間體（d)之合成：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)及 4.3 g的三級丁醇納（sodium t-butoxide)混合在一起，並在套手工作箱中溶解在200 mL的茬（xylene)中。攪拌15分鐘，然後加入25 g的3-琪基-漠苯（3-iodo-bromobenzene)。撥拌15分鐘，然後再加入10 g的咔唑’然後回流該混合液。使用空氣冷凝器執行回流程序（Refluxed o/n.)。溶液立即變成暗紫/標色，但是只要溫度一達到〜8〇。(：，則溶液會變成渾濁的暗紅棕色。在加熱接近整夜的回流後，該溶液會變成清澈的暗棕色。在套手工作箱外於氮氣流環境下蒸發該溶液並將其溶解在DCM中，然後使用DCM/己烷，透過一二氧化矽與鹼性氧化鋁之床（堆疊在索式萃取器中）索式萃取 (soxhlet)該溶液。收集暗橙色溶液，i蒸發至乾燥。剩下暗橙色㈣m醇絲，接著將其溶解在乙财， ^以甲醇再沈澱。該撥棕色的油在乙㈣境中蒸發至低容 f ’然後加入丙綱/甲醇，以沈澱出一灰白色的固體，產 :為6·4 g。#由過濾作用收集該灰白色固體，然後以少曰_洗;k ’並真空乾燥。使用NMR分析確認該結構。中間體（e)之合成·· 145481.doc -45- 201109291Bis(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

在套手工作箱中將4.8 g(〇.〇i M)的中間體（d)加入i 7 g(0.01 Μ)的胺中。加入0.10 g的 pd2DBA3(0_ll ηιΜ)、 0.045 g的 P(t-Bu)3(0.22 mM)和 l.l g的t_BuONa，然後將所有的物質溶解在25 mL的曱苯中。一旦加入催化劑材料，即會出現一輕微的放熱反應。於套手工作箱的加熱包中將所得產物於80°C的溫度下於氮氣環境中加熱2小時，直到呈現暗棕色溶液（濃）。於冷卻後，藉由以DCM層析之β_氧化紹層析法激發該溶液。然後收集一具有亮紫色/藍色光致發光體的暗黃色溶液。將該溶液於氮氧環境下蒸發至低容量’以形成一黏性橙色油，其經冷卻後會固化成一暗黃色玻璃。將其攪拌至甲醇/DCM中，並使其結晶成一淺黃色/白色固體，產量為〜5 g。使用NMR分析確認該結構。摻雜劑D6之合成：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 在套手工作箱中，將2.81 g(5 mM)的中間體（e)和0.5 g(5 mM)的t-Bu〇Na中及50 mL的甲苯加入至1.32 g(2_5 mM)的中間體（b)中。再加入溶解在10 mL甲苯中之0.2 g的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）和〇.〇8 g 的p(t-Bu)3(0.4 mM)。於混合後，該溶液緩慢地放熱並變成黃棕色。於套手工作箱的加熱包中將所得產物於〜丨〇〇〇c的溫度下於氮氣環境中混合並加熱1小時。溶液立即變成暗紫色，但是只要溫度一達到〜80 C，其會變成暗黃綠色，且具有明顯的綠色發光體。於最低的變阻器設定點下攪拌一整夜。於冷卻之後，從套手工作箱中移出該材料，並透過以甲苯和氯化甲烧層析之酸性氧化鋁栓塞過濾之。接著將暗橙色溶液蒸發至低容量。將此溶液通過二氧化矽管柱（使用6〇:4〇比例的甲苯：己烷）。收集黃橙色溶液，其在TLC上顯示藍色的導向點 (leadmg Sp〇t)。將此溶液再溶解於己烷：甲苯（80:20)中，並使其通過以80%己烧/甲苯溶析之酸性氧化铭。摒棄快速流動的藍帶（蒽和單胺蒽）。將所得的黃帶蒸發至低容量，並從甲苯/丙酮/甲醇中結晶。以甲醇和己烧洗務所得產物’且真空乾燥’以獲得自由流動的單晶黃色粉末。使用 NMR分析確認該結構。 ⑺換雜劑 D12，N6，N12_ 二（2,4_ 二甲基苯基）_N6，二 (4 _異丙聯三苯_4_基浓池仏二胺（NhNm叫Μ — dimethylphenyl)-N65Nl2-bis(4--is〇pr〇pylterphenyl.4_ yl)chrySene-6，12-diamine)，的製備過程如下。 145481.doc -47· 201109291Pd2DBA3 (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

在一乾燥相中’將 6，12-二溴获（6,12-dibromochrysene) (0.54 g，1.38毫莫耳）、N-(2,4-二曱基苯基）_N-(4，-異丙聯三苯-4-基）胺（1.11 g，2.82毫莫耳）、三（三級_ 丁基）膦 (tris(ieri-butyl)phosphine) (0.028 g，〇· 1 4 毫莫耳）和三 (一亞午基丙酮）二飽（〇) (tris(dibenzylideneacetone) dipalladiUm(0)) (0.063 g’0_069毫莫耳）組合在圓底燒瓶中’並將其溶解於20 ml的乾曱苯中。授拌該溶液一分鐘，接著加入三級丁醇鈉（0.29 g，3.03 mmol)和10 ml的乾甲苯。加入一個加熱包’將反應物加熱至6〇°c持續3天。然後冷卻反應混合液至室溫，及透過一 1英叫·的碎膠栓塞和1英吋的矽藻土（Celite)過濾之，再以500 mL的曱苯洗蘇。在經減小的壓力下移除揮發物，得出一黃色固體。進一步以矽膠管柱層析法純化粗製品，其係使用氯仿 (chloroform)於己烧（hexane)中的梯度分布（〇%至40%)。從 DCM及乙腈中再結晶，及所得產物的產量為〇.54〇 g(4〇%) ’其為一黃色固體。1H NMR (CDC13)的結果與該結構一致。 (3)使用類似於摻雜劑D12之合成的程序製成摻雜劑〇13， N6，N12-二（2,4-二甲基苯基）-N6，N12-二（4，，-三級-辛基聯三 145481.doc •48- 201109291 苯-4-基）疾-6，12- 二胺（N6，N12-bis(2,4-dimethylphenyl)- N6,N12-bis(4"-tert-octylterphenyl-4-yl)chrysene-6,12-diamine)。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"- Tert-octylterphenyl-4-yl)chrysene-6,12-diamine).

比較性實例A 此貫例說明非氘化化合物’即比較化合物A的製備。Comparative Example A This example illustrates the preparation of a non-deuterated compound, i.e., Comparative Compound A.

可根據下列方法製備此化合物：This compound can be prepared according to the following method:

145481.doc • 49- 201109291 b心；>8 —- —- ϊβ^-8145481.doc • 49- 201109291 b heart; >8 —- —- ϊβ^-8

化合物2之合成：在附有機械攪拌器（mechanical stirrer)、滴液漏斗 (dropping funnel)、溫度計（thermometer)及 N2 鼓泡器（N2 bubbler)的3 L燒瓶中，於1.5 L的乾氣化曱烷中加入54 g(275.2 mmol)的蔥酮。在一冰槽中冷卻該燒瓶，然後用滴液漏斗加入83.7 ml (559.7毫莫耳）的1，8-二吖雙環[5.4.0]十一-7-烯（l，8-diazabicyclo[5.4.0]undec-7-ene，DBU)直到超過1，5小時。該溶液變成不透明橙色狀，然後再變成深紅色。經由注射器（syringe)，將58 ml(345.0 mmol)的三敗曱確酸針（triflic anhydride)加至仍處於冷卻狀態的溶液中持續約超過1.5小時，該溶液的溫度需保持低於。使該反應於室溫下持續3小時，之後，另外再加入1 mL的三氟甲磺酸酐，並繼續於室溫下攪拌達3〇分鐘。緩慢地加入5〇〇 mL的水然後为離所形成之層。以3份200 mL的二氯曱烧 (DCM)萃取水層（aque〇us Uyer)，且在硫酸鎂上乾燥經組 5之有機物，再用旋轉減壓蒸發（r〇tary evap〇rati〇n)過濾並濃縮之，得出一紅油。執行矽膠管柱層析法，接著從己烷中再結晶，產出43.i g的淺棕色粉末（43%)。 145481.doc •50· 201109291 化合物3之合成：在一個充滿氮氣的套手工作箱中，將三氟甲磺酸蔥-9-基（anthracen-9-yl trifluoromethanesulfonate) (6.0 g，18.40 mmol)、萘-2-基-棚酸（Napthalen-2-yl-boronic acid) (3.78 g ’ 22.1 mmol)、罐酸三卸（potassium phosphate tribasic) (17.50 g» 82.0 mmol)、醋酸纪（II) (palladium(II) acetate) (0.41 g，1.8 mmol)、三環己膦（tricyclohexylphosphine) (0.52 g，1.8 mmol)和THF (100 mL)加入配備有磁授拌子 (magnetic stirring bar)的 200 mL克耳達（Kjeldahl)反應燒瓶中。將反應混合液從乾燥箱中移除後，以氮氣沖洗該反應混合液，再用注射器加入50 mL的除氣水（degassed water)。接著加入一冷凝器，然後使該反應物回流一整夜。使用TLC監控該反應物^ 一旦反應完成即將反應混合液冷卻至室溫。分離該有機層並以DCM萃取水層。組合該等有機物組份’以鹽水洗滌，然後以硫酸鎂乾燥。在經減小的壓力下移除該溶劑。以丙酮和己烷洗滌所得的固體，並過濾之。以矽膠管柱層析法執行純化，產出4.03 g的產物（72%) ’其為淺黃色結晶材料。化合物4之合成：將 11 · 1 7 g(36.7 毫莫耳）的 9-( 萘 -2-基）蒽（9-(naphthalen-2-yl)anthracene)懸浮於 100 mL 的 DCM 中。加入 6.86 g(38.5 毫莫耳）的N-溴琥珀醯亞胺（NBS)，及在100 W燈的照度下攪拌該混合液。首先形成清澈的黃色溶液，然後出現沈澱物。使用TLC監控該反應物。於丨5小時後，部分濃縮該反 145481.doc •51· 201109291 應混合液’以移除氣化甲烷，然後從乙腈中結晶，產出 12·2 g的淺黃色晶體（87%)。化合物7之合成：在一個充滿氮氣的套手工作箱中，將萘-1 -基_ 1 _硼酸 (naphthalen-l-yl-l-boronic acid) (14.2 g，82.6 mmol)、1-漠基-2-埃苯（l-bromo-2-iodobenzene) (25.8 g，91.2 mmol)、四（三苯構）二！巴（〇) (tetrakis(triphenylphospine) palladium(O)) (1.2 g，1.4 mmol)、碳酸鈉（25.4 g，240 mmol)和甲苯（120 mL)加入配備有攪拌子的500 mL圓底燒瓶中。將反應混合液從乾燥箱中移除後，以氮氣沖洗該反應混合液，再用注射器加入120 mL的除氣水。接著，將一冷凝器附設至反應燒瓶，回流該反應物達1 5小時。使用 TLC監控該反應物。將反應混合液冷卻至室溫《分離該有機層並以DCM萃取水層。組合該等有機物組份，且在經減小的壓力下移除溶劑，得出一黃油。藉由使用石夕膠的管柱層析法執行純化，產出13.6 g的清澈油（58%)。化合物6之合成：將 4-漠苯-1-萘（4_bromophenyl-l-naphthalene) (28.4 g， 10.0 mmol)、二（戊醜）二硼（bis(pinacolate) diboron) (40.8 g ’ 16.0 mmol)、Pd(dppf)2Cl2 (1.64 g ’ 2.0 mmol).乙酸If (potassium acetate) (19.7 g，200 mmol)和 DMSO(350 mL) 加入配備有磁攪拌子和回流冷凝器的1公升燒瓶中，該回流冷凝器連接至一氮導管（nitrogen line)及一油槽（oil bath) ^以氮氣鼓泡該混合液達15分鐘，然後加入 145481.doc -52- 201109291Synthesis 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)。在此過程期間，該混合液逐漸地轉變成暗掠色。在氮氣環境下，於油槽）授掉該反應物達18小時。於冷卻該混合液後，將該混合液倒入冰水中，並以氣仿萃取（3x)。接著以水（3x)及飽和鹽水 (1X)洗滌該有機層，然後以MgS04乾燥。在過濾及移除溶劑之後，使用矽膠管柱層析法純化殘餘物。組合含有組份之產物，且使用旋轉減壓蒸發（r〇tary evap〇rati〇n)移除溶劑。從己烧/氣仿中結晶所得之白色固體，並在4(rc於一真空烘箱中乾燥’得出白色片狀結晶的產物’產量為15〇 g(45%)。1H及13C-NMR光譜的結果與所預期的結構一致。比較化合物A的合成在套手工作箱中將4,4,5,5-四甲基-2-(4-(萘-4-基）苯基）-1，3,2-二。惡 ^^(4,4,5,5-tetramethyl-2-(4-(naphthalen-4-yl)phenyl)-1,3,2-dioxaborolane) (1.90 g > 5.74 mmol) ' 二（一亞卞基丙酮）二纪（O)(tris(dibenzylideneacetone) dipalladium(O)) (0.24 g，0.26 mmol)、和甲苯（50 mL)加入 250 mL的燒瓶中（2·00 g，5.23 mmol)。自乾燥箱中移除該反應燒瓶’將一冷凝器及氮氣進氣口附設至該反應燒瓶。經由注射器加入除氣並溶於水之碳酸鈉（2 Μ，20 mL)。於 90°C的溫度下攪拌並加熱該反應物一整夜《使用HPLC監控該反應物。在該反應物冷卻至室溫後，分離該有機層。以DCM洗條水層兩次，及使用旋轉減壓蒸發（rotary evaporation)濃縮經組合之有機層，產出一灰色粉末。藉由 145481.doc -53· 201109291 中性氧化鋁之過濾作用、己烷之沈澱作用及矽膠管柱層析法的純化，產出2.28 g的白色粉末（86%)。進一步純化所得之產物，如在已公開之美國專利申請案第2008-01:38655號中所述般，以達到至少99.9%的HPLC純度且雜質吸光度不大於〇.〇1。圖2說明化合物a的1H NMR光譜。實例1 此實例說明具有化學式I之化合物，即化合物Η14的製備過程。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 > 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.

比較化合物A H14 於氮氣環境中，將A1C13(0.48 g，3.6 mmol)加入得自比較性實例A之比較化合物A的全氘化苯（perdeuterobenzene) 或苯-D6(C6D6) (1〇〇 mL)溶液中（5 g，9.87毫莫耳）。添加 D2〇(50 mL)至所得之混合液後，於室溫下攪拌該混合液達 6小時。分離該等層，接著以CH2Cl2(2x30 mL)洗滌水層。在硫酸鎂上乾燥經組合之有機層，並使用旋轉減壓蒸發移除揮發物。經由管柱層析法純化粗製品。所獲得氘化的產物 Hl(x+y+n+m=21-23)為一白色粉末（4.5 g)。 145481.doc •54· 201109291 進一步純化所得之產物，如在已公開之美國專利申請案第2008 0138655號中所述般，以達到至少99 9%的册1^純度且雜質吸光度不大於0.0卜從上文中得知，所決定之材料具有與比較化合物A相同的純度位準。圖3及圖4分別顯示iH NMR⑽心咖ASAp MS。化合物具有的結構如下： D ΠComparative 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

其中’「D/H」指示Η或D有近似相等的機率處在此原子位置。使用 H NMR、13C NMR、2d NMR及1H-13C HSQC(異核單量子相干性）確認該結構。貫例2及實例3與比較性實例b及比較性實例c 這些實例展示具有一藍色發射體之裝置的產製及性能。該裝置在一玻璃基板上具有下列結構：陽極=氧化銦錫（IT0) : 5〇 nm 電洞注入層=HIJ1 (50 nm)，其係一導電聚合物和一氟化聚合續酸的含水分散液。已於例如在已公開之美國專利申請案第 2004/0102577 號、第 2004/0127637 號、第 2005/ 0205860號和已公開之pCT申請案第w〇 2009/018009號中描述此種材料。電洞傳輸層=聚合物Pi，其係一非交聯性芳胺聚合物（2〇 145481.doc -55· 201109291 nm) 電活性層=13 :1的主體材料和摻雜劑（40 nm)，如表1所示電子傳輸層=ET 1，其係一金屬喧淋衍生物（10 nm) 陰極=CsF/Al (1.0/100 nm) 表1.裝置電活性層實例主體材料摻雜劑比較性實例B-1 比較化合物A D12 比較性實例B-2 比較化合物A D12 比較性實例B-3 比較化合物A D12 比較性實例B-4 比較化合物A D12 實例2-1 H14 D12 實例2-2 H14 D12 實例2-3 H14 D12 實例2-4 H14 D12 比較性實例C-1 比較化合物A D13 比較性實例C-2 比較化合物A D13 實例3-1 H14 D13 實例3-2 H14 D13 藉由溶液加工處理及熱蒸鍍技術之一結合而產製OLED 裝置。使用來自薄膜裝置公司（Thin Film Device, Inc)之經圖案化的氧化銦錫（ITO)塗布玻璃基板。此等ITO基板係基於塗布有ΙΤΟ之Corning 1737玻璃，其具有30歐姆/平方的薄片電阻及80%的光透射率。在含水清潔劑溶液中超音波式地清潔該經圖案化之ITO基板，並以蒸餾水加以沖洗。隨後，在丙酮中超音波式地清潔該經圖案化之ITO，以異丙醇加以沖洗之，然後在氮氣流環境中乾燥。就在要製造該裝置之前，以紫外光臭氧（UV ozone)處理該等已清潔之經圖案化的ITO基板達1 0分鐘。於冷卻之 145481.doc -56- 201109291 後，隨即在該ITO表面上旋塗HIJ1之含水分散液，然後再加熱以移除溶劑。於冷卻之後，接著以一電洞傳輸材料之溶液旋塗該等基板，然後再加熱以移除溶劑。於冷卻之後，以發射層溶液旋塗該等基板，然後再加熱以移除溶劑。遮罩該等基板’並將其放入一真空室中。使用熱蒸鍵來沉積電子傳輸層，接著為一 CsF層。隨後於真空中更換遮罩，並使用熱蒸鍍來沉積一 A1層。排氣該真空室，及使用一玻璃蓋、乾燥劑（dessicant)及UV可固化環氧化物封裝該等裝置。藉由量測下列數據來描述OLED樣本之特徵，（1)電流_電壓（I-V)曲線，（2)電致發光輻射強度對電壓，及（3)電致發光光譜對電壓。以上所有三個測量皆於相同時間執行，並由一電腦控制。藉由把LED之電致發光輻射強度除以該裝置運轉所需之電流而決定該裝置在某一特定電壓處的電流效率。其單位為cd/A。將該電流效率乘以ρί(π)，再除以操作電壓，得出功率效率❶其單位為lm/w。表2說明該裝置之資料。表2·裝置性能實例 CIE (x，y) 電壓 (V) C.E. (cd/A) E.Q.E. (%) P.E. (lm/W) 壽命測試電流密度 (mA/cm2) 壽命測試發光強度 (nits) 原始 T50 ⑻ 預測壽命期T50 @1000 nits 比較性實例 B-1 0.135, 0.124 4.4 6.1 6.0 4.3 129 6837 410 10766 比較性實例 B-2 0.135, 0.127 4.3 6.4 6.1 4.7 125 7002 410 11211 比較性實例 B-3 0.136， 0.123 4.4 5.7 5.6 4.1 127 5906 430 8804 145481.doc -57- 201109291 比較性實例 Β-4 0.134, 0.129 4.3 6.4 6.1 4.7 123 7021 430 11813 實例 2-1 0.136， 0.119 4.4 5.7 5.7 4.1 136 7040 870 24010 實例 2-2 0.137， 0.117 4.2 5.4 5.5 4.1 126 6244 830 18679 實例 2-3 0-136， 0.118 4.2 5.7 5.7 4.2 129 6467 830 19828 實例 2-4 0.136, 0.118 4.3 5.5 5.6 4.1 121 6148 870 19071 比較性實例c_ 1 0.135, 0.128 4.3 6.2 6.0 4.6 141 8018 490 16871 比較性實例C-2 0.135， 0.128 4.3 6.3 6.0 4.6 125 7136 510 14403 實例 3-1 0.135， 0.122 4.3 6.0 5.9 4.4 121 6741 950 24356 實例 3-2 0.135, 0.124 4.2 6 5.8 4.4 126 6974 930 25257 *所有的資料為@ 1000 nits，CE=電流效率；ciEx和CIEy 係根據C.I.E.色度圖的x和y顏色座標（CommissionWhere '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)。原始T50 係一裝置達到初始發光強度一半時的時間（以小時計），該初始發光強度係於壽命測試發光強度時所給定。預測T50係於1 〇〇〇 nits時的預測壽命期，其使用一加速因子丨.7。由此看出’若具有本發明之氘化的主體材料，裝置的使用壽命會大幅度地增加，同時維持其它裝置特性。當使用發射體D12時，具有非氘化之主體材料的比較裝置（比較性實例B-1至B-4)具有一平均預測T5〇為1〇,649小時。當使用氘化類似主體材料Η14(實例2-1至2-4)時，該等裝置具有的平均預測了50為20,379小8夺。當使用發射體1)13時，比較裝置（比較性實例C-1及C-2)具有的平均預測15〇為15,637小時。當使用說化類似主體材料Η14(實例31及3_2)時，平均預測Τ50為24,807小時。 145481.doc •58- 201109291 實例4 此實例說明一些氘化中間體化合物的製備過程，渠等可用以使用氘化作用之受控位準合成具有化學式χ之化合中間體4A :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:

將一部分的無水二溴化銅（45 g，0.202 mole)加至CC14 (500 mL)中的蒽-dl0(18.8 g，0.10 mole)之溶液中。於回流條件下，攪拌並加熱該反應混合液達12小時棕色的二氯化銅逐漸地轉變成白色的二溴化銅，且逐漸地釋出漠化氫 (連接至鹼性浴池吸收體（base bath absorber))。在反應結束之時，藉由過濾作用移除二溴化銅，然後使四氣化碳溶液通過填有200 g氧化鋁的35-mm層析管柱。以200 ml的 CH2C12洗析該管柱。蒸發經組合之析出液至乾燥，得出 24 g 的 9-溴蒽 d9(9-bromoanthracene-d9) ’ 其為一檸檬黃色的固體（87%)。該固體包括原料之雜質（〜2%)和二溴副產物 (〜2%)。此材料直接使用在另外的偶聯反應中且無需純化。藉由使用己烷或環己烷的再結晶，可進一步純化該中間體，以得出純^化合物。中間體4B :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/HACL2/Nal〇4 ^------ H2SO4/HAC

201109291 於室溫下，將93 mL的50% H2S04和494 mL的HOAc的混合溶劑加至d5-溴苯（MW 162，100 g，0.617 mol)中。接著，加入粉末化之I2(MW 254，61.7 g ’ 0.243莫耳），之後再加入粉末化之NaIO4(MW214，26.4g，0.l23莫耳）。劇烈地擾拌該混合物，並加熱至90°C達4小時。暗紫色的溶液變成淺橙色的混合物，其含有一極細的白色沈澱物。然後冷卻該混合物至室溫一整夜。在此期間，所得產物沈澱成板狀微晶體。過遽該混合物，並以1 〇 %硫代硫酸納 Na2S2〇3(5 0 mL)洗條該混合液兩次，然後再以水洗務。將 s玄混合物溶解於CHAl2中，然後執行快速管柱層析（fiash column)。獲得124 g淡黃色的結晶材料（70%) 〇以CH2cl2 (50 mLx3)萃取濾液，且組合以1〇。/。硫代硫酸鈉Na2S2〇3(5〇 mL)洗務兩次及以水洗滌的ci^ci2 ^在乾燥及蒸發該溶劑並執行快速快速管柱層析之後，得出另一個32 g的純產物 (17.5%)。總重為 156 g(產量 88%)。中間體4C :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:

於的溫度下，將過氧化氫（FW:34，d=11 g/mL， 56 g，51.5 mL的3 0°/。含水溶液；〇 5 m〇1)緩慢地加入 CH2C12 (800 mL) : H20(80 mL)中的萘 _d8(MW 136，68 g’ Ο·5 莫耳）與氫溴酸（MW:81，d=1.49, 100 g; 67.5 mL 的 49%含水溶液；〇6莫耳）之經攪拌溶液中達3〇分鐘的—時 145481.doc -60· 201109291 間週期。使該反應物保持於室溫中達4 〇小時’同時使用 TLC監控其過程《於溴化作用完成後，在經減小的壓力下移除該溶劑，且以ίο%硫代硫酸鈉Na2S2O3(50 mL)洗滌兩次及以水洗滌所得之粗製品。使用己烷（1〇〇%)藉由矽膠快速官柱層析法（100-200篩孔），然後蒸餾之，來隔離純產物，以得出85 g的純1-溴-萘_d7，其為一清澈液體，產量約為80%。中間體4D :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:

以氮氣鼓泡300 ml的乾1，4-二氧陸圜中的丨-溴萘_d7(21 4 g，〇·1〇 mol)、二（品納可）二硼（bis(pinac〇lat〇)dib〇r〇n)(38 g，〇·15莫耳）、乙酸鉀（19.6 g，0.20 mol)的混合液達15分鐘°然後添加卩(1咐1^)2(：12-(^2(：12(1.63§，0.002 111〇1)。於 ioo°c(油槽）加熱該混合液達18小時。於冷卻該混合液後，透過矽藻土過濾該混合液，接著將其濃縮至5〇 mL，然後加入水，並以***萃取三次（1〇〇 mLx3)。以水（3x)及鹽水 (lx)洗滌該有機層，然後在MgSCU上乾燥，接著過濾並濃縮。將殘餘物提交至矽膠管柱（溶析液：己烷），得出一白色液體，其具有副產物萘及二硼酯（diboronic ester)。因此藉由蒸餾執行進一步純化作用，以得出清澈的黏性液體。產量為21 g，82%。 145481.doc •61 · 201109291 中間體4E :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:

:故: So

D DD D

Pd(Ph3P)4 甲笨-H20/2M Na2C03 將 Na2C03(12.6 g，〇·12 mol)和 H2O(50 mL)，Aliquat®(3 g)加至曱苯（300 mL)中的1-溴-4-碘-苯-D4 (10.95 g， 0.0382 mole)及 1·萘硼酯-D7(10.0 g，0.0383 mole)的混合物中。以氮氣鼓泡該混合物達15分鐘。然後加入pd (PPh3)4(0.90 g ’ 2°/。）。在一氮氣環境下回流該混合液達1 2 小時。於冷卻該反應混合液後，分離該反應混合液，然後以水洗滌有機層，並分離、乾燥及濃縮。加入二氧化矽濃縮。在蒸發殘餘的溶劑之後，使用己烷作為溶析液執快速管柱層析，以得出粗製品。藉由蒸餾執行進一步… 化作用（於135-140 C/100 mt〇rr下收集），得出清澈的液體（8.76 g，產量78%)。、黏' 中間體4F :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 1,4二氡陸囿，90〇C, 18hPd(dppf)2CI2, AcOK 1,4 氡氡, 90〇C, 18h

145481.doc -62- 201109291 以氮氣鼓泡200 ml的乾丨，4_二氧陸圜中的^溴-苯‘萘― dll(22 g ’ 0.075 mole)、二（品納可）二硼（23 g，〇〇9〇 mole)、乙酸鉀（22 g，0.224 mole)的混合液達15分鐘。然後添加Pd(dppf)2Cl2 CH2C12(1.20 g，〇_〇〇147莫耳）。於 100°C(油槽）加熱該混合液達18小時》於冷卻該混合液後，透過碎藤土過濾該混合液，接著將其濃縮至5〇 mL，然後加入水’並以乙趟萃取三次（1 〇〇 mL><3)。以水（3x)及鹽水 (lx)洗滌該有機層’然後在MgS〇4上乾燥，接著過渡並濃縮。將殘餘物提交至石夕膠管柱（溶析液：己烧），得出一白色液體’其具有副產物萘及二硼酯。因此，藉由使用己烧作為浴析液再度執行發膠管柱層析而執行進一步純化作用。在蒸發溶劑並將其濃縮至約80 mL的己烷，且形成白色晶體產物之後，濾得產物為20.1 g，產量8 1 %。中間體4G: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><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:

將 Na2C〇3(31.8 g)和 H2〇(120 mL)，Aliquat®(5 g)加至曱苯（500 mL)中的中間體4A (18.2 g)和中間體4F之硼酯（25.5 g)中。以氮氣鼓泡該混合液達15分鐘。然後加入Pd(PPh3)4 (1.5 g，1.3%)。在一氮氣環境下回流該混合液達12小時。於冷卻該反應混合液後，分離該反應混合液，然後以水洗 145481.doc -63- 201109291 滌有機層，並分離、乾燥及濃縮至〜50 mL，然後倒入 MeOH中。過濾該固體以得出黃色的粗製品（〜28.0 g)。以水、HC1( 10%)、水及甲醇洗滌該粗製品。將該粗製品再溶解於CHCh中，然後於MgS04上乾燥，並過濾。把矽膠加入該濾液中’濃縮並乾燥，然後使用己烷僅作為溶析液 (全部50 L的己烧皆通過—僅回收5 L的己烧）執行石夕膠（〇.5 Kg)純化，以得出白色產物。中間體4H :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:

將溶解於CH2C12(150 mL)中的溴（MW 160，8.0 g，〇.〇5 mole)緩慢（20 分鐘）加入 CH2C12(450 mL)中的 9-(4-萘-1-基）苯蔥-D20，中間體4G(MW 400.6，20.3 g，0.05莫耳）之溶液（經冰槽冷卻）中。反應立即發生，及顏色變成淡黃色。加入Na2S203(2 Μ 100 mL)的溶液並攪拌達15分鐘。然後，分離水層，且以Na2CO3(10%，50 mL)然後以水洗滌該有機相三次。接著，使用MgS〇4分離並乾燥，然後蒸發該溶劑直到剩下1〇〇 mL為止。注入至甲醇（200 mL)中且過濾之，得出23.3 g的純化合物（MW 478.5，產量97.5%) HPLC顯示其為1〇〇。/。的純度。 145481.doc -64- 201109291 中間體41 :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 DD D

將萘-D8(13_6 g ’ 0.10莫耳）、二（品納可）二硼（27 93 g， 0.11莫耳）、二-μ-甲氧基（1，5-環辛二烯）二銥（i)(di-mu-methox〇bis( 1,5-cyclooctadiene)diiradium(I)) [Ir(OMe) COD]2(1.35 g，2 mmole，2%)及 4,4'-雙三級丁基-2,2'-聯。比咬（1·1 g，4 mmole)的混合物加入環己烷（200 mL)中。以 N2除氣該混合物達15分鐘，然後於85它（油槽）加熱一整夜 (暗棕色溶液）。使該混合物通過矽膠襯墊（pad)。收集組份’並濃縮直到乾燥。添加己烷。濃縮濾液（液體）並使其通過矽膠管柱，以己烷沖洗，得出清澈的液體，其並非純液體’故藉由矽膠管柱再次純化，然後以己烷沖洗，接著於13 51： /1 〇〇 mmtorr下蒸餾’得出純白色的黏性液體，再將其固化以得出白色粉末（18.5 g，產量70%)。中間體4J :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:

在—圓底燒瓶（100 mL)中加入9-溴蒽-d9(MW 266，2.66 g ’ 0.01 mole)、萘-2-硼酸（MW 172，1.72 g，0.01 m〇ie)，再接著加入曱苯（30 mL)。以N2沖洗該混合液達1 〇分鐘。 145481.doc • 65- 201109291 然後加入溶解於水（l〇 mL)中的Na2C03(2 Μ，10 mL(2.12 g)0_02 mole)。以A吹掃該混合液達10分鐘。加入催化劑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(劑量為0.25 g，2.5%，0.025毫莫耳）。回流該混合液一整夜。分離該有機層，然後將其倒入甲醇中，以水、HC1(10〇/〇)、水及曱醇洗滌之。得出2.6 g的純白色產物。（產量：83%)。中間體4K :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:

將 CH2C12(50 mL)中的 9-21-萘-蔥-d9，中間體4J(2.6 g， 0.0083莫耳）的溶液滴狀加入ch2C12(5 mL)中的溴（1.33 g， 0.0083 mole)溶液中，並攪拌達3〇分鐘。加入Na2S2〇3(2 Μ ’ 10 mL)的溶液並攪拌達丨5分鐘。然後分離水層，並以 Na2CO3(10% ’ 1〇 mL)接著以水洗滌有機相三次。接著，使用MgS04分離並乾燥，然後蒸發該溶劑直到剩下2〇 mL 為止。注入甲醇（1〇0 mL)中並過濾得出純化合物（3」g，產量96%)。 145481.doc -66 - 201109291 中間體4L :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% ' 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:

將 Na2CO3(4.0 g，0.04 mole)和 H2O(20 mL)加入甲笨（〜6〇 mL)中的9-溴蒽-D9 ’中間體4K (2.66 g，0.01莫耳）及 4,4,5,5_ 四甲基 _2-(萘-2-基-D7)-l,3,2_ 二0惡硼院（2.7 g， 0.011莫耳）的混合物中。以氮氣鼓泡該混合物達丨5分鐘。然後加入Pd(PPh3)4(0.20 g，2.0%)。在一氮氣環境下回流該混合液達18小時（黃色固體）。於冷卻該反應混合物後，將其倒入MeOH(2〇〇 mL)中。過濾該固體’以得出黃色粗製。π。以水和甲醇洗滌該粗製品。將其再溶解於，在MgS04上乾燥’並過濾之。把矽膠加入濾液中，然後濃縮並乾燥，使用己烧作為溶析液執行石夕膠純化，得出純產物（3.0 g，產量 94%)。中間體4M :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 將 CH2C12(50 mL)中的 9-2，-萘-蔥-d9，中間體 4L(2.8 g， 0.00875 mole)的溶液滴狀加入ch2C12(5 mL)中的溴（1·4 g，0.00875 mole)溶液中，並搜拌達3〇分鐘。加入 Na2S203(2 Μ，10 mL)的溶液並攪拌該混合液達15分鐘。然後分離水層，並以Na2CO3(10%，1〇 mL)接著以水洗滌有機相三次。接著，使用MgS04分離並乾燥，然後蒸發該溶劑直到剩下20 mL為止。注入曱醇（丨00 mL)中並過濾得出純化合物（3·3 g，產量95%)。實例5 此實例說明得自中間體4H和中間體41之化合物H8的合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.

將 K2C03(12.8 g，0.093 mole)和 H20(4〇 mL)加入 DME (350 mL)中的9-溴-l〇-(4-萘-1-基）苯蔥-D19中間體4H (14.84 g，0.03 1 mole)及 2-萘硼酯中間體 41(10.0 g，0.038 mole)的混合液中。以氮氣鼓泡該混合液達15分鐘。然後加入Pd(PPh3)4(0.45 g，1.3%)。在一氮氣環境下回流該混合液達12小時。於冷卻該反應混合物之後，濃縮該反應混 145481.doc -68 · 201109291 S物至〜150 mL，然後倒入MeOH中。過濾該固體，以得出淡黃色粗製品。以水和曱醇洗滌該粗製品。將其再溶解於CHCU中，在MgS〇4上乾燥，並過濾之。將矽膠加入據液中，濃縮並乾燥，使用己烷：氣仿（3:1)作為溶析液執行矽膠純化（0.5 Kg)，得出白色產物。（15 g，產量91%) 實例6 此實例說明來自中間體4K之化合物H1丨的合成。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.

將 9-漠-10-(萘 _2_基）蒽中間體 4Κ〇 96 g，〇〇5 *9-Deep-10-(naphthalene-2-yl)anthracene intermediate 4Κ〇 96 g, 〇〇5 *

g » 0.06 mol)加入—圓底燒瓶（丨〇〇 mL)中，然後再加入曱苯（3〇 mL)。#N2吹掃該混合液達⑺ 分鐘。接著加入溶解於水（8 mL)中的Na2C〇3(1 9〇 ^， .018 mole)，然後是AHquat⑧（1 mL)。繼續以掃該混合液達10分鐘。加入催化劑Pd(PPh3)4(劑量為116 mg)。回流該混合液一整夜。於分離含水相後，將有機層倒入曱醇 (100 mL)中以收集白色固體。過濾之’且藉由使用氣仿_· 己烷（1:3)執行矽膠管柱層析而執行進一步純化作用，得出純白色化合物（2.3〇 g，產量9〇〇/0)。 145481.doc -69- 201109291 實例7 此實例說明得自中間體4K和中間體4F之化合物H9的合成0g » 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.

將 9-溴-10-(萘-2-基）蒽-D8 中間體 4K(0.70 g，0.0018 mol)、4-(萘-1-基）苯硼酸-Dll 中間體4F(0.7 g，0.002 mol) 加入一圓底燒瓶（1 0 0 mL)中，然後再加入甲苯（1 〇 mL)。以 N2吹掃該混合物達10分鐘。接著加入溶解於水（3 mL)中的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)，然後是Aliquat®(0.1 mL)。繼續以N2沖洗該混合物達1 〇分鐘。加入催化劑pd(pph3)4 (劑量為0.10 g)。回流該混合液一整夜。於分離含水相後，將有機層倒入曱醇（1 00 mL)中以收集白色固體。過據之，且藉由使用氣仿：己烷（1:3)執行矽膠管柱層析而執行進一步純化作用，.得出純白色化合物（〇 9〇 g，產量95〇/〇)。以一類似方法製備化合物Η10、Η12和Η13。實例8 -10和比較性實例D及Ε 這些貫例展示具有一藍色發射體之裝置的產製及性能。該裝置在一玻璃基板上具有下列結構： 145481.doc •70· 201109291 陽極=ΙΤΟ (50 nm) 電洞注入層=HIJ1 (50 nm) 電洞傳輸層=聚合物P1 (20 nm) 電活性層=13 : 1的主體材料：摻雜劑（40 nm)，如表3所電子傳輸層=ET1 (10 nm) 陰極=CsF/Al (1.0/100 nm) 表3.裝置電活性層實例主體材料 D13 比較性實例D-1 比較化合物A D13 比較性實例D-2 比較化合物A D13 實例8-1 H11 D13 實例8-2 H11 D13 實例9-1 H8 D13 實例9-2 H8 D13 比較性實例E-1 比較化合物A D13 比較性實例E-2 比較化合物A D13 實例10-1 H10 D13 實例10-2 H10 D13 藉由溶液加工處理及熱蒸鍍技術之一結合而產製OLED 裝置。使用來自薄膜裝置公司（Thin Film Device, Inc)之經圖案化的氧化銦錫（ITO)塗布玻璃基板。此等ITO基板係基於塗布有ΙΤΟ之Corning 1737玻璃，其具有30歐姆/平方的薄片電阻及80%的光透射率。在含水清潔劑溶液中超音波式地清潔該經圖案化之ITO基板，並以蒸餾水加以沖洗。隨後，在丙酮中超音波式地清潔該經圖案化之ITO，以異丙醇加以沖洗之，然後在氮氣流環境中乾燥。 145481.doc -71 - 201109291 就在要產製該裝置之前，以紫外光臭氧（uv 〇z〇ne)處理該等已清潔之經圖案化的IT0基板達10分鐘。於冷卻之後，隨即在該ΙΤΟ表面上旋塗HIJ1之含水分散液，然後再加熱以移除溶劑。於冷卻之後，接著以一電洞傳輸材料之溶液旋塗該等基板，然後再加熱以移除溶劑。於冷卻之後，以發射層溶液旋塗該等基板，然後再加熱以移除溶劑。遮罩該等基板，並將其放入一真空室中。使用熱蒸鍍來沉積電子傳輸層，接著為一CSF層。接著於真空中更換遮罩，並使用熱蒸鍍來沉積一八丨層。排氣該真空室，及使用一玻璃蓋、乾燥劑及UV可固化環氧化物封裝該等裝置。 ’ 藉由量測下列數據可描述〇LED樣本之特徵，（”電流-電壓（ΐ-v)曲線，（2)電致發光輻射強度對電壓，及電致發光光譜對電壓。以上所有三個測量皆於相同時間執行，並由-電腦控制。藉由把LED之電致發光輻射強度除以該裝置運轉所需之電流而決定該裝置在某一特定電屢處的電‘ 效率。其單位為Cd/A。將該電流效率乘以pi(7t)，再除以操作電壓，得出功率效率。其單位為lm/w。表4說明該農置之資料。 145481.doc -72- 201109291 表4.裝置性能實例 CIE (、y) 電壓 (V) C.E. (cd/A) E.Q.E. (%) P.E. (!m/W) 壽命測試電流密度 (mA/cm2) 壽命測試發光強度 (nits) 原始 T50 (h) 預測壽命期 T50@1000 nits 比較性實例 D-1 0.136, 0.126 4.4 5.7 5.5 -_ — 4.1 127 6686 455 11503 比較性實例 D-2 0.136， 0.123 4.4 5.8 5.7 4.2 129 6572 450 11048 實例 8-1 0.136， 0.121 4.4 5.S 5.8 4.2 128 6669 555 13970 實例 8-2 0.136， 0.124 4.3 5.9 5.7 4.2 130 6599 590 14587 實例 9-1 0.136, 0.121 4.3 5.8 5.8 4.2 127 6475 940 22503 實例 9-2 0.136， 0.121 4.4 5.8 5.8 4.2 124 6254 955 21551 比較性實例 E-1 0.136, 0.123 4.4 6.1 6.0 4.3 124 6670 400 10071 比較性實例 E-2 0.135， 0.124 4.4 5.8 5.6 4.1 131 7006 388 10620 實例 10-1 0.136, 0.121 4.4 6.0 5.9 4.2 123 6403 622 14610 實例 10-2 0.136, 0.118 4.4 5.7 5.8 4.1 121 6050 675 14398 *所有的資料為@ 1000 nits，CE=電流效率；ciEx和CIEy 係根據C.I.E·色度圖的X和y顏色座標（c〇mmissi〇nNa2CO3 (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)。原始T50 係一裝置達到初始發光強度一半時的時間（以小時計），該初始發光強度係於壽命測试發光強度時所給定。預測T5〇係於1 〇〇〇 nits時的預測壽命期，其使用一加速因子丨7。由此看出，右具有本發明之氘化的主體材料，裝置的使用壽命會大幅度地增加，同時維持其它裝置特性。下列表 5說明用於不同主體材料之平均預測壽命期。 -73- 145481.doc 201109291Internationale 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

表5.裝置壽命期主體材料平均預測壽命期T50@ 1000nits，以小時計比較化合物A 11，276及 10,346 H8 22,027 H10 14,504 H11 14,279 實例11及比較性實例F 此實例展示具有一電活性層之裝置的產製及性能，該電活性層具有一綠色摻雜劑、一具有化學式I之第一主體材料及一第二主體材料。電子傳輸材料為ET2，說明如下。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.

該裝置在一玻璃基板上具有下列結構：陽極=ITO (50 nm) 電洞注入層=HIJ2，（50 nm)，其係一導電聚合物和一氟化聚合續酸的含水分散液。’已於例如在已公開之美國專利申請案第 2004/0102577 號、第 2004/0127637 號、第 2005/0205 860號和已公開之PCT申請案第WO 2009/018009 號中描述此種材料。電洞傳輸層=聚合物P1 (20 nm) 電活性層=82.5 : 5 : 12.5的第一主體材料：第二主體材 145481.doc -74- 201109291 料：摻雜劑（60 nm)，如表6所示電子傳輸層=ET2 (10 nm) 陰極=CsF/Al (0.7/100 nm) 表6.裝置電活性層實例第一主體材料第二主體材料摻雜劑比較性實例F 比較化合物A D12 D6 實例11 H8 D12 D6 實例8-10描述裝置之製作及評估。表7說明該裝置之資料。表7.裝置性能實例 CIE (x，y) 電壓 (V) C.E. (cd/A) E.Q.E. (%) P.E, (lm/W) 壽命測試電流密度 (mA/cm2) 壽命測試發光強度 (nits) 原始 T50 ⑻ 預測壽命期T50 @1000 nits 比較性實例F 0.265, 0.649 4.8 26.1 7.2 17.1 134 29167 1800 557,000 實例 11 0.257， 0.650 4.7 25.4 7.1 16.9 127 27232 4160 1,144,800 *所有的資料為@ 1000 nits，ACE=電流效率，CIEx和CIEy 係根據C.I.E.色度圖的X和y顏色座標（Commission Internationale de L’Ecl air age，1931)。原始T50係一裝置達到初始發光強度一半時的時間（以小時計），該初始發光強度係於壽命測試發光強度時所給定。預測T50係於1 000 nits時的預測壽命期，其使用一加速因子1.7。由此看出，若具有本發明之氘化的主體材料，裝置的使用壽命會大幅度地增加，同時維持其它裝置特性。預測之壽命期超出兩倍，甚至具有非氘化之第二主體材料亦然。應注意的是，上面在一般性描述或實例中所述之活動並 145481.doc -75- 201109291 以是不必要的’並且除個或多個其他活動。此些活動的順序。非都是必要的，一部份具體活動可了所述的那些活動以外，可執行— 外，所列活動順序不必然是執行這在上述說明中，已描述關於特定具體實施例之概念。然而’熟習此項技藝者應理解在不脫離以下申請專利範圍所述之本發明範4的情況下，可進.行各種修改和變更。因此’本說明書及附圖應視為說明性，而不應視為限制性，並且所有此類的修改皆屬本發明範疇之内。前文已描述關於特定具體實施例之效益、其他優點及問題解決方案。’然而，效益、優點、問題解決方案，以及可能產生或彰顯任何這些效益、優點或問題解決方案的任何特徵’不可解釋為是任何或所有專利中請範圍之關鍵必需或基本特徵。應明白，為清楚起見而在上文及下文所述之不同具體實施例内容中說日月的本發明之特定特徵亦可結合提供於單一具體實施例中。反之了簡明扼要之故而在單一具體實施例内容中說明的本發明之各項特徵也可分開提供或提供於任何子la合中。此外，範目内描述的相關數值係指所述範圍内的每個值。【圖式簡單說明】在所附圖式中描述具體實施例，以增進在此所呈現之觀念的理解。圖1包括一有機電子裝置之實例的說明；圖2包括比較性實例A之比較化合物的1H NMR光譜； 145481.doc -76- 201109291 圖3包括實例1之氘化化合物的NMR光譜；及圖4包括實例1之氣化化合物的質谱。熟習技藝者可以理解’為了簡明及清楚起見，圖中的元件不疋按比例繪製。例如，相對於其它物件，可誇大圖式中之某些物件的尺寸，以增進具體實施例之理解。【主要元件符號說明】 100 有機電子裝置 110 第一電接觸層/陽極層 120 電洞注入層 130 電洞傳輸層 140 電活性層 150 電子傳輸層 160 第二電接觸層/陰極層 145481.doc -77-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' 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

201109291 七、申請專利範圍： 1. 一種取代芳基蒽化合物，其具有化學式I : R2 R3201109291 VII. Patent application scope: 1. A substituted aryl hydrazine compound having the chemical formula I: R2 R3

R4 Ar2—Ar4 化學式I R1 其中： R1至R8在每次出現時係相同或不同的’及係選自由 H、D、烷基、烷氧基、芳基、芳氧基、矽氧烷及石夕院基所組成之群； Ar1及Ar2係相同或不同的，及係選自由芳基基團所組成之群；以及 Ar3及Ar4係相同或不同的，及係選自由H、D及芳基基團所組成之群；其中該化合物具有至少一個D。 2·如申請專利範圍第1項所述之化合物，其係至少10%氘化的。 3.如申請專利範圍第1項所述之化合物，其係至少50%氘化的。 4·如申請專利範圍第1項所述之化合物，其係100%氘化的。 145481.doc 1 ·如申請專利範圍第1項所述之化合物，其中該至少一個D 201109291 係位在一芳環上的一取代基（基團）上。 6. 如申請專利範圍第1項所述之化合物，其中R1至R8之至少一者係D。 7. 如申請專利範圍第1項所述之化合物，其中R1至R8係選自Η及D。 8. 如申請專利範圍第1項所述之化合物，其中Ri至R8之至少一者係選自烷基、烷氧基、芳基、芳氧基、矽氧烷及石夕烧基’及1〇至1^之其餘部分係選自Η及〇。 9. 如申請專利範圍第8項所述之化合物，其中R2係選*** 基及芳基。 10. 如申請專利範圍第〖項所述之化合物，其中Ari至Ar4之至少一者係氘化芳基。 11 ·如申請專利範圍第1項所述之化合物，其中Ar3及Ar4係選自D及氣化芳基。 1 2.如申請專利範圍第1項所述之化合物，其中Ari至Ar4係至少20%氣化的。 13. 如申請專利範圍第1項所述之化合物，其中Ari及Ar2係選自由本基（phenyl)、秦基（naphthyl)、菲基（phenanthryl)、蔥基（anthracenyl)及它們的氘化衍生物所組成之群。 14. 如申請專利範圍第5項所述之化合物，其中Ar3及Ar4係選自由苯基（phenyl)、萘基（naphthyl)、菲基（phenanthryl)、蒽基（anthracenyl)、苯伸萘基（phenylnaphthylene)、萘伸苯基（naphthylphenylene) '它們的氘化衍生物及具有化學式Π之基團所組成之群： 145481.doc 201109291R4 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

化學式π 其中： R9在每次出現時係相同或不同的，及係選自由Η、 D、烷基、烷氧基、矽氧烷及矽烷基所組成之群，或可將相鄰R9基聯集在一起以形成一芳族環；以及 m在每次出現時係相同或不同的，及係由1至6之整數。 15.如申請專利範圍第1項所述之化合物，其中Ar3及Ar4係選自由苯基（phenyl)、萘基（naphthyl)、苯伸萘基 (phenylnaphthylene)、萘伸苯基（naphthylphenylene)、它們的氘化衍生物及具有化學式ΙΠ之基團所組成之群：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 其中： R9在每次出現時係相同或不同的，及係選自由Η、d、烷基、烷氧基、矽氧烷及矽烷基所組成之群，或可將相鄰R9基聯集在一起以形成一芳族環；以及 m在每次出現時係相同或不同的，及係1至6之整數。 145481.doc 201109291 16·如申請專利範圍第丨項所述之化合物，其中Afi至a〆之至少一者係雜芳基基團。 17.如申請專利範圍第16項所述之化合物，其中該雜芳基基團係選自由咔唑（carbazole)、苯并呋喃、二苯并吱喃（dibenzofuran) 〇 18·如申請專利範圍第1項所述之化合物，其中Ri至R8之至少一者係D，且Ari至Ar4之至少一者係氘化芳基。 i9· 一種化合物，其係選自中間體八至中間體m和中間體出至 H14。 20. -種有機t子裝置，其包括一第一電接㈣、一第二電接觸層及位於其間的至少—活性層，其中該活性層包括一取代芳基蒽化合物，其具有化學式工·· R2 R3R9 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 Ar2一Ar4 化學式I R5 其中： R至R在每次出現時係相同或不同的，及係選自由 H、D、貌基、院氧基、芳基、芳氧基、石夕氧烧及矽烷基所組成之群； Ar〗及Ar2係相同或不同的，及係選自由芳基基團所組 145481.doc 201109291 成之群；以及 Ar及Ar係相同或不同的，及係選自由η、ρ及芳基基團所組成之群；其中該化合物具有至少一個D。 21. 22. 23. 24. 25. 26. 如申請專利範圍第20項所述之裝置，其中該活性層係一電活性層，其進一步包括一電活性摻雜劑化合物。如申請專利範圍第20項所述之裝置，其中該活性層係一電活性層，且基本上係由一具有化學式I之化合物和一電活性摻雜劑化合物構成。如申請專利範圍第20項所述之裝置，其中該活性層係一電活性層，且基本上係由一具有化學式I之化合物、一第二主體材料及一電活性摻雜劑化合物構成。如申租專利範圍第21項所述之裝置，其中該電致發光化 &物係L自由取代胺基获（amin〇 substituted chrysenes)及取代胺基蒽所組成之群。如申明專利範圍第23項所述之裝置，其進一步包括—電洞注入層，該電洞注入層位於該第一電接觸層及該活性層之間。如申明專利範圍第25項所述之裝置，其中該電洞注入層包括至；一個導電聚合物及至少一個氟化酸聚合物。 145481.docR4 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 & 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